CN102870045B - Positive Radiation-sensitive Composition For Discharge Nozzle Coating Method, Interlayer Insulating Film For Display Element, And Formation Method For Same - Google Patents

Positive Radiation-sensitive Composition For Discharge Nozzle Coating Method, Interlayer Insulating Film For Display Element, And Formation Method For Same Download PDF

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CN102870045B
CN102870045B CN201180021053.6A CN201180021053A CN102870045B CN 102870045 B CN102870045 B CN 102870045B CN 201180021053 A CN201180021053 A CN 201180021053A CN 102870045 B CN102870045 B CN 102870045B
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methyl
organic solvent
ether
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CN102870045A (en
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一户大吾
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers

Abstract

Disclosed is a positive radiation-sensitive composition for use in a discharge nozzle coating method, said positive radiation sensitive composition containing: a polymer [A] having, in the same or different polymer molecules, a structural unit (I) containing a group represented by formula (1), and an epoxy group-containing structural unit; at least one compound [B] selected from a group comprising oxime sulfonate compounds and onium salt compounds; and an organic solvent [C]. The concentration of solid content is 10 -30 mass%, and the viscosity at 25 DEG C is 2.0 mPa DEG s-12 mPa DEG s, and at least an organic solvent (C1) having a vapor pressure of at least 0.1 mmHg and less than 1 mmHg at 20 DEG C is used as the organic solvent [C].

Description

Eurymeric radiation sensitive composition, display element interlayer dielectric and forming method thereof for jetting nozzle formula rubbing method
Technical field
The present invention is about jetting nozzle formula rubbing method eurymeric radiation sensitive composition, by the formed display element of said composition interlayer dielectric and forming method thereof, and this eurymeric radiation sensitive composition is to be suitable as the formation material of interlayer dielectric for the display element of the display elements such as liquid crystal display cells, organic EL display element.
Background technology
In display element, generally take insulating as object between the distribution of stratiform configuration, display element interlayer dielectric is set.Formation material as display element with interlayer dielectric, is widely used eurymeric radiation sensitive composition, and this is few because obtain the required process number of necessary pattern form, and the display element of gained requires the flatness of height with interlayer dielectric.
About this eurymeric radiation sensitive composition, a kind of eurymeric X-ray sensitive resin composition is proposed in TOHKEMY 2004-264623 communique, it contains resin and acid producing agent containing acetal structure and/or ketal structure and epoxy radicals.Yet this eurymeric X-ray sensitive resin composition radiation-sensitive degree is insufficient, the material of using with interlayer dielectric as formation display element cannot be satisfied.
On the other hand, in TOHKEMY 2002-131896 communique, disclosed spin-coating method, as be coated with the method for radiation sensitive composition on small-sized substrate.If based on this spin-coating method, can drip after radiation sensitive composition to the central authorities of substrate, so that the coating process of substrate rotation obtains good coating homogeneity.Yet, during with this spin-coating method coating large substrate, there is following not good situation, the radiation sensitive composition going out of use that rotation is got rid of becomes many, and breaking of substrate due to High Rotation Speed may occur, and must guarantee the productive temp time etc.Again, while being used in further large-scale substrate, in order to obtain rotating needed acceleration, need the special motor of ordering, unfavorable aspect manufacturing cost.
Therefore, instead the coating process of spin-coating method, adopts by nozzle ejection radiation sensitive composition, coats the jetting nozzle formula rubbing method on substrate.Jetting nozzle formula rubbing method skims over for making to be coated with nozzle at certain orientation, on substrate, form the coating process film, with spin-coating method relatively under, the amount of needed radiation sensitive composition in the time of can lowering coating, and seek the shortening of the time that is coated with, favourable at manufacturing cost face.Yet, with radiation sensitive composition in the past, when being coated with based on jetting nozzle formula rubbing method, can there is crawling, to realizing display element, with the desired height flatness of characteristic of interlayer dielectric, form obstacle.Again, although for example record the main idea that the radiation sensitive composition recorded with this communique also can be coated with by the method beyond spin-coating method in TOHKEMY 2009-98673 communique, but there is no concrete suitable viscosity, solid component concentration, the solvent etc. of disclosing, in embodiment, do not carry out the coating of jetting nozzle formula rubbing method etc. yet.
In view of situation so, wish to develop eurymeric radiation sensitive composition for a kind of jetting nozzle formula rubbing method, it has high radiation-sensitive degree, and can form the display element interlayer dielectric with height flatness (film thickness uniformity) without crawling, and can high-speed coating.
Background technology document
[patent documentation]
[patent documentation 1] TOHKEMY 2004-264623 communique
[patent documentation 2] TOHKEMY 2002-131896 communique
[patent documentation 3] TOHKEMY 2009-98673 communique
Summary of the invention
The problem that invention will solve
The situation that the present invention be take as above completes as basis, its object is to provide eurymeric radiation sensitive composition for jetting nozzle formula rubbing method, interlayer dielectric and forming method thereof for display element, said composition has high radiation-sensitive degree, and can form the display element interlayer dielectric with height flatness (film thickness uniformity) without crawling, and can high-speed coating.
The means of dealing with problems
The present invention who completes in order to address the above problem is eurymeric radiation sensitive composition for a kind of jetting nozzle formula rubbing method, and it contains:
[A] has the structural unit (I) and the polymkeric substance (below also referred to as " [A] polymkeric substance ") that contains the structural unit of epoxy radicals containing the group shown in following formula (1) in same or different polymer molecules,
At least one compound (below also referred to as " [B] compound ") of selecting in the group that [B] is comprised of oxime sulfonates compound and salt compound, and
[C] organic solvent, and
The solid component concentration of said composition is below the above 30 quality % of 10 quality %, the viscosity of 25 ℃, is below the above 12mPas of 2.0mPas, and,
As [C] organic solvent, at least containing (C1) is more than 0.1mmHg and lower than the organic solvent of 1mmHg the vapor pressure of 20 ℃,
(in formula (1), R 1and R 2be hydrogen atom, alkyl, naphthenic base or aryl independently of one another; Wherein, part or all hydrogen atom that abovementioned alkyl, naphthenic base or aryl have can be substituted; There is not R again, 1and R 2it is the situation of hydrogen atom simultaneously; R 3for alkyl, naphthenic base, aralkyl, aryl or-M (R 3m) 3shown group, wherein, part or all hydrogen atom that these groups have can be substituted; M is Si, Ge or Sn; R 3mfor alkyl; Wherein, R 1with R 3can connect, can form cyclic ether with together with the carbon atom of institute's bond).
Said composition above-mentioned owing to containing [A] polymkeric substance, [B] compound and [C] organic solvent have high radiation-sensitive degree when exposure.Again, solid component concentration based on making said composition becomes above-mentioned particular range, can effectively suppress the generation of crawling, further make the viscosity of said composition become above-mentioned particular range, can maintain film thickness uniformity on one side, even if there is crawling on one side, also can balance reach well the viscosity of degree of uniformity that can be spontaneous, and can realize high-speed coating.Again, based on use, there is [C] organic solvent of the vapor pressure of above-mentioned particular range, even if adopt jetting nozzle formula rubbing method, also can prevent crawling, simultaneously can high-speed coating.
In said composition, as [C] organic solvent, further containing (C2) is the organic solvent below the above 20mmHg of 1mmHg the vapor pressure of 20 ℃, (C2) content of organic solvent, with respect to (C1) organic solvent and (C2) for the total amount of organic solvent, be preferably below the above 90 quality % of 10 quality %, (C2) content of organic solvent, with respect to (C1) organic solvent and (C2) total amount of organic solvent, more preferably below the above 50 quality % of 10 quality %.By making the mass ratio of (C2) organic solvent that (C1) organic solvent that steam forces down and vapor pressure are high become above-mentioned particular range, the mobility that remaining quantity of solvent in special filming after prebake conditions is optimization, film is balanced, result can suppress the generation of crawling (striped inequality, pin trace inequality, vaporific unequal), can further improve film thickness uniformity.Again, based on making remaining quantity of solvent optimization, sour generation and sour decomposability group height balance, radiation-sensitive degree has the good tendency of further change.
In said composition, further contain at least one surfactant (below also referred to as " [D] surfactant ") of selecting in the group that [D] be comprised of fluorine class surfactant or polysiloxane-based surfactant, the content of [D] surfactant, with respect to [A] polymkeric substance 100 mass parts, is preferably below above 2 mass parts of 0.01 mass parts.Because said composition further contains [D] surfactant, can improve the surface smoothness of filming, result can further improve the film thickness uniformity of interlayer dielectric for formed display element.Moreover, based on making the content of [D] surfactant at above-mentioned particular range, can further improve the surface smoothness of filming.
In said composition, be preferably further and contain [E] multifunctional (methyl) acrylate compounds.Because said composition further contains [E] multifunctional (methyl) acrylate compounds, can improve transmittance and the heat-resisting transparency of interlayer dielectric for display element.
In said composition, be preferably further and contain [F] antioxidant.Because said composition further contains [F] antioxidant, can improve transmittance and the heat-resisting transparency of interlayer dielectric for display element.
In said composition, be preferably further and contain [G] epoxy compound.Because said composition further contains [G] epoxy compound, can improve transmittance and the heat-resisting transparency of interlayer dielectric for display element.
(C1) organic solvent is preferably at least one organic solvent of selecting in the group who is comprised of diethylene glycol ethyl-methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, phenmethylol, DPGME, and (C2) organic solvent is preferably at least one organic solvent of selecting in the group who is comprised of diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol list propyl ether acetic acid esters, propylene glycol monomethyl ether, cyclohexanone, n-butyl acetate, methyl isobutyl ketone, 3-methoxy methyl propionate.From above-mentioned specific compound, select (C1) organic solvent and (C2) organic solvent, can further suppress to be coated with irregular generation, further improve film thickness uniformity.
In the present invention, also comprise aptly by the formed display element interlayer dielectric of said composition.
Display element of the present invention has by the formation method of interlayer dielectric:
(1) jetting nozzle and substrate are relatively moved on one side, on one side said composition is coated on substrate, form the operation of filming,
(2) operation to above-mentioned formed at least a portion useful to irradiation of rays of filming,
(3) by the operation of the painting film development after above-mentioned radiation exposure, and
(4) by the operation of the heating of filming after above-mentioned development.
According to this formation method, use can be at a high speed coating, there is excellent radiation-sensitive degree simultaneously, can form the said composition of interlayer cured film for the display element of film thickness uniformity excellence, based on utilizing exposure, video picture, the heating of radiation sensitive linear to form pattern, can easily form the display element interlayer cured film with fine and exquisite pattern.Moreover thus formed display element interlayer dielectric, for have the flatness of height without crawling, applicable to the display element of liquid crystal display cells, organic EL display element etc.
Moreover " the jetting nozzle formula rubbing method " sayed in this instructions, refers to, by nozzle, coated article is sprayed to the method that said composition is coated with, for example, can enumerate use and there is a plurality of nozzle bores with the method for the nozzle coating said composition of the ejiction opening of row shape arrangement; Use has the nozzle of the ejiction opening of slit-shaped, and the method for coating said composition etc., are included on substrate and are coated with after said composition, make substrate rotation, till adjust the concept of the operation of thickness.The concept of said in this instructions [A] polymkeric substance is also included within has structural unit (I) in a polymer molecule, and has the structural unit containing epoxy radicals in the polymer molecule different from this polymer molecule.The concept of " ray " of said in this instructions " X-ray sensitive resin composition " comprises luminous ray, ultraviolet ray, far ultraviolet, X ray, charged particle line etc.
The effect of invention
As described above, jetting nozzle formula rubbing method of the present invention is to have high radiation-sensitive degree and can form the display element interlayer dielectric with height flatness (film thickness uniformity) without crawling with eurymeric radiation sensitive composition, further and can high-speed coating.Therefore, said composition is suitable as and forms the material that the display element of liquid crystal display cells, organic EL display element etc. is used with interlayer dielectric.
Embodiment
Jetting nozzle formula rubbing method of the present invention contains [A] polymkeric substance, [B] compound and [C] organic solvent with eurymeric radiation sensitive composition.Again, said composition also can contain [D] surfactant, [E] multifunctional (methyl) acrylate compounds, [F] antioxidant, [G] epoxy compound as suitable component.Moreover, only otherwise damage effect of the present invention, also can contain other optional member.Below, each composition is described in detail in detail.
<[A] polymkeric substance >
[A] polymkeric substance, for have structural unit (I) and the structural unit that contains epoxy radicals in same or different polymer molecules, optionally also can have other structural unit.There is structural unit (I) and there is no particular limitation containing the sample state of [A] polymkeric substance of the structural unit of epoxy radicals, can enumerate:
(i) in same polymer molecule, have structural unit (I) and containing the structural unit of epoxy radicals the two, in [A] polymkeric substance, there is the situation of a kind of polymer molecule;
(ii) in a polymer molecule, there is structural unit (I), in the polymer molecule different from it, there is the structural unit containing epoxy radicals, in [A] polymkeric substance, have the situation of 2 kinds of polymer molecules;
(iii) in a polymer molecule, have structural unit (I) and containing the structural unit of epoxy radicals the two, in the polymer molecule different from it, there is structural unit (I), in the polymer molecule different from these, there is the structural unit containing epoxy radicals, in [A] polymkeric substance, have the situation of 3 kinds of polymer molecules;
(iv), except the polymer molecule of (i)～(iii) regulation, in [A] polymkeric substance, also further contain the situation of another one kind or two or more polymer molecule etc.
[structural unit (I)]
In structural unit (I), contain the group shown in above-mentioned formula (1), the form of this group group (sour decomposability group) of polarization base with decomposition in the presence of acid exists, so the acid being produced by [B] compound via the irradiation of ray causes decomposing, the insoluble polymkeric substance of result alkali [A] becomes alkali-soluble.Above-mentioned sour decomposability group has the more stable ethylidene ether structure of alkali or ketal structure, the effect that these can be based on sour and decomposing.
In above-mentioned formula (1), R 1and R 2be hydrogen atom, alkyl, naphthenic base or aryl independently of one another.Wherein, part or all hydrogen atom that abovementioned alkyl, naphthenic base and aryl have can be substituted.There is not R again, 1and R 2it is the situation of hydrogen atom simultaneously.R 3for alkyl, naphthenic base, aralkyl, aryl or-M (R 3m) 3shown base.Part or all hydrogen atom that wherein these groups have can be substituted.M is Si, Ge or Sn.R 3mfor alkyl.Wherein, R 1with R 3can connect, can form cyclic ether with together with connected carbon atom.
As above-mentioned R 1and R 2shown alkyl, is preferably the straight chain shape of carbon number 1～30 and the alkyl of a chain.Again, this alkyl can have oxygen atom, sulphur atom, nitrogen-atoms in alkyl chain.As the alkyl of the straight chain shape of above-mentioned carbon number 1～30 and a chain, such as the alkyl etc. of a chain that can enumerate the straight chain-like alkyl, isopropyl, isobutyl, the tert-butyl group, neopentyl, 2-hexyl, 3-hexyl etc. of methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-octyl, positive dodecyl, positive tetradecyl, positive octadecyl etc.
As above-mentioned R 1and R 2shown naphthenic base, is preferably the naphthenic base of carbon number 3～20.Again, the naphthenic base of this carbon number 3～20 can be many rings, in ring, can have oxygen atom.As the naphthenic base of above-mentioned carbon number 3～20, such as enumerating cyclopropyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, bornyl, norborny, adamantyl etc.
As above-mentioned R 1and R 2shown aryl, is preferably the aryl of carbon number 6～14.The aryl of this carbon number 6～14 can be monocycle, also can be the structure that monocycle links, and also can be condensed ring.As the aryl of above-mentioned carbon number 6～14, such as enumerating phenyl, naphthyl etc.
As above-mentioned R 1and R 2the shown alkyl being substituted, the substituting group of naphthenic base and aryl, for example, can enumerate halogen atom, hydroxyl, nitro, cyano group, carboxyl, carbonyl, naphthenic base (cyclopropyl for example, cyclopentyl, cyclohexyl, suberyl, ring octyl group, bornyl, norborny, adamantyl etc.), aryl (phenyl for example, naphthyl etc.), alkoxy (methoxyl for example, ethoxy, propoxyl group, n-butoxy, amoxy, own oxygen base, heptan oxygen base, the alkoxy of the carbon number 1～20 of octyloxy etc. etc.), acyl group (acetyl group for example, propiono, bytyry, the acyl group of the carbon number 2～20 of isobutyryl etc. etc.), acyloxy (acetoxyl group for example, propionyloxy, butyryl acyloxy, tertiary butyryl acyloxy, the acyloxy of the carbon number 2～10 of uncle's penta acyloxy etc. etc.), alkoxy carbonyl group (methoxycarbonyl group for example, carbethoxyl group, the alkoxy carbonyl group of the carbon number 2～20 of the third oxygen carbonyl etc.), haloalkyl (methyl for example, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-octyl, positive dodecyl, positive tetradecyl, the straight chain-like alkyl of positive octadecyl etc., isopropyl, isobutyl, the tert-butyl group, neopentyl, 2-hexyl, the alkyl of the branched-chain alkyl of 3-hexyl etc. etc., perfluoro-methyl, perfluor ethyl, perfluoro propyl, fluorine cyclopropyl, the base that part or all hydrogen atom of the naphthenic base of fluorine cyclobutyl etc. replaces through halogen atom etc.) etc.
As above-mentioned R 3the example of shown alkyl, naphthenic base and aryl, for example, can adopt above-mentioned R 1and R 2illustrated group.As above-mentioned R 3shown aralkyl, such as the aralkyl etc. that can enumerate the carbon number 7～20 of benzyl, phenethyl, menaphthyl, naphthalene ethyl etc.As above-mentioned R 3shown-M (R 3m) 3, such as enumerating TMS, trimethyl germyl etc.As above-mentioned R 3shown aralkyl or-M (R 3m) 3substituting group, can adopt above-mentioned R 1and R 2illustrated substituting group.
As R 1with R 3can connect and can with the cyclic ether forming together with the carbon atom of institute's bond, such as enumerating 2-oxetanyl, 2-tetrahydrofuran base, 2-THP trtrahydropyranyl, 2-dioxane base etc.
Structural unit (I) has based on being attached on other carbon atom and becomes the functional group can with ethylidene ether structure or ketal structure, can have thus this ethylidene ether structure or ketal structure.
As above-mentioned, based on being attached on other carbon atom and become the functional group can with ethylidene ether structure, for example, can enumerate 1-methoxy ethoxy, 1-ethoxy ethoxy, 1-positive propoxy ethoxy, 1-isopropoxy ethoxy, 1-n-butoxy ethoxy, 1-isobutoxy ethoxy, 1-sec-butoxy ethoxy, 1-tert-butoxy ethoxy, 1-cyclopentyloxy ethoxy, 1-cyclohexyloxy ethoxy, 1-norborneol oxygen base oxethyl, 1-borneol oxygen base oxethyl, 1-phenoxy group ethoxy, 1-(1-naphthoxy) ethoxy, 1-benzyloxy ethoxy, 1-phenethyl oxygen base oxethyl, (cyclohexyl) (methoxyl) methoxyl, (cyclohexyl) (ethoxy) methoxyl, (cyclohexyl) (positive propoxy) methoxyl, (cyclohexyl) (isopropoxy) methoxyl, (cyclohexyl) (cyclohexyloxy) methoxyl, (cyclohexyl) (phenoxy group) methoxyl, (cyclohexyl) (benzyloxy) methoxyl, (phenyl) (methoxyl) methoxyl, (phenyl) (ethoxy) methoxyl, (phenyl) (positive propoxy) methoxyl, (phenyl) (isopropoxy) methoxyl, (phenyl) (cyclohexyloxy) methoxyl, (phenyl) (phenoxy group) methoxyl, (phenyl) (benzyloxy) methoxyl, (benzyl) (methoxyl) methoxyl, (benzyl) (ethoxy) methoxyl, (benzyl) (positive propoxy) methoxyl, (benzyl) (isopropoxy) methoxyl, (benzyl) (cyclohexyloxy) methoxyl, (benzyl) (phenoxy group) methoxyl, (benzyl) (benzyloxy) methoxyl, 2-tetrahydrofuran oxygen base, 2-tetrahydro-pyran oxy, 1-TMS oxygen base oxethyl, 1-trimethyl germyl oxygen base oxethyl etc.In these, be preferably 1-ethoxy ethoxy, 1-cyclohexyloxy ethoxy, 2-tetrahydro-pyran oxy, 1-positive propoxy ethoxy, 1-n-butoxy ethoxy, 2-tetrahydro-pyran oxy.
As above-mentioned, based on being attached on other carbon atom and can become the functional group with ketal structure, for example, can enumerate 1-methyl isophthalic acid-methoxy ethoxy, 1-methyl isophthalic acid-ethoxy ethoxy, 1-methyl isophthalic acid-positive propoxy ethoxy, 1-methyl isophthalic acid-isopropoxy ethoxy, 1-methyl isophthalic acid-n-butoxy ethoxy, 1-methyl isophthalic acid-isobutoxy ethoxy, 1-methyl isophthalic acid-sec-butoxy ethoxy, 1-methyl isophthalic acid-tert-butoxy ethoxy, 1-methyl isophthalic acid-cyclopentyloxy ethoxy, 1-methyl isophthalic acid-cyclohexyloxy ethoxy, 1-methyl isophthalic acid-norborneol oxygen base oxethyl, 1-methyl isophthalic acid-borneol oxygen base oxethyl, 1-methyl isophthalic acid-phenoxy group ethoxy, 1-methyl isophthalic acid-(1-naphthoxy) ethoxy, 1-methyl isophthalic acid-benzyloxy ethoxy, 1-methyl isophthalic acid-phenethyl oxygen base oxethyl, 1-ethyl-1-methoxy ethoxy, 1-ethyl-1-ethoxy ethoxy, 1-ethyl-1-positive propoxy ethoxy, 1-ethyl-1-isopropoxy ethoxy, 1-ethyl-1-n-butoxy ethoxy, 1-ethyl-1-isobutoxy ethoxy, 1-ethyl-1-sec-butoxy ethoxy, 1-ethyl-1-tert-butoxy ethoxy, 1-ethyl-1-cyclopentyloxy ethoxy, 1-ethyl-1-cyclohexyloxy ethoxy, 1-ethyl-1-norborneol oxygen base oxethyl, 1-ethyl-1-borneol oxygen base oxethyl, 1-ethyl-1-phenoxy group ethoxy, 1-ethyl-1-(1-naphthoxy) ethoxy, 1-ethyl-1-benzyloxy ethoxy, 1-ethyl-1-phenethyl oxygen base oxethyl, 1-cyclohexyl-1-methoxy ethoxy, 1-cyclohexyl-1-ethoxy ethoxy, 1-cyclohexyl-1-positive propoxy ethoxy, 1-cyclohexyl-1-isopropoxy ethoxy, 1-cyclohexyl-1-cyclohexyloxy ethoxy, 1-cyclohexyl-1-phenoxy group ethoxy, 1-cyclohexyl-1-benzyloxy ethoxy, 1-phenyl-1-methoxy ethoxy, 1-phenyl-1-ethoxy ethoxy, 1-phenyl-1-positive propoxy ethoxy, 1-phenyl-1-isopropoxy ethoxy, 1-phenyl-1-cyclohexyloxy ethoxy, 1-phenyl-1-phenoxy group ethoxy, 1-phenyl-1-benzyloxy ethoxy, 1-benzyl-1-methoxy ethoxy, 1-benzyl-1-ethoxy ethoxy, 1-benzyl-1-positive propoxy ethoxy, 1-benzyl-1-isopropoxy ethoxy, 1-benzyl-1-cyclohexyloxy ethoxy, 1-benzyl-1-phenoxy group ethoxy, 1-benzyl-1-benzyloxy ethoxy, 2-(2-methyl-tetrahydrofuran base) oxygen base, 2-(2-methyl-THP trtrahydropyranyl) oxygen base, 1-methoxyl-cyclopentyloxy, 1-methoxyl-cyclohexyloxy etc.In these, be preferably 1-methyl isophthalic acid-methoxy ethoxy, 1-methyl isophthalic acid-cyclohexyloxy ethoxy.
As the above-mentioned structural unit (I) with acetal structure or ketal structure, such as enumerating the structural unit shown in following formula (1-1)～(1-3) etc.
In above-mentioned formula (1-1)～(1-3), R 1, R 2and R 3with above-mentioned formula (1) synonym.Above-mentioned formula (1-1) and (1-3) in, R ' is hydrogen atom or methyl.
As the monomer (below also referred to as " containing the monomer of acetal structure ") that gives the structural unit shown in above-mentioned formula (1-1)～(1-3), for example, can enumerate:
(methyl) esters of acrylic acid of (methyl) acrylic acid 1-alkoxy alkane ester, (methyl) acrylic acid 1-(cycloalkyloxy) alkane ester, (methyl) acrylic acid 1-(halogen alkoxy) alkane ester, (methyl) acrylic acid 1-(aralkoxy) alkane ester, (methyl) acrylic acid tetrahydropyrans ester etc. is containing the monomer of acetal structure;
2,3-bis-(1-(trialkylsilanyl oxygen base) alkoxy) carbonyl)-5-norborene, 2,3-bis-(1-(trialkyl germyl oxygen base) alkoxy) carbonyl)-5-norborene, 2,3-bis-(1-alkoxy alkoxy carbonyl group)-5-norborene, 2,3-bis-(1-(cycloalkyloxy) alkoxy carbonyl group)-5-norborene, 2, the norborene of 3-bis-(1-(aralkoxy) alkoxy carbonyl group)-5-norborene etc. is the monomer containing acetal structure;
The styrene of 1-alkoxy alkoxystyrene, 1-(halogen alkoxy) alkoxystyrene, 1-(aralkoxy) alkoxystyrene, tetrahydro-pyran oxy styrene etc. is the monomer containing acetal structure.
Further concrete example as above-mentioned (methyl) acrylate for the monomer containing acetal structure, for example, can enumerate methacrylic acid 1-ethoxy ethyl ester, methacrylic acid 1-methoxyl ethyl ester, methacrylic acid 1-n-butoxy ethyl ester, methacrylic acid 1-isobutoxy ethyl ester, methacrylic acid 1-tert-butoxy ethyl ester, methacrylic acid 1-(2-chloroethoxy) ethyl ester, methacrylic acid 1-(2-ethyl hexyl oxy) ethyl ester, methacrylic acid 1-positive propoxy ethyl ester, methacrylic acid 1-cyclohexyloxy ethyl ester, methacrylic acid 1-(2-cyclohexyl ethoxy) ethyl ester, methacrylic acid 1-benzyloxy ethyl ester, methacrylic acid 2-tetrahydropyrans ester, acrylic acid 1-ethoxy ethyl ester, acrylic acid 1-methoxyl ethyl ester, acrylic acid 1-n-butoxy ethyl ester, acrylic acid 1-isobutoxy ethyl ester, acrylic acid 1-tert-butoxy ethyl ester, acrylic acid 1-(2-chloroethoxy) ethyl ester, acrylic acid 1-(2-ethyl hexyl oxy) ethyl ester, acrylic acid 1-positive propoxy ethyl ester, acrylic acid 1-cyclohexyloxy ethyl ester, acrylic acid 1-(2-cyclohexyl ethoxy) ethyl ester, acrylic acid 1-benzyloxy ethyl ester, acrylic acid 2-tetrahydropyrans ester etc.
Further concrete example as above-mentioned norborene for the monomer containing acetal structure, for example can enumerate 2,3-bis-(1-(TMS oxygen base) ethoxy) carbonyl)-5-norborene, 2,3-bis-(1-(trimethyl germyl oxygen base) ethoxy) carbonyl)-5-norborene, 2,3-bis-(1-methoxyl carbethoxyl group)-5-norborene, 2,3-bis-(1-(cyclohexyloxy) carbethoxyl group)-5-norborene, 2,3-bis-(1-(benzyloxy) carbethoxyl group)-5-norborene etc.
Further concrete example as above-mentioned phenylethylene containing the monomer of acetal structure, for example can enumerate to or m-1-ethoxy ethoxy styrene, to or m-1-methoxy ethoxy styrene, to or m-1-n-butoxy ethoxybenzene ethene, to or m-1-isobutoxy ethoxybenzene ethene, to or m-1-(1, 1-dimethyl ethoxy) ethoxybenzene ethene, to or m-1-(2-chloroethoxy) ethoxybenzene ethene, to or m-1-(2-ethyl hexyl oxy) ethoxybenzene ethene, to or m-1-positive propoxy ethoxybenzene ethene, to or m-1-cyclohexyloxy ethoxybenzene ethene, to or m-1-(2-cyclohexyl ethoxy) ethoxybenzene ethene, to or m-1-benzyloxy ethoxybenzene ethene etc.
As structural unit (I), be preferably the structural unit shown in above-mentioned formula (1-1).As the monomer containing acetal structure, be preferably (methyl) acrylic acid 1-alkoxy alkane ester, (methyl) acrylic acid tetrahydropyrans ester, (methyl) acrylic acid 1-alkoxy alkoxystyrene, tetrahydro-pyran oxy styrene, more preferably (methyl) acrylic acid 1-alkoxy alkane ester, is particularly preferably methacrylic acid 1-ethoxy ethyl ester, methacrylic acid 1-n-butoxy ethyl ester, methacrylic acid 2-tetrahydropyrans ester, methacrylic acid 1-benzyloxy ethyl ester.
Monomer containing acetal structure can be used commercially available product, also can use the monomer with well-known method synthesized.For example, give the monomer containing acetal structure of the structural unit shown in above-mentioned formula (1-1), for example can be based on as shown in following, make method that (methyl) acrylic acid reacts with vinethene under the existence of sour catalyst etc. and synthesize.
In above-mentioned formula, R ', R 1and R 3with above-mentioned formula (1-1) synonym.R 21and R 22as-CH (R 21) (R 22) and with above-mentioned formula (1-1) in R 2synonym.
[A] polymkeric substance is for can have one kind or two or more structural unit (I).The content of the structural unit (I) in [A] polymkeric substance, as long as [A] polymkeric substance shows alkali-soluble, the performance display element required thermotolerance of interlayer dielectric via acid, there is no particular limitation, in a polymer molecule, contain structural unit (I) with containing the structural unit of epoxy radicals the two time, in monomer add than, be more preferably 5 quality %～70 quality %, more preferably 10 quality %～60 quality %, are particularly preferably 20 quality %～50 quality %.
On the other hand, in a polymer molecule, there is structural unit (I), and while thering is the structural unit containing epoxy radicals in another polymer molecule, the content with the structural unit (I) in a polymer molecule of structural unit (I), in monomer add than, be preferably 40 quality %～99 quality %, more preferably 50 quality %～98 quality %, are particularly preferably 55 quality %～95 quality %.
[containing the structural unit of epoxy radicals]
When having said structure unit (I), [A] polymkeric substance contains the structural unit of epoxy radicals.Structural unit containing epoxy radicals is the structural unit that carrys out the monomer of self-contained epoxy radicals.Moreover so-called epoxy radicals, comprises the concept of Oxyranyle (1,2-epoxy structure) and oxetanyl (1,3-epoxy structure) exactly.[A] polymkeric substance, due to the structural unit having in molecule containing epoxy radicals, can improve the hardness by the cured film of said composition gained, further improves thermotolerance.
As the monomer containing epoxy radicals that contains the structural unit of epoxy radicals, for example, can enumerate:
(methyl) Glycidyl Acrylate, (methyl) acrylic acid 3,4-epoxy radicals butyl ester, acrylic acid 3-methyl-3,4-epoxy radicals butyl ester, methacrylic acid 3-ethyl-3,4-epoxy radicals butyl ester, (methyl) acrylic acid 5, the own ester of 6-epoxy radicals, methacrylic acid 5-methyl-5, the own ester of 6-epoxy radicals, methacrylic acid 5-ethyl-5, the own ester of 6-epoxy radicals, (methyl) acrylic acid 6,7-epoxy radicals heptyl ester, methacrylic acid 3,4-epoxy radicals cyclohexyl, methacrylic acid 3,4-epoxy radicals cyclohexyl methyl esters, (methyl) acrylic acid 3,4-epoxy radicals cyclohexyl ethyl ester, methacrylic acid 3,4-epoxy radicals cyclohexyl propyl ester, methacrylic acid 3,4-epoxy radicals cyclohexyl butyl ester, (methyl) acrylic acid 3, the own ester of 4-epoxy radicals cyclohexyl, acrylic acid 3,4-epoxy radicals cyclohexyl methyl esters, acrylic acid 3,4-epoxy radicals cyclohexyl ethyl ester, acrylic acid 3,4-epoxy radicals cyclohexyl propyl ester, acrylic acid 3,4-epoxy radicals cyclohexyl butyl ester, acrylic acid 3, (methyl) acrylic compounds containing Oxyranyle of 4-epoxy radicals cyclohexyl hexyl etc.,
Adjacent vinyl benzyl glycidyl ethers, a vinyl benzyl glycidyl ethers, the vinyl benzyl glycidyl ethers to vinyl benzyl glycidyl ethers, Alpha-Methyl-adjacent vinyl benzyl glycidyl ethers, an Alpha-Methyl-vinyl benzyl glycidyl ethers, Alpha-Methyl-to vinyl benzyl glycidyl ethers etc.;
Adjacent ethenylphenyl glycidyl ethers, an ethenylphenyl glycidyl ethers, the ethenylphenyl glycidyl ethers to ethenylphenyl glycidyl ethers etc.;
3-(acryloyl-oxy ylmethyl) oxetanes, 3-(acryloyl-oxy ylmethyl)-3-methyl oxetanes, 3-(acryloyl-oxy ylmethyl)-3-Ethyloxetane, 3-(acryloyl-oxy ylmethyl)-3-phenyl oxetanes, 3-(2-acryloxy ethyl) oxetanes, 3-(2-acryloxy ethyl)-3-Ethyloxetane, 3-(2-acryloxy ethyl)-3-Ethyloxetane, 3-(2-acryloxy ethyl)-3-phenyl oxetanes, 3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-3-methyl oxetanes, 3-(methacryloxy methyl)-3-Ethyloxetane, 3-(methacryloxy methyl)-3-phenyl oxetanes, 3-(2-methacryloxyethyl) oxetanes, 3-(2-methacryloxyethyl)-3-Ethyloxetane, 3-(2-methacryloxyethyl)-3-Ethyloxetane, 3-(2-methacryloxyethyl)-3-phenyl oxetanes, 2-(acryloyl-oxy ylmethyl) oxetanes, 2-(acryloyl-oxy ylmethyl)-2-methyl oxetanes, 2-(acryloyl-oxy ylmethyl)-2-Ethyloxetane, 2-(acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 2-(2-acryloxy ethyl) oxetanes, 2-(2-acryloxy ethyl)-2-Ethyloxetane, 2-(2-acryloxy ethyl)-2-Ethyloxetane, 2-(2-acryloxy ethyl)-2-phenyl oxetanes, 2-(methacryloxy methyl) oxetanes, 2-(methacryloxy methyl)-2-methyl oxetanes, 2-(methacryloxy methyl)-2-Ethyloxetane, 2-(methacryloxy methyl)-2-phenyl oxetanes, 2-(2-methacryloxyethyl) oxetanes, 2-(2-methacryloxyethyl)-2-Ethyloxetane, 2-(2-methacryloxyethyl)-2-Ethyloxetane, (methyl) acrylic compounds of the oxygen heterocycle butane group of 2-(2-methacryloxyethyl)-2-phenyl oxetanes etc. etc.
Above-mentioned, contain in the monomer of epoxy radicals, viewpoint from the developability of the copolymerization with other free radical polymerization monomer and said composition, be preferably glytidyl methacrylate, methacrylic acid 2-methyl epoxy propyl ester, methacrylic acid 3,4-epoxy radicals cyclohexyl, methacrylic acid 3,4-epoxy radicals cyclohexyl methyl esters, 3-(methacryloxy methyl)-3-methyl oxetanes, 3-(methacryloxy methyl)-3-Ethyloxetane.
[A] polymkeric substance is for having the one kind or two or more structural unit containing epoxy radicals.The content of the structural unit containing epoxy radicals in [A] polymkeric substance, as long as can bring into play the required thermotolerance of interlayer dielectric for display element, there is no particular limitation, when containing structural unit (I) and containing the structural unit of epoxy radicals in a polymer molecule, for structural unit (I) contained in [A] polymkeric substance, in monomer add than, be preferably 1 quality %～60 quality %, more preferably 15 quality %～55 quality %, are particularly preferably 20 quality %～50 quality %.
On the other hand, in a polymer molecule, there is structural unit (I), and while thering is the structural unit containing epoxy radicals in another polymer molecule, the content with the structural unit containing epoxy radicals contained in a polymer molecule of the structural unit that contains epoxy radicals, in monomer add than, be preferably 1 quality %～80 quality %, more preferably 30 quality %～70 quality %, are particularly preferably 35 quality %～65 quality %.
[other structural unit]
[A] polymkeric substance can contain structural unit (I) and containing other structural unit beyond the structural unit of epoxy radicals.As the monomer that gives other structural unit, such as enumerating, there are the monomer of carboxyl or derivatives thereof, the monomer with hydroxyl, other monomer etc.
As the above-mentioned monomer with carboxyl or derivatives thereof, such as the monocarboxylic acid that can enumerate acrylic acid, methacrylic acid, crotonic acid, 2-acryloxy ethyl succinic acid, 2-methacryloxyethyl succinic acid, 2-acryloxy ethyl hexahydrobenzene dioctyl phthalate, 2-methacryloxyethyl hexahydrobenzene dioctyl phthalate etc.; The dicarboxylic acid of maleic acid, fumaric acid, citric acid, mesaconic acid, Yi Kang acid etc.; The acid anhydrides of above-mentioned dicarboxylic acid etc.At these, have in the monomer of carboxyl or derivatives thereof, be preferably methacrylic acid.
As the above-mentioned monomer with hydroxyl, such as the hydroxyalkyl acrylate that can enumerate acrylic acid 2-hydroxyl ethyl ester, acrylic acid-3-hydroxypropyl acrylate, acrylic acid 4-hydroxy butyl ester, acrylic acid 4-methylol cyclohexyl methyl esters etc.; The hydroxyalkyl methacrylate of HEMA, methacrylic acid 3-hydroxypropyl acrylate, methacrylic acid 4-hydroxy butyl ester, methacrylic acid 5-hydroxy pentane ester, the own ester of methacrylic acid 6-hydroxyl, methacrylic acid 4-methylol-cyclohexyl methyl esters etc. etc.These have hydroxyl monomer in, the stable on heating viewpoint of using interlayer dielectric from the display element of gained, is preferably acrylic acid 2-hydroxyl ethyl ester, acrylic acid 3-hydroxypropyl acrylate, acrylic acid 4-hydroxy butyl ester, HEMA, methacrylic acid 4-hydroxy butyl ester, acrylic acid 4-methylol-cyclohexyl methyl esters, methacrylic acid 4-methylol-cyclohexyl methyl esters.
As other monomer, for example, can enumerate:
The alkyl acrylate of methyl acrylate, isopropyl acrylate etc.;
The alkyl methacrylate of methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, the secondary butyl ester of methacrylic acid, Tert-butyl Methacrylate etc.;
Cyclohexyl acrylate, acrylic acid 2-methyl cyclohexyl, acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, acrylic acid 2-(three ring [5.2.1.0 2,6] decane-8-base oxygen base) the acrylate ring type alkane ester of ethyl ester, isobornyl acrylate etc.;
Cyclohexyl methacrylate, methacrylic acid 2-methyl cyclohexyl, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, methacrylic acid 2-(three ring [5.2.1.0 2,6] decane-8-base oxygen base) the methacrylic acid ester ring type alkane ester of ethyl ester, isobornyl methacrylate etc.;
Acrylic acid aromatic ester of phenyl acrylate, benzyl acrylate etc. and acrylic acid aralkyl ester;
The aralkyl ester of the aromatic ester of the methacrylic acid of phenyl methacrylate, benzyl methacrylate etc. and methacrylic acid;
The dicarboxylic acid dialkyl of diethyl maleate, DEF, Yi Kang diethyl phthalate etc.;
The unsaturated assorted five-membered ring methacrylate that contains 1 oxygen atom and the unsaturated assorted six membered ring methacrylic acid of tetrahydrofurfuryl methacrylate, THFMA, methacrylic acid oxinane-2-methyl esters etc.;
4-methacryloxy methyl-2-methyl-2-ethyl-1,3-dioxolanes, 4-methacryloxy methyl-2-methyl-2-isobutyl-1,3-dioxolanes, 4-methacryloxy methyl-2-cyclohexyl-1,3-dioxolanes, 4-methacryloxy methyl-2-methyl-2-ethyl-1, the unsaturated assorted five-membered ring methacrylic acid that contains 2 oxygen atoms of 3-dioxolanes, 4-methacryloxy methyl-2-methyl-2-isobutyl-DOX etc.;
4-acryloyl-oxy ylmethyl-2, 2-dimethyl-1, 3-dioxolanes, 4-acryloyl-oxy ylmethyl-2-methyl-2-ethyl-1, 3-dioxolanes, 4-acryloyl-oxy ylmethyl-2, 2-diethyl-1, 3-dioxolanes, 4-acryloyl-oxy ylmethyl-2-methyl-2-isobutyl-1, 3-dioxolanes, 4-acryloyl-oxy ylmethyl-2-cyclopentyl-1, 3-dioxolanes, 4-acryloyl-oxy ylmethyl-2-cyclohexyl-1, 3-dioxolanes, 4-acryloxy Ethyl-2-Methyl-2-ethyl-1, 3-dioxolanes, 4-acryloxy propyl group-2-methyl-2-ethyl-1, 3-dioxolanes, 4-acryloxy butyl-2-methyl-2-ethyl-1, the unsaturated assorted five-membered ring acrylic acid that contains 2 oxygen atoms of 3-dioxolanes etc.,
Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, the vinyl aromatic compounds to methoxy styrene, 4-isopropenyl phenol etc.;
The N position substituted maleimide amine of N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridinyl) maleimide etc.;
1,3-butadiene, isoprene, 2, the conjugated diene compound of 3-dimethyl-1,3-butadiene etc.;
The unsaturated compound of vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate etc. etc.
In these other monomers, from with the above-mentioned monomer with carboxyl or derivatives thereof, there is the copolymerization of monomer of hydroxyl and the viewpoint of the developability of said composition, be preferably styrene, 4-isopropenyl phenol, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, tetrahydrofurfuryl methacrylate, 1,3-butadiene, 4-acryloyl-oxy ylmethyl-2-methyl-2-ethyl-DOX, N-N-cyclohexylmaleimide, N-phenylmaleimide, benzyl methacrylate.
The polystyrene conversion weight average molecular weight (Mw) of being measured by gel permeation chromatography (GPC) of [A] polymkeric substance is preferably 2.0 * 10 3～1.0 * 10 5, more preferably 5.0 * 10 3～5.0 * 10 4.By making the Mw of [A] polymkeric substance in above-mentioned scope, can improve radiation-sensitive degree and the alkali-developable of said composition.
The polystyrene conversion number-average molecular weight (Mn) of being measured by GPC of [A] polymkeric substance is preferably 2.0 * 10 3～1.0 * 10 5, more preferably 5.0 * 10 3～5.0 * 10 4.Based on making the Mn of [A] polymkeric substance in above-mentioned particular range, can improve said composition film curing time solidification reactivity.
The molecular weight distribution (Mw/Mn) of [A] polymkeric substance is preferably below 3.0, more preferably below 2.6.Based on making the Mw/Mn of [A] polymkeric substance in below 3.0, can improve the developability of interlayer dielectric for the display element of gained.
Moreover Mw and the Mn GPC based on following condition measures.
Device: GPC-101 (clear and electrician's system)
Post: in conjunction with GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804
Mobile phase: tetrahydrofuran
Column temperature: 40 ℃
Flow velocity: 1.0mL/ minute
Test portion concentration: 1.0 quality %
Test portion injection rate IR: 100 μ L
Detecting device: differential refractometer
Standard substance: monodisperse polystyrene
<[A] the synthetic method > of polymkeric substance
[A] polymkeric substance can synthesize by the free-radical polymerized incompatible of monomer based on giving above-mentioned each structural unit.When synthesizing, in same polymer molecule, contain structural unit (I) and during containing the two [A] polymkeric substance of the structural unit of epoxy radicals, as long as use at least to contain containing the monomer of acetal structure, make copolymerization with the potpourri of monomer containing epoxy radicals.On the other hand, in being manufactured on a polymer molecule, there is structural unit (I), and while thering is [A] polymkeric substance containing the structural unit of epoxy radicals in the polymer molecule different from it, as long as following, the polymerism solution that makes at least to contain containing the monomer of ethylidene ether structure carries out free radical polymerization, obtain in advance having the polymkeric substance of structural unit (I), at least make in addition the polymerism solution containing containing epoxy radicals monomer carry out free radical polymerization, and obtain thering is the polymkeric substance containing the structural unit of epoxy radicals, finally both are mixed to form to [A] polymkeric substance.
As the solvent using in the polyreaction at [A] polymkeric substance, such as enumerating alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetic acid esters, diethylene glycol alkyl ether, propylene-glycol monoalky lether, propylene-glycol monoalky lether acetic acid esters, propylene-glycol monoalky lether propionic ester, aromatic hydrocarbon based, ketone, other ester class etc.
As alcohols, such as enumerating methyl alcohol, ethanol, phenmethylol, 2-phenylethyl alcohol, 3-phenyl-1-propanol etc.
As ethers, such as enumerating tetrahydrofuran etc.
As glycol ethers, such as enumerating ethylene glycol monomethyl ether, ethylene glycol monomethyl ether etc.
As ethylene glycol alkyl ether acetic acid esters, such as enumerating methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol monomethyl ether acetate etc.
As diethylene glycol alkyl ether, such as enumerating diethylene glycol monomethyl ether, TC, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether etc.
As propylene-glycol monoalky lether, such as enumerating propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, propylene glycol single-butyl ether etc.
As propylene-glycol monoalky lether acetic acid esters, such as enumerating propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, propylene glycol single-butyl ether acetic acid esters etc.
As propylene-glycol monoalky lether propionic ester, such as enumerating propylene glycol monomethyl ether propionic ester, propylene glycol list ethylether propionic ester, propylene glycol list propyl ether propionic ester, propylene glycol single-butyl ether propionic ester etc.
As aromatic hydrocarbon based, such as enumerating toluene, dimethylbenzene etc.
As ketone, such as enumerating methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone etc.
As other ester class, for example, can enumerate methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, Butyl Glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid propyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxyl group methyl acetate, propoxyl group ethyl acetate, propoxyl group propyl acetate, propoxyl group butyl acetate, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, 3-butoxy butyl propionate etc.
In these solvents, being preferably ethylene glycol alkyl ether acetate esters, diethylene glycol alkyl ether, propylene-glycol monoalky lether class, propylene-glycol monoalky lether acetate esters, methoxyacetic acid butyl ester, is particularly preferably diethylene glycol dimethyl ether, diethylene glycol ethyl-methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, methoxyacetic acid butyl ester.
As the polymerization initiator using in polyreaction, can use general as radical polymerization initiator and known initiating agent, for example can enumerate: 2,2 '-azobis isobutyronitrile, 2,2 '-azo two-(2,4-methyl pentane nitrile) (ADVN), 2,2 '-azo is two-(4-methoxyl-2,4-methyl pentane nitrile), 2,2 '-azo is two-azo-compound of (2 Methylpropionic acid methyl esters) etc., benzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, 1, the organic peroxide of 1 '-bis--(t-butyl peroxy) cyclohexane etc., and hydrogen peroxide.
In the polyreaction for the manufacture of [A] polymkeric substance, in order to adjust molecular weight, can use molecular weight adjusting agent.As molecular weight adjusting agent, such as enumerating: the halogenated hydrocarbons of chloroform, carbon tetrabromide etc.; The thio-alcohol of n-hexyl mercaptan, n-octyl mercaptan, positive dodecyl mercaptan, three grades of dodecyl mercaptan, mercaptoacetic acid etc.; The xanthate classes such as sulfuration dimethyl yellow ortho esters, dithiodiisopropyl xanthate; Terpinolene, α-methylstyrenedimer etc.
<[B] compound >
[B] compound is the mass selection that is comprised of oxime sulfonates compound and salt compound at least one compound in going out, and is the acidic compound of the irradiation based on ray.Herein, as ray, such as using luminous ray, ultraviolet ray, far ultraviolet, electron ray, X ray etc.Said composition has [A] polymkeric substance of [B] compound and sour decomposability base because containing, and can bring into play the sense ray characteristics of eurymeric.
[oxime sulfonates compound]
As oxime sulfonates compound, such as enumerating compound that contains the oxime sulfonates base shown in following formula (2) etc.
In above-mentioned formula (2), R b1the aryl that maybe can be substituted for the straight chain shape that can be substituted, a chain, cyclic alkyl.
As above-mentioned R b1shown alkyl, is preferably the straight chain shape of carbon number 1～10 or the alkyl of a chain.The alkyl of the straight chain shape of above-mentioned carbon number 1～10 or a chain also can be substituted, and substituting group for example can be enumerated the alkoxy, 7 that contains carbon number 1～10, the ester ring type base that has bridge-type alicyclic group of 7-dimethyl-2-oxo norborny etc. etc.Moreover preferred ester ring type base is bicyclic alkyl.As above-mentioned R b1shown aryl, is preferably the aryl of carbon number 6～11, more preferably phenyl or naphthyl.Above-mentioned aryl also can be substituted, as substituting group, such as enumerating alkyl, alkoxy, halogen atom of carbon number 1～5 etc.
As the compound that contains the oxime sulfonates base shown in above-mentioned formula (2), such as enumerating the oxime sulfonates compound shown in following formula (3) etc.
In above-mentioned formula (3), R b1with above-mentioned formula (2) synonym.X is alkyl, alkoxy or halogen atom.M is 0～3 integer.Wherein, when X is a plurality of, a plurality of X can be identical or different.
The denotable alkyl of above-mentioned X, is preferably the straight chain shape of carbon number 1～4 or the alkyl of a chain.As the alkoxy shown in above-mentioned X, be preferably the straight chain shape of carbon number 1～4 or the alkoxy of a chain.Halogen atom as shown in above-mentioned X, is preferably chlorine atom, fluorine atom.M is preferably 0 or 1.In above-mentioned formula (3), the compound that the position of substitution that m is 1, X is methyl, X is ortho position is for preferably.
As the oxime sulfonates compound shown in above-mentioned (3), such as enumerating the compound shown in respectively of following formula (i)～(v) etc.
Moreover, above-claimed cpd (i) (the sub-thiophene-2-yl of 5-sulfonyl propyl oxygen base imido grpup-5H-)-(2-aminomethyl phenyl) acetonitrile, compound (ii) (the sub-thiophene-2-yl of 5-octyl group sulfonyloxy imido grpup-5H-)-(2-aminomethyl phenyl) acetonitrile, compound (iii) (the sub-thiophene-2-yl of camphor sulfonyloxy imido grpup-5H-)-(2-aminomethyl phenyl) acetonitrile, compound (iv) (the sub-thiophene-2-yl of 5-tolysulfonyl oxygen base imido grpup-5H-)-(2-aminomethyl phenyl) acetonitrile and compound (v) (5-octyl group sulfonyloxy imido grpup)-(4-methoxyphenyl) acetonitrile are for being obtained by commercially available product.
[salt]
As salt, such as enumerating two benzene base Iodonium salt, triphenyl sulfonium salt, sulfonium salt, benzothiazolium salt, thiophane salt etc.
As Er Ben Ji Iodonium salt, for example can enumerate Er Ben Ji Iodonium tetrafluoroborate, Er Ben Ji Iodonium hexafluorophosphate, Er Ben Ji Iodonium hexafluoro arsenate, Er Ben Ji Iodonium trifluoro-methanyl sulfonate, Er Ben Ji Iodonium trifluoro-acetate, Er Ben Ji Iodonium-tosilate, Er Ben Ji Iodonium butyl three (2, 6-difluorophenyl) borate, 4-methoxyphenyl Ben Ji Iodonium tetrafluoroborate, two (4-tert-butyl-phenyl) Iodonium tetrafluoroborates, two (4-tert-butyl-phenyl) Iodonium hexafluoro arsenates, two (4-tert-butyl-phenyl) Iodonium trifluoro-methanyl sulfonates, two (4-tert-butyl-phenyl) Iodonium trifluoro-acetates, two (4-tert-butyl-phenyl) Iodonium-tosilate, two (4-tert-butyl-phenyl) Iodonium camphorsulfonic acids etc.
As triphenyl sulfonium salt, for example can enumerate triphenylsulfonium trifluoro-methanyl sulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoro-acetate, triphenylsulfonium-tosilate, triphenylsulfonium butyl three (2,6-difluorophenyl) borate etc.
As sulfonium salt, such as enumerating benzyl sulfonium salt of alkyl sulfonium salt, benzyl sulfonium salt, dibenzyl sulfonium salt, replacement etc.
As alkyl sulfonium salt, such as enumerating 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, dimethyl-4-(benzyloxycarbonyloxy base) phenyl sulfonium hexafluoro antimonate, dimethyl-4-(benzoyloxy) phenyl sulfonium hexafluoro antimonate, dimethyl-4-(benzoyloxy) phenyl sulfonium hexafluoro arsenate, the chloro-4-acetoxyl group of dimethyl-3-phenyl sulfonium hexafluoro antimonate etc.
As benzyl sulfonium salt, such as enumerating benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, benzyl-4-methoxybenzene ylmethyl sulfonium hexafluoro antimonate, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-3-chloro-4-hydroxyl phenyl methyl sulfonium hexafluoro arsenate, 4-methoxy-benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate etc.
As dibenzyl sulfonium salt, such as enumerating dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl dibenzyl sulfonium hexafluoro antimonate, dibenzyl-4-methoxyphenyl sulfonium hexafluoro antimonate, dibenzyl-3-chloro-4-hydroxyl phenyl sulfonium hexafluoro arsenate, dibenzyl-3-methyl-4-hydroxyl-5-tert-butyl-phenyl sulfonium hexafluoro antimonate, benzyl-4-methoxy-benzyl-4-hydroxy phenyl sulfonium hexafluorophosphate etc.
As the benzyl sulfonium salt replacing, for example can enumerate p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, to nitrobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, to nitrobenzyl-3-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 3,5-dichloro benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, o-chlorobenzyl-3-chloro-4-hydroxyl phenyl methyl sulfonium hexafluoro antimonate etc.
As benzothiazolium salt, such as enumerating 3-benzyl benzothiazole hexafluoro antimonate, 3-benzyl benzothiazole hexafluorophosphate, 3-benzyl benzothiazole tetrafluoroborate, 3-(to methoxy-benzyl) benzothiazole hexafluoro antimonate, 3-benzyl-2-methyl mercapto benzo thiazole hexafluoro antimonate, 3-benzyl-5-chloro benzothiazole hexafluoro antimonate etc.
As thiophane salt, for example can enumerate 4, 7-bis--n-butoxy-1-naphthyl thiophane trifluoro-methanyl sulfonate, 1-(4-n-butoxy naphthalene-1-yl) thiophane trifluoro-methanyl sulfonate, 1-(4-n-butoxy naphthalene-1-yl) the fluoro-normal butane sulfonate of thiophane nine, 1-(4-n-butoxy naphthalene-1-yl) thiophane-1, 1, 2, 2-tetrafluoro-2-(norbornane-2-yl) ethane sulfonate, 1-(4-n-butoxy naphthalene-1-yl) thiophane-2-(5-tertbutyloxycarbonyl oxygen base dicyclo [2.2.1] heptane-2-yl)-1, 1, 2, 2-HFC-134a sulfonate, 1-(4-n-butoxy naphthalene-1-yl) thiophane-2-(6-tertbutyloxycarbonyl oxygen base dicyclo [2.2.1] heptane-2-yl)-1, 1, 2, 2-HFC-134a sulfonate etc.
Moreover, as [B] compound, also can contain sulfimine compound, halogen-containing compound, diazomethane compound, sulphones, sulfonate compound, carbonate etc.
As sulfimine compound, for example, can enumerate N-(trimethyl fluoride sulfonyl oxygen base) succinimide, N-(camphor sulfonyloxy) succinimide, N-(4-aminomethyl phenyl sulfonyloxy) succinimide, N-(2-trifluoromethyl sulfonyloxy) succinimide, N-(4-fluorophenyl sulfonyloxy) succinimide, N-(trimethyl fluoride sulfonyl oxygen base) BIDA, N-(camphor sulfonyloxy) BIDA, N-(2-trifluoromethyl sulfonyloxy) BIDA, N-(2-fluorophenyl sulfonyloxy) BIDA, N-(trimethyl fluoride sulfonyl oxygen base) diphenyl maleimide, N-(camphor sulfonyloxy) diphenyl maleimide, 4-aminomethyl phenyl sulfonyloxy) diphenyl maleimide, N-(2-trifluoromethyl sulfonyloxy) diphenyl maleimide, N-(4-fluorophenyl sulfonyloxy) diphenyl maleimide, N-(4-fluorophenyl sulfonyloxy) diphenyl maleimide, N-(phenyl sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(4-aminomethyl phenyl sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(fluoroform sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(nine fluorine butane sulfonyloxies) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(camphor sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(camphor sulfonyloxy)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(trimethyl fluoride sulfonyl oxygen base)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(4-aminomethyl phenyl sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(4-aminomethyl phenyl sulfonyloxy)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(2-trifluoromethyl sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(2-trifluoromethyl sulfonyloxy)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(4-fluorophenyl sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(4-fluorophenyl sulfonyloxy)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(trimethyl fluoride sulfonyl oxygen base) dicyclo [2.2.1] heptane-5,6-oxo-2,3-dicarboximide, N-(camphor sulfonyloxy) dicyclo [2.2.1] heptane-5,6-oxo-2,3-dicarboximide, N-(4-aminomethyl phenyl sulfonyloxy) dicyclo [2.2.1] heptane-5,6-oxo-2,3-dicarboximide, N-(2-trifluoromethyl sulfonyloxy) dicyclo [2.2.1] heptane-5,6-oxo-2,3-dicarboximide, N-(4-fluorophenyl sulfonyloxy) dicyclo [2.2.1] heptane-5,6-oxo-2,3-dicarboximide, N-(trimethyl fluoride sulfonyl oxygen base) naphthyl dicarboximide, N-(camphor sulfonyloxy) naphthyl dicarboximide, N-(4-aminomethyl phenyl sulfonyloxy) naphthyl dicarboximide, N-(phenyl sulfonyloxy) naphthyl dicarboximide, N-(2-trifluoromethyl sulfonyloxy) naphthyl dicarboximide, N-(4-fluorophenyl sulfonyloxy) naphthyl dicarboximide, N-(pentafluoroethyl group sulfonyloxy) naphthyl dicarboximide, N-(seven fluoropropyl sulfonyloxies) naphthyl dicarboximide, N-(nine fluorine butyl sulfonyloxies) naphthyl dicarboximide, N-(ethyl sulfonyloxy) naphthyl dicarboximide, N-(sulfonyl propyl oxygen base) naphthyl dicarboximide, N-(butyl sulfonyloxy) naphthyl dicarboximide, N-(amyl group sulfonyloxy) naphthyl dicarboximide, N-(hexyl sulfonyloxy) naphthyl dicarboximide, N-(heptyl sulfonyloxy) naphthyl dicarboximide, N-(octyl group sulfonyloxy) naphthyl dicarboximide, N-(nonyl sulfonyloxy) naphthyl dicarboximide etc.
As halogen-containing compound, such as can enumerate hydrocarbon compound containing alkylhalide group, containing the assorted ring compound of alkylhalide group etc.
As diazomethane compound; for example can enumerate two (trifluoromethyl sulfonyl) diazomethanes, two (cyclohexyl sulfonyl) diazomethane, two (phenyl sulfonyl) diazomethane, two (p-methylphenyl sulfonyl) diazomethane, two (2; 4-xylyl sulfonyl) diazomethane, two (rubigan sulfonyl) diazomethane, methyl sulphonyl-p-toluenesulfonyl diazomethane, cyclohexyl sulfonyl (1; 1-dimethyl ethyl sulfonyl) diazomethane, two (1,1-dimethyl ethyl sulfonyl) diazomethane, phenyl sulfonyl (benzoyl) diazomethane etc.
As sulphones, such as enumerating beta-keto sulphones, 'Beta '-sulfonyl sulphones, diaryl two sulphones etc.
As sulfonate compound, such as enumerating sulfonic acid alkane ester, sulfonic acid alkyl halide ester, sulfonic acid aromatic ester, sulfimide ester etc.
As carbonate, such as enumerating the adjacent p-Nitrobenzyl of carboxylic acid etc.
As oxime sulfonates compound, be preferably the compound that contains the oxime sulfonates base shown in above-mentioned formula (2), the oxime sulfonates compound shown in above-mentioned formula (3) more preferably, it is particularly preferably (the sub-thiophene-2-yl of 5-sulfonyl propyl oxygen base imido grpup-5H-)-(2-aminomethyl phenyl) acetonitrile that can be obtained by commercially available product, (the sub-thiophene-2-yl of 5-octyl group sulfonyloxy imido grpup-5H-)-(2-aminomethyl phenyl) acetonitrile, (the sub-thiophene-2-yl of 5-tolysulfonyl oxygen base imido grpup-5H-)-(2-aminomethyl phenyl) acetonitrile, (the sub-thiophene-2-yl of camphor sulfonyloxy imido grpup-5H-)-(2-aminomethyl phenyl) acetonitrile, (5-octyl group sulfonyloxy imido grpup)-(4-methoxyphenyl) acetonitrile.As salt, be preferably thiophane salt, benzyl sulfonium salt, more preferably 4,7-bis--n-butoxy-1-naphthyl thiophane trifluoro-methanyl sulfonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate.
[B] compound can be used alone, and also can mix two or more use.The content of [B] compound in said composition, for [A] polymkeric substance 100 mass parts, is preferably 0.1 mass parts～10 mass parts, more preferably 1 mass parts～5 mass parts.Based on making the content of [B] compound become above-mentioned particular range, can make the radiation-sensitive degree optimization of said composition, while can form, maintain the high display element interlayer dielectric of transparency skin hardness.
<[C] organic solvent >
Said composition is based on mix [A] polymkeric substance, [B] compound and suitable component, other optional members such as [D] surfactant optionally in [C] organic solvent, so that dissolve or the state that disperses and modulating.As [C] organic solvent, at least containing (C1) is more than 0.1mmHg and lower than the organic solvent of 1mmHg the vapor pressure of 20 ℃.Again, as (C2) organic solvent, being preferably the vapor pressure containing at 20 ℃ is the organic solvent below the above 20mmHg of 1mmHg.[C] organic solvent based on use with the vapor pressure of above-mentioned particular range, even if adopt jetting nozzle formula rubbing method, on one side also can prevent crawling, Yi Bian high-speed coating.Moreover the mensuration of vapor pressure can be used known method, but the value of measuring based on the method for evapotranspiring (gas communication method) in this instructions middle finger.
As [C] organic solvent, can use suitably and each composition can be dissolved equably or disperses, and the organic solvent not reacting with each inscape.As [C] organic solvent, such as enumerating phenmethylol, ethylene glycol monoalkyl ether class, glycol dialkyl ether class, propylene-glycol monoalky lether class, diethylene glycol monoalkyl ethers, 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, lactic acid ester, aliphatic carboxylic acid esters,'s class, amide-type, ketone etc.These can be used alone, and also can mix two or more use.
As (C1) organic solvent, for example, can enumerate:
Phenmethylol;
The ethylene glycol monoalkyl ether class of ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list propyl ether, ethylene glycol monobutyl ether etc.;
The glycol dialkyl ether class of ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol bisthioglycolate propyl ether etc.;
The propylene-glycol monoalky lether class of propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, propylene glycol single-butyl ether etc.;
The diethylene glycol monoalkyl ethers of diethylene glycol monomethyl ether, TC etc.;
The diethylene glycol dialkyl ether class of diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether etc.;
The diethylene glycol monoalky lether acetate esters of diethylene glycol monomethyl ether acetic acid esters, TC acetic acid esters, diethylene glycol list propyl ether acetic acid esters, diethylene glycol single-butyl ether acetic acid esters etc.;
The dipropylene glycol monoalkyl ethers of DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol list propyl ether, dipropylene glycol single-butyl ether etc.;
The dipropylene glycol dialkyl ether of dipropylene glycol dimethyl ether, dipropylene glycol Anaesthetie Ether etc.;
The dipropylene glycol monoalky lether acetate esters of DPGME acetic acid esters, dihydroxypropane single-ethyl ether acetic acid esters, dipropylene glycol list propyl ether acetic acid esters, dipropylene glycol single-butyl ether acetic acid esters etc.;
The lactic acid ester of lactic acid n-propyl ester, isopropyl lactate, n-butyl lactate, isobutyl lactate, lactic acid n-pentyl ester, isoamyl lactate etc.;
Hydroxyl ethyl acetate, 2-hydroxy-2-methyl ethyl propionate, 2-hydroxy-3-methyl ethyl butyrate, ethoxy ethyl acetate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butyl propionic ester, 3-methyl-3-methoxyl butyl butyric ester, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, aliphatic carboxylic acid esters,'s class of ethyl pyruvate etc.,
The amide-type of N-METHYLFORMAMIDE, DMF, N-methylacetamide, DMA etc.;
The ketone of N-methylpyrrole pyridine ketone, gamma-butyrolacton etc. etc.
(C1) organic solvent can be used alone, and also can mix two or more use.As (C1) organic solvent, be preferably at least one organic solvent of selecting in the group who is formed by diethylene glycol ethyl-methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, phenmethylol, DPGME.
As (C2) organic solvent, such as enumerating diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol list propyl ether acetic acid esters, ethylene glycol monobutyl ether acetic acid esters, propylene glycol monomethyl ether, cyclohexanone, ethyl acetate, propyl acetate, n-butyl acetate, methyl propyl ketone, methyl isobutyl ketone, 3-methoxy methyl propionate, methyl lactate, ethyl lactate etc.
(C2) organic solvent can be used alone, and also can mix two or more use.As (C2) organic solvent, be preferably by diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol list propyl ether acetic acid esters, propylene glycol monomethyl ether, cyclohexanone, n-butyl acetate, methyl isobutyl ketone, 3-methoxy methyl propionate, formed group in select at least one organic solvent.
When mixing use (C1) organic solvent and (C2) organic solvent, be preferably the combination of diethylene glycol ethyl-methyl ether/diethylene glycol dimethyl ether, diethylene glycol ethyl-methyl ether/propylene glycol monomethyl ether, diethylene glycol ethyl-methyl ether/cyclohexanone, diethylene glycol diethyl ether/diethylene glycol dimethyl ether, diethylene glycol diethyl ether/propylene glycol monomethyl ether, diethylene glycol diethyl ether/cyclohexanone, diethylene glycol diethyl ether/3-methoxy methyl propionate, diethylene glycol diethyl ether/methyl isobutyl ketone, diethylene glycol diethyl ether/n-butyl acetate.
(C2) content of organic solvent, for the total amount of (C1) organic solvent and (C2) organic solvent, is preferably below the above 90 quality % of 10 quality %, more preferably below the above 50 quality % of 10 quality %.The mass ratio of (C2) organic solvent that (C1) organic solvent based on steam is forced down and vapor pressure are high becomes above-mentioned particular range, in special filming after prebake conditions, remaining quantity of solvent is optimization, the mobility of filming is balanced, result can suppress the generation of crawling (striated inequality, pin trace inequality, vaporific unequal), can further improve film thickness uniformity.Again, based on making remaining quantity of solvent optimization, sour generation and sour decomposability base height balance, radiation-sensitive degree has the tendency that becomes good.
The solid component concentration of said composition is below the above 30 quality % of 10 quality %, is preferably below the above 25 quality % of 20 quality %.Solid component concentration based on making said composition becomes above-mentioned particular range, can effectively suppress the generation of crawling.
Said composition is below the above 12mPas of 2.0mPas the viscosity of 25 ℃, is preferably below the above 10mPas of 2.0mPas.Viscosity based on making said composition becomes above-mentioned particular range, on one side can maintain film thickness uniformity, Yi Bian even if there is crawling, also can balance reach well the viscosity of the degree of energy automatic uniform, and can realize high-speed coating.
<[D] surfactant >
Said composition can further contain [D] surfactant as the suitable component of the overlay film formative for further raising said composition.As surfactant, such as enumerating fluorine class surfactant, polysiloxane (シ リ コ mono-Application) class surfactant etc.Said composition, owing to containing [D] surfactant, can improve the surface smoothness of filming, and result can further improve the film thickness uniformity of interlayer dielectric for formed display element.
As fluorine class surfactant, be preferably endways, at least arbitrary position of main chain and side chain has the compound that fluoroalkyl and/or fluorine are stretched alkyl, for example can enumerate 1, 1, 2, 2-tetrafluoro n-octyl (1, 1, 2, 2-tetrafluoro n-pro-pyl) ether, 1, 1, 2, 2-tetrafluoro n-octyl (n-hexyl) ether, six ethylene glycol bisthioglycolates (1, 1, 2, 2, 3, 3-hexafluoro n-pentyl) ether, eight ethylene glycol bisthioglycolates (1, 1, 2, 2-tetrafluoro normal-butyl) ether, six propylene glycol two (1, 1, 2, 2, 3, 3-hexafluoro n-pentyl) ether, eight propylene glycol two (1, 1, 2, 2-tetrafluoro normal-butyl) ether, perfluor n-dodecane sodium sulfonate, 1, 1, 2, 2, 3, 3-hexafluoro n-decane, 1, 1, 2, 2, 3, 3, 9, 9, 10, 10-ten fluorine n-dodecanes, fluoroalkyl benzene sodium sulfonate, fluoroalkyl sodium phosphate, fluoroalkyl carboxylic acid sodium, two glycerine four (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl poly(ethylene oxide)polymers, perfluoroalkyl alkoxide, carboxylic acid fluoroalkyl ester etc.
As the commercially available product of fluorine class surfactant, for example, can enumerate BM-1000, BM-1100 (being BM CHEMIE system above), Megafac F142D, Megafac F172, Megafac F173, Megafac F183, Megafac F178, Megafac F191, Megafac F471, Megafac F476 (being large Japanese ink chemical industry system above), Florad FC-170C, Florad FC-171, Florad FC-430, Florad FC-431 (being Sumitomo 3M system above), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (being Asahi Glass system above), Eftop EF301, Eftop EF303, Eftop EF352 (changing into system for new autumn fields above), Ftergent FT-100, Ftergent FT-110, Ftergent FT-140A, Ftergent FT-150, Ftergent FT-250, Ftergent FT-251, Ftergent FT-300, Ftergent FT-310, Ftergent FT-400S, Ftergent FTX-218, Ftergent FT-251 (being NEOS system above) etc.
As polysiloxane-based surfactant, Toray Silicone DC3PA for example, Toray Silicone DC7PA, Toray Silicone SH11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH-190, Toray Silicone SH-193, Toray Silicone SZ-6032, Toray Silicone SF-8428, Toray Silicone DC-57, Toray Silicone DC-190, SH 8400 FLUID (being the poly-silica system of eastern beautiful DOW CORNING above), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (the above WeiGE シ リ コ of Toshiba mono-Application system), organic siloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry system) etc.
[D] surfactant can be used alone, and also can mix two or more use.The content of [D] surfactant in said composition, for [A] polymkeric substance 100 mass parts, is preferably below above 2 mass parts of 0.01 mass parts, more preferably below above 1 mass parts of 0.05 mass parts.Based on making the content of [D] surfactant become above-mentioned particular range, can further improve the surface smoothness of filming.
<[E] multifunctional (methyl) acrylate >
Said composition further contains [E] multifunctional (methyl) acrylate as suitable component.Said composition, owing to further containing [E] multifunctional (methyl) acrylate compounds, can improve transmittance and the heat-resisting transparency of interlayer dielectric for display element.As [E] multifunctional (methyl) acrylate, can (methyl) acrylate such as enumerating 2 officials, 3 officials can be above (methyl) acrylate etc.
As 2 officials' energy (methyl) acrylate, for example ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, 1,6-hexane diol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate etc.
Commercially available product as 2 officials' energy (methyl) acrylate, for example Aronix M-210, Aronix M-240, Aronix M-6200 (being the synthetic system in East Asia above), KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (be Japanese chemical drug system above), Biscoat 260, Biscoat 312, Biscoat 335HP (being Osaka organic chemistry industry system above), Light Acrylate 1,9-NDA (common prosperity society chemistry is made) etc.
(methyl) acrylate that can be above as 3 officials, for example, can enumerate trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, new penta tetrol triacrylate, new penta tetrol trimethyl acrylic ester, new penta tetrol tetraacrylate, new penta tetrol tetramethyl acrylate, two new penta tetrol five acrylate, two new penta tetrol pentamethyl acrylate, two new penta tetrol six acrylate, the potpourri of two new penta tetrol five acrylate and two new penta tetrol six acrylate, two new penta tetrol hexamethyl acrylate, new penta tetrol six acrylate of oxirane modification two, three (2-acryloxy ethyl) phosphate, three (2-methacryloxyethyl) phosphate, the new penta tetrol triacrylate of succinic acid modification, make to there is the compound that straight chain is stretched alkyl and ester ring type structure and had 2 above isocyanate group, react with the compound that there is more than 1 hydroxyl and there are 3～5 (methyl) acryloxies in molecule and polyfunctional amine carbamate acrylic ester compound etc.
The commercially available product of (methyl) acrylate that can be above as 3 officials, for example can enumerate Aronix M-309, Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix TO-1450 (being the synthetic system in East Asia above), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD DPEA-12 (being Japanese chemical drug system above), Biscoat 295, Biscoat 300, Biscoat 360, Biscoat GPT, Biscoat 3PA, Biscoat 400 (being Osaka organic chemistry industry system above) etc.As containing the commercially available product that polyfunctional amine carbamate acrylate is compound, such as enumerating New Forntier R-1150 (the first industrial pharmacy system), KAYARAD DPHA-40H (Japanese chemical drug system) etc.
In these [E] multifunctional (methyl) acrylate, be preferably and contain ethylene glycol bisthioglycolate (methyl) acrylate, ω-carboxyl polycaprolactone single-acrylate, 1, 9-nonanediol dimethylacrylate, diethylene glycol dimethylacrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, new penta tetrol triacrylate, new penta tetrol tetraacrylate, two new penta tetrol five acrylate, two new penta tetrol six acrylate, the potpourri of two new penta tetrol five acrylate and two new penta tetrol six acrylate, new penta tetrol six acrylate of oxirane modification two, the new penta tetrol triacrylate of succinic acid modification, the commercially available product of polyfunctional amine carbamate acrylic ester compound.
[E] multifunctional (methyl) acrylate can be separately or mixes two or more use.The content of [E] multifunctional (methyl) acrylate in said composition, for [A] polymkeric substance 100 mass parts, is preferably 1 mass parts～30 mass parts, more preferably 5 mass parts～15 mass parts.Based on making the content of [E] multifunctional (methyl) acrylate become above-mentioned particular range, can further improve transmittance and the heat-resisting transparency of interlayer dielectric for display element.
<[F] antioxidant >
Said composition can further contain [F] antioxidant as suitable component.Said composition, owing to further containing [F] antioxidant, can improve transmittance and the heat-resisting transparency of interlayer dielectric for display element.[F] antioxidant in this instructions, just refer to phenolic compounds, have hindered phenol structure compound, have hindered amine structure compound, there is the compound of alkyl phosphate structure and there is the compound of thioether structure.
As phenolic compounds, such as enumerating 4-metoxyphenol, 4-thanatol etc.
As the compound with hindered phenol structure, for example, can enumerate 2,6-, bis--tert-butyl group-4-cresols, new penta tetrol four [3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester], sulphur two is stretched ethyl two [3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester, 1,3,5-trimethyl-2,4,6-tri-(3,5-, bis--tertiary butyl-4-hydroxy benzyl) benzene, N, N '-hexane-1, the two [3-(3,5-, bis--tert-butyl-hydroxy phenyl propionamide) of 6-bis-bases, 3,3 ', 3 ", 5 ', 5 "-six-tert-butyl group-a, a ', a "-(sym-trimethyl benzene-2,4,6-, tri-bases) three-paracresol, two (octyl group the sulfidomethyl)-orthoresols of 4,6-, two (dodecyl the sulfidomethyl)-orthoresols of 4,6-, stretch two (ethylene oxide) two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic esters of ethyl, hexa-methylene two [3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester], 1,3,5-tri-(3,5-, bis--tertiary butyl-4-hydroxy benzyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones, 1,3,5-tri-[(the 4-tert-butyl group-3-hydroxyl-2,6-xylyl) methyl]-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones, 2,6-, bis--tert-butyl group-4-(two (the pungent sulfenyl)-1,3,5-triazines-2-base amine of 4,6-) phenol, three-(3,5-, bis--tertiary butyl-4-hydroxy benzyl)-fulminuric acid esters etc.
As the commercially available product with the compound of hindered phenol structure, for example, can enumerate Adkstab AO-20, Adkstab AO-30, Adkstab AO-40, Adkstab AO-50, Adkstab AO-60, Adkstab AO-70, Adkstab AO-80, Adkstab AO-330 (being ADEKA system above), sumilizer GM, sumilizer GS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX-R, sumilizer GA-80 (being Sumitomo Chemical system above), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX 1425WL, IRGANOX 1520L, IRGANOX 245, IRGANOX 259, IRGANOX 3114, IRGANOX 565, IRGAMOD 295 (being CIBA Japan system above), Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314 (being API Corporation system above) etc.
As the commercially available product with the compound of hindered amine structure, for example can enumerate Adkstab LA-52, Adkstab LA57, Adkstab LA-62, Adkstab LA-67, Adkstab LA-63P, Adkstab LA-68LD, Adkstab LA-77, Adkstab LA-82, Adkstab LA-87 (being ADEKA system above), sumilizer 9A (Sumitomo Chemical system), CHIMASSORB 119FL, CHIMASSORB 2020FDL, CHIMASSORB 944FDL, TINUVIN 622LD, TINUVIN 144, TINUVIN 765, TINUVIN 770DF (being CIBA Japan system above).
As the commercially available product with the compound of alkyl phosphate structure, such as enumerating Adkstab PEP-4C, Adkstab PEP-8, Adkstab PEP-8W, Adkstab PEP-24G, Adkstab PEP-36, Adkstab HP-10, Adkstab 2112, Adkstab 260, Adkstab 522A, Adkstab 1178, Adkstab 1500, Adkstab C, Adkstab 135A, Adkstab 3010, Adkstab TPP (being ADEKA system above), IRGAFOS 168 (CIBA Japan system) etc.
As the commercially available product with the compound of thioether structure, such as enumerating Adkstab AO-412S, Adkstab AO-503 (being ADEKA system above), sumilizer TPL-R, sumilizer TPM, sumilizer TPS, sumilizer TP-D, sumilizer MB (being Sumitomo Chemical system above), IRGANOX PS800FD, IRGANOX PS802FD (being CIBA Japan system above), DLTP, DSTP, DMTP, DTTP (being API Corporation system above) etc.
In these [F] antioxidants, be preferably there is phenolic compounds, the compound of hindered phenol structure, 4-metoxyphenol, 2 more preferably, 6-bis--tert-butyl group-4-cresols, 1,3,5-trimethyl-2,4,6-tri-(3,5-, bis--tertiary butyl-4-hydroxy benzyl) benzene, three-(3,5-bis--tertiary butyl-4-hydroxy benzyl)-fulminuric acid ester, new penta tetrol four [3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester].
[F] antioxidant can be separately or mixes two or more use.The content of [F] antioxidant in said composition, for [A] polymkeric substance 100 mass parts, is preferably 0.1 mass parts～10 mass parts, more preferably 0.2 mass parts～5 mass parts.Based on making the content of [F] antioxidant become above-mentioned particular range, can further improve transmittance and the heat-resisting transparency of interlayer dielectric for display element.
<[G] epoxy compound >
Said composition can further contain compound that [G] have more than 2 epoxy radicals in 1 molecule as suitable component.Said composition, owing to further containing [G] epoxy compound, can improve transmittance and the heat-resisting transparency of interlayer dielectric for display element.
As [G] epoxy compound, so long as have the compound of more than 2 epoxy radicals in 1 molecule, there is no particular limitation, but except [A] polymkeric substance.As epoxy radicals, can enumerate Oxyranyle (1,2-epoxy structure), oxetanyl (1,3-epoxy structure), 3,4-epoxy radicals cyclohexyl.
As there is the compound of more than 2 Oxyranyles in 1 molecule, for example, can enumerate:
Bisphenol-A diepoxy propyl ether (4,4 '-isopropylidene biphenol and 1-are chloro-2, the bunching compound of 3-epoxy radicals propane), the diepoxy propyl ether of the bisphenol compound of Bisphenol F diepoxy propyl ether, bisphenol S diepoxy propyl ether, hydrogenated bisphenol A diepoxy propyl ether, A Hydrogenated Bisphenol A F diepoxy propyl ether, hydrogenated bisphenol A D diepoxy propyl ether, brominated bisphenol A diepoxy propyl ether, brominated bisphenol F diepoxy propyl ether, brominated bisphenol S diepoxy propyl ether etc.;
1,4-butylene glycol diepoxy propyl ether, 1, many glycidyl ethers of the polyvalent alcohol of 6-hexanediol diepoxy propyl ether, glycerine three glycidyl ethers, trimethylolpropane tris glycidyl ethers, polyglycol diepoxy propyl ether, polypropylene glycol diepoxy propyl ether etc.;
The one kind or two or more alkylene oxide of addition on aliphatic polyol based at ethylene glycol, propylene glycol, glycerine etc. and many glycidyl ethers of polyether glycol;
Phenol novolak type epoxy resin;
Cresols phenolic resin varnish type epoxy resin;
Many phenol-type epoxy resins;
Cyclic aliphatic epoxy resin;
The diepoxy propyl diester of aliphatic long-chain dibasic acid;
The glycidyl ester of higher fatty acid;
Epoxidised soybean oil, epoxidised linseed oil etc.
As there is more than 2 oxetanyl (1 in 1 molecule, 3-epoxy structure) compound, such as enumerating Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxetanes methoxyl) methyl] benzene, two { [1-ethyl (3-oxetanes)] methyl } ether etc.
As have more than 23 in 1 molecule, the compound of 4-epoxy radicals cyclohexyl, for example can enumerate 3, 4-epoxy radicals cyclohexyl methyl-3 ', 4 '-epoxy-cyclohexane carboxylate, 2-(3, 4-epoxy radicals cyclohexyl-5, 5-spiral shell-3, 4-epoxy radicals) cyclohexane-trimethylene-formal, two (3, 4-epoxy radicals cyclohexyl methyl) adipate, two (3, 4-epoxy radicals-6-methyl cyclohexane ylmethyl) adipate, 3, 4-epoxy radicals-6-methylcyclohexyl-3 ', 4 '-epoxy radicals-6 '-methylcyclohexanecarboxylic acid ester, di-2-ethylhexylphosphine oxide (3, 4-epoxy-cyclohexane), bicyclopentadiene diepoxide, two (3 of ethylene glycol, 4-epoxy radicals cyclohexyl methyl) ether, ethylidine two (3, 4-epoxy-cyclohexane carboxylate), interior ester modified 3, 4-epoxy radicals cyclohexyl methyl-3 ', 4 '-epoxy-cyclohexane carboxylate etc.
As the commercially available product of [G] epoxy compound, for example, can enumerate:
As bisphenol A type epoxy resin, can enumerate Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (being japan epoxy resin system above) etc.;
As bisphenol f type epoxy resin, can enumerate Epicoat 807 (japan epoxy resin system) etc.;
As phenol novolak type epoxy resin, can enumerate Epicoat 152, Epicoat 154, Epicoat 157S65 (being japan epoxy resin system above), EPPN201, EPPN 202 (being Japanese chemical drug system above) etc.;
As cresols phenolic resin varnish type epoxy resin, can enumerate EOCN102, EOCN103S, EOCN104S, 1020,1025,1027 (being Japanese chemical drug system above), Epicoat 180S75 (japan epoxy resin system) etc.;
As many phenol-type epoxy resins, can enumerate Epicoat 1032H60, Epicoat XY-4000 (being japan epoxy resin system above) etc.;
As cyclic aliphatic epoxy resin, can enumerate CY-175, CY-177, CY-179, Araldite CY-182, Araldite CY-192,184 (being CIBA speciality chemical system above), ERL-4234,4299,4221,4206 (being U.C.C system above), Shodyne 509 (clear and electrician's system), Epiclon 200, Epiclon 400 (being large Japanese ink system above), Epicoat 871, Epicoat 872 (being japan epoxy resin system above), ED-5661, ED-5662 (being Celanese Coating system above) etc.;
As the many glycidyl ethers of aliphatics, can enumerate Epolight 100MF (common prosperity society chemistry system), Epiol TMP (Japanese grease system), Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxetanes methoxyl) methyl] benzene, two { [1-ethyl (3-oxetanes)] methyl } ether etc.
In these, be preferably bisphenol-A diepoxy propyl ether (4,4 '-isopropylidene biphenol and 1-chloro-2, the bunching compound of 3-epoxy radicals propane), Bisphenol F diepoxy propyl ether, 1, two [(3-ethyl-3-oxetanes methoxyl) methyl] benzene of 4-, two { [1-ethyl (3-oxetanes)] methyl } ether, 3,4-epoxy radicals cyclohexyl methyl-3 ', 4 '-epoxy-cyclohexane carboxylate.
[G] epoxy compound can separately or mix two or more use.The content of [G] epoxy compound in said composition, for [A] polymkeric substance 100 mass parts, is preferably 1 mass parts～30 mass parts, more preferably 3 mass parts～15 mass parts.Based on making the content of [G] epoxy compound in above-mentioned particular range, can further improve transmittance and the heat-resisting transparency of interlayer dielectric for display element.
Other optional member of < >
Said composition above-mentioned except containing [A]～[G] composition, in not damaging the scope of desired effect, optionally also can contain other optional members such as [H] closely sealed auxiliary agent, [I] alkali compounds, [J] quinone di-azido compound.These other optional members can be used alone, and also can mix two or more use.Below, each composition is described in detail in detail.
[[H] closely sealed auxiliary agent]
In order to improve as the inorganics of substrate and the adhesion of dielectric film, can use closely sealed auxiliary agent, this inorganics is such as the silicon compound that comprises silicon, monox, silicon nitride etc., the metal of gold, copper, aluminium etc.As closely sealed auxiliary agent, be preferably functional silanes coupling agent.As functional silanes coupling agent, such as enumerating, there is carboxyl, methacryl, isocyanate group, epoxy radicals (being preferably Oxyranyle), the substituent silane coupling agent of mercapto isoreactivity etc.
As functional silanes coupling agent, for example can enumerate trimethoxy silane yl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanates propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group alkyl-dialkoxysilanes, γ-chloropropyl trialkoxy silane, γ-sulfydryl propyl trialkoxy silane, β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane etc.In these, be preferably γ-glycidoxy propyl group alkyl-dialkoxysilanes, β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane.
The content of [H] the closely sealed auxiliary agent in said composition, for [A] polymkeric substance 100 mass parts, is preferably below above 20 mass parts of 0.5 mass parts, more preferably below above 10 mass parts of 1 mass parts.Based on making the content of [H] closely sealed auxiliary agent in above-mentioned particular range, further improve the adaptation of interlayer dielectric and substrate for formed display element.
[[I] alkali compounds]
As [I] alkali compounds, can be in chemically amplified photo resist agent be used choice for use at random.Such as enumerating fatty amine, aromatic amine, hetero ring type amine, quaternary ammonium hydroxide, carboxylic acid quaternary ammonium salt etc.Based on contain [I] alkali compounds in said composition, can moderately control the sour diffusion length producing from [B] compound because of exposure, can make pattern development for good.
As fatty amine, such as enumerating trimethylamine, diethylamine, triethylamine, di-n-propylamine, Tri-n-Propylamine, two n-amylamines, tri-n-amyl amine, diethanolamine, triethanolamine, dicyclohexyl amine, dicyclohexyl methyl amine etc.
As aromatic amine, such as enumerating aniline, benzylamine, DMA, diphenylamine etc.
As hetero ring type amine, for example can enumerate pyridine, 2-picoline, 4-picoline, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl 4-phenyl pyridine, 4-dimethyl amine yl pyridines, 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.
As quaternary ammonium hydroxide, such as enumerating just own ammonium etc. of tetramethylammonium hydroxide, tetraethylammonium hydroxide, the positive fourth ammonium of hydroxide four, hydroxide four.
As carboxylic acid quaternary ammonium salt, such as enumerating tetramethyl ammonium acetate, tetramethylbenzene ammonium formate, tetra-n-butyl ammonium acetate, tetra-n-butyl ammonium benzoate etc.
In these [I] alkali compounds, be preferably hetero ring type amine, 4-dimethyl amine yl pyridines, 1 more preferably, 5-diazabicyclo [4,3,0]-5-nonene.
The content of [I] alkali compounds in said composition, for [A] polymkeric substance 100 mass parts, is preferably 0.001 mass parts～1 mass parts, more preferably 0.005 mass parts～0.2 mass parts.Based on making the content of [I] alkali compounds in above-mentioned particular range, further improve pattern development.
[[J] quinone di-azido compound]
[J] quinone di-azido compound produces the compound of carboxylic acid for the irradiation via ray.As [J] quinone di-azido compound, can use phenoloid or alcohol compound (below also referred to as " parent nucleus ") and 1, the condensation product of 2-naphthoquinones two nitrine sulfonic acid halides.
As above-mentioned parent nucleus, such as enumerating trihydroxy diphenylketone, tetrahydroxy diphenylketone, penta hydroxy group diphenylketone, hexahydroxy diphenylketone, (polyhydroxy phenyl) alkane, other parent nucleus etc.
As trihydroxy diphenylketone, for example, can enumerate 2,3,4-trihydroxy diphenylketone, 2,4,6-trihydroxy diphenylketone etc.
As tetrahydroxy diphenylketone, for example, can enumerate 2,2 ', 4,4 '-tetrahydroxy diphenylketone, 2,3,4,3 '-tetrahydroxy diphenylketone, 2,3,4,4 '-tetrahydroxy diphenylketone, 2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl base ketone, 2,3,4,4 '-tetrahydroxy-3 '-methoxyl diphenylketone etc.
As penta hydroxy group diphenylketone, for example, can enumerate 2,3,4,2 ', 6 '-penta hydroxy group diphenylketone etc.
As hexahydroxy diphenylketone, for example, can enumerate 2,4,6,3 ', 4 ', 5 '-hexahydroxy diphenylketone, 3,4,5,3 ', 4 ', 5 '-hexahydroxy diphenylketone etc.
As (polyhydroxy phenyl) alkane, for example can enumerate two (2, 4-dihydroxy phenyl) methane, two (p-hydroxybenzene) methane, three (p-hydroxybenzene) methane, 1, 1, 1-tri-(p-hydroxybenzene) ethane, two (2, 3, 4-trihydroxy phenyl) methane, 2, 2-two (2, 3, 4-trihydroxy phenyl) propane, 1, 1, 3-tri-(2, 5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane, 4, 4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol, two (2, 5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane, 3, 3, 3 ', 3 '-tetramethyl-1, 1 '-spirobindene-5, 6, 7, 5 ', 6 ', 7 '-hexanol, 2, 2, 4-trimethyl-7, 2 ', 4 '-trihydroxy flavane etc.,
As other parent nucleus, for example can enumerate 2-methyl-2-(2,4-dihydroxy phenyl)-4-(4-hydroxy phenyl)-7-hydroxychroman, 1-[1-(3-{1-(4-hydroxy phenyl)-1-Methylethyl }-4,6-dihydroxy phenyl)-1-Methylethyl] and-3-(1-(3-{1-(4-hydroxy phenyl)-1-Methylethyl }-4,6-dihydroxy phenyl)-1-Methylethyl) benzene, 4, two { 1-(4-the hydroxy phenyl)-1-Methylethyls }-1 of 6-, 3-dihydroxy benzenes etc.
In these parent nucleus, be preferably 2,3,4,4 '-tetrahydroxy diphenylketone, 1,1,1-tri-(p-hydroxybenzene) ethane, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol.
As 1,2-naphthoquinones, two nitrine sulfonic acid halides, be preferably 1,2-naphthoquinones, two nitrine sulfonic acid chlorides.As 1,2-naphthoquinones, two nitrine sulfonic acid chlorides, for example, can enumerate 1,2-naphthoquinones, two nitrine-4-sulfonic acid chloride, 1,2-naphthoquinones two nitrine-5-sulfonic acid chloride etc.In these, be preferably 1,2-naphthoquinones, two nitrine-5-sulfonic acid chloride.
As phenoloid or alcohol compound and 1, the condensation product of 2-naphthoquinones two nitrine sulfonic acid halides, be preferably 1,1,1-tri-(p-hydroxybenzene) ethane and 1, the condensation product, 4 of 2-naphthoquinones two nitrine-5-sulfonic acid chloride, 4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] condensation product of bis-phenol and 1,2-naphthoquinones, two nitrine-5-sulfonic acid chloride.
In phenoloid or parent nucleus and 1, in the condensation reaction of 2-naphthoquinones two nitrine sulfonic acid halides, with respect to the OH radix in phenoloid or alcohol compound, can use be equivalent to be preferably 30～85 % by mole, more preferably 50～70 % by mole 1,2-naphthoquinones two nitrine sulfonic acid halides.Condensation reaction can be implemented based on well-known method.
As [J] quinone di-azido compound, be also applicable to use and the ester bond of above-mentioned illustrative parent nucleus is changed into 1 of amido link, 2-naphthoquinones two nitrine sulfonamidess, for example 2,3,4-tri-amido diphenylketone-1,2-naphthoquinones two nitrine-4-sulfonamide etc.
The modulator approach > of eurymeric radiation sensitive composition for < jetting nozzle formula rubbing method
Said composition is based on mix [A] polymkeric substance, [B] compound, suitable component optionally, other optional member in [C] organic solvent, so that the state modulated of dissolving or disperseing.For example, in [C] organic solvent, based on mixing each composition with the ratio of appointment, can modulate said composition.
The formation method > of interlayer dielectric for < display element
In the present invention, be also applicable to containing by the formed display element interlayer dielectric of said composition.Display element of the present invention has by the formation method of interlayer dielectric:
(1) jetting nozzle and substrate are relatively moved on one side, on one side said composition is coated on substrate, to form the operation of filming,
(2) operation to above-mentioned formed at least a portion useful to irradiation of rays of filming,
(3) by the operation of the painting film development through above-mentioned radiation exposure, and
(4) by the operation of the heating of filming through above-mentioned development.
According to this formation method, use can be at a high speed coating, there is excellent radiation-sensitive degree simultaneously, can form the said composition of interlayer dielectric for the display element of film thickness uniformity excellence, based on utilizing exposure, video picture, the heating of radiation sensitive linear to form pattern, can easily form the display element interlayer dielectric film with fine and exquisite pattern.Moreover thus formed display element interlayer dielectric, has flatness highly, applicable to the display element of liquid crystal display cells, organic EL display element etc. without crawling.
[operation (1)]
In this operation, Yi Bian jetting nozzle and substrate are relatively moved, Yi Bian said composition is coated on substrate based on jetting nozzle rubbing method, and form, film.Preferably pass through coated face prebake conditions to remove [C] organic solvent.
As substrate, such as enumerating glass, quartz, silicone, resin etc.As resin, such as enumerating the ring-opening polymerization polymer of polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, cyclic olefin and hydride thereof etc.The condition of prebake conditions is also different along with the kind of each composition, blending ratio etc., can carry out about 1～10 minute at 70～120 ℃.
[operation (2)]
In this operation, to above-mentioned formed at least a portion useful to irradiation of rays of filming to expose.During exposure, conventionally by thering is the photomask of given pattern, expose.The ray using during as exposure, is preferably wavelength at the ray of the scope of 190nm～450nm, more preferably contains the ultraviolet ray of 365nm.Exposure be based on illuminometer (OAI model 356, OAI Optical Associates Inc. manufacture) measure the intensity of ray under wavelength 365nm and value, be preferably 500J/m 2～6,000J/m 2, more preferably 1,500J/m 2～1,800J/m 2.
[operation (3)]
In this operation, by the painting film development of above-mentioned useful to irradiation of rays.Based on by the painting film development after exposure, remove unwanted part (illuminated portion of ray), form the pattern of appointment.Developer solution as using in developing procedure, is preferably alkaline aqueous solution.As alkali, such as the inorganic base that can enumerate NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia etc.; The quaternary ammonium salt of tetramethylammonium hydroxide, tetraethylammonium hydroxide etc. etc.
In aqueous alkali, also can add water-miscible organic solvent or the surfactant of appropriate methyl alcohol, ethanol etc.From obtaining the viewpoint of suitable developability, the concentration of the alkali in aqueous alkali is preferably below the above 5 quality % of 0.1 quality %.As developing method, such as enumerating, contain liquid method (revolve and cover immersion method), infusion process, shake infusion process, spray process etc.Development time is according to the composition of said composition and difference, but is generally about 10～180 seconds.So after development treatment, after the flowing water then for example carrying out 30～90 seconds is cleaned, for example air-dry based on pressurized air or compressed nitrogen, can form needed pattern.
[operation (4)]
In this operation, heat above-mentioned through filming of developing.Add the heating arrangement of hankering using hot plate, baking oven etc., to the film heating of patterning, to promote the curing reaction of [A] polymkeric substance, can obtain solidfied material.Heating-up temperature is for example 120 ℃～250 ℃ left and right.Heat time is different along with the kind of heating machine, for example, about hot plate upper 5 minute～30 minute, in baking oven about 30 minutes～90 minutes.Can also use interim baking of carrying out more than twice heating process etc. again.So, can on the surface of substrate, form the pattern-like film corresponding to the interlayer dielectric of object.
The thickness of interlayer dielectric for formed display element, is preferably 0.1 μ m～8 μ m, and more preferably 0.1 μ m～6 μ m, is particularly preferably 0.1 μ m～4 μ m.
[embodiment]
Below, the embodiment of take describes the present invention in detail as basis, but the present invention should not limit according to the record of this embodiment.
<[A] the synthetic > of polymkeric substance
[synthesis example 1]
In possessing the flask of condenser pipe and stirrer, add 7 mass parts as the ADVN of polymerization initiator and 200 mass parts the diethylene glycol ethyl-methyl ether as solvent.Then, add 40 mass parts to give the methacrylic acid 1-ethoxy ethyl ester of structural unit (I), glytidyl methacrylate that 40 mass parts contain the structural unit of epoxy radicals, methacrylic acid, the styrene of 5 mass parts and the HEMA of 10 mass parts that 5 mass parts give other structural unit, the 3 mass parts α-methylstyrenedimer as molecular weight adjusting agent, after nitrogen displacement, start lentamente to stir.Make the temperature of solution rise to 70 ℃, in this temperature maintenance 5 hours, obtain the polymer solution that contains polymkeric substance (A-1).The Mw of polymkeric substance (A-1) is 9,000.The solid component concentration of polymer solution is 32.1 quality %.
[synthesis example 2]
In possessing the flask of condenser pipe and stirrer, add 7 mass parts as the ADVN of polymerization initiator and 200 mass parts the diethylene glycol ethyl-methyl ether as solvent.Then, add 40 mass parts to give the styrene of the methacrylic acid 2-tetrahydropyrans ester of structural unit (I), glytidyl methacrylate that 40 mass parts contain the structural unit of epoxy radicals, methacrylic acid that 5 mass parts give other structural unit, 5 mass parts and 10 mass parts HEMAs, the 3 mass parts α-methylstyrenedimer as molecular weight adjusting agent, after nitrogen displacement, start lentamente to stir.Make the temperature of solution rise to 70 ℃, in this temperature maintenance 5 hours, obtain the polymer solution that contains polymkeric substance (A-2).The Mw of polymkeric substance (A-2) is 9,000.The solid component concentration of polymer solution is 31.3 quality %.
[synthesis example 3]
In possessing the flask of condenser pipe and stirrer, add 8 mass parts as 2 of polymerization initiator, 2 '-azo two (2 Methylpropionic acid methyl esters) and 300 mass parts are as the methyl isobutyl ketone of solvent.Then, the methacrylic acid 2-tetrahydropyrans ester, 3-(methacryloxy the methyl)-3-Ethyloxetane of 40 mass parts, 5 mass parts that add 40 mass parts to give structural unit (I) give the methacrylic acid of other structural unit and the HEMA of 15 mass parts, after nitrogen displacement, start lentamente to stir.Make the temperature of solution rise to 80 ℃, in this temperature maintenance 6 hours, obtain polymer solution.Secondly, the polymer solution of gained is injected in superfluous heptane, makes polymkeric substance Shen Dian again.Based on decant, remove the heptane of supernatant.Then, filter, make the polymkeric substance vacuum drying 24 hours of gained, obtain polymkeric substance (A-3).The Mw of polymkeric substance (A-3) is 8,000.The solid component concentration of polymer solution is 29.8 quality %.
[synthesis example 4]
In possessing the flask of condenser pipe and stirrer, add 7 mass parts as the ADVN of polymerization initiator and 200 mass parts the diethylene glycol ethyl-methyl ether as solvent.Then, add 35 mass parts to give the methacrylic acid 1-n-butoxy ethyl ester of structural unit (I), the methacrylic acid glycidyl that 30 mass parts contain the structural unit of epoxy radicals, the benzyl methacrylate that 35 mass parts give other structural unit, after nitrogen displacement, start lentamente to stir.Make the temperature of solution rise to 80 ℃, in this temperature maintenance 6 hours, obtain the polymer solution that contains polymkeric substance (A-4).The Mw of polymkeric substance (A-4) is 10,000.The solid component concentration of polymer solution is 32.3 quality %.
[synthesis example 5]
In possessing the flask of condenser pipe and stirrer, add 7 mass parts as 2 of polymerization initiator, 2 '-azo two (2 Methylpropionic acid methyl esters) and 200 mass parts are as the propylene glycol monomethyl ether of solvent.Then, the methacrylic acid 1-n-butoxy ethyl ester, 10 mass parts that add 67 mass parts to give structural unit (I) give the methacrylic acid of other structural unit and the benzyl methacrylate of 23 mass parts, after nitrogen displacement, start lentamente to stir.Make the temperature of solution rise to 80 ℃, in this temperature maintenance 6 hours, obtain the polymer solution that contains polymkeric substance (a-1).The Mw of polymkeric substance (a-1) is 9,000.The solid component concentration of polymer solution is 30.3 quality %.
[synthesis example 6]
In possessing the flask of condenser pipe and stirrer, add 7 mass parts as 2 of polymerization initiator, 2 '-azo two (2 Methylpropionic acid methyl esters) and 200 mass parts are as the propylene glycol monomethyl ether of solvent.Then, the methacrylic acid 1-benzyloxy ethyl ester, 6 mass parts that add 90 mass parts to give structural unit (I) give the HEMA of other structural unit and the methacrylic acid of 4 mass parts, after nitrogen displacement, start lentamente to stir.Make the temperature of solution rise to 80 ℃, in this temperature maintenance 6 hours, obtain the polymer solution that contains polymkeric substance (a-2).Polymkeric substance (a-2) Mw is 9,000.The solid component concentration of polymer solution is 31.2 quality %.
[synthesis example 7]
In possessing the flask of condenser pipe and stirrer, add 7 mass parts as 2 of polymerization initiator, 2 '-azo two (2 Methylpropionic acid methyl esters) and 200 mass parts are as the propylene glycol monomethyl ether of solvent.Then, add 85 mass parts to give the methacrylic acid 2-tetrahydropyrans ester of structural unit (I), HEMA that 7 mass parts give other structural unit and the methacrylic acid of 8 mass parts, after nitrogen displacement, start lentamente to stir.Make the temperature of solution rise to 80 ℃, in this temperature maintenance 6 hours, obtain the polymer solution that contains polymkeric substance (a-3).The Mw of polymkeric substance (a-3) is 10,000.The solid component concentration of polymer solution is 29.2 quality %.
[synthesis example 8]
In possessing the flask of condenser pipe and stirrer, add 7 mass parts as the ADVN of polymerization initiator and 200 mass parts the diethylene glycol ethyl-methyl ether as solvent.Then, add 52 mass parts to contain the glytidyl methacrylate of the structural unit of epoxy radicals, the benzyl methacrylate that 48 mass parts give other structural unit, after nitrogen displacement, start lentamente to stir.Make the temperature of solution rise to 80 ℃, in this temperature maintenance 6 hours, obtain the polymer solution that contains polymkeric substance (a-4).The Mw of polymkeric substance (a-4) is 10,000.The solid component concentration of polymer solution is 32.3 quality %.
[synthesis example 9]
In possessing the flask of condenser pipe and stirrer, add 7 mass parts as the ADVN of polymerization initiator and 200 mass parts the diethylene glycol ethyl-methyl ether as solvent.Then, add 45 mass parts to contain the methacrylic acid 3 of the structural unit of epoxy radicals, 4-epoxy radicals cyclohexyl methyl esters, 45 mass parts give the benzyl methacrylate of other structural unit and the methacrylic acid of 10 mass parts, after nitrogen displacement, start lentamente to stir.Make the temperature of solution rise to 80 ℃, in this temperature maintenance 6 hours, obtain the polymer solution that contains polymkeric substance (a-5).The Mw of polymkeric substance (a-5) is 10,000.The solid component concentration of polymer solution is 33.2 quality %.
The modulation > of eurymeric radiation sensitive composition for < jetting nozzle formula rubbing method
Composition used while below, in detail the modulation of radiation sensitive composition of embodiment and comparative example being described in detail.
<[B] compound >
B-1～B-5 is oxime sulfonates compound.B-6 and B-7 are salt (B-6 is thiophane salt, and B-7 is sulfonium salt).
B-1: (the sub-thiophene-2-yl of 5-sulfonyl propyl oxygen base imido grpup-5H-)-(2-aminomethyl phenyl) acetonitrile (CIBA speciality chemical system, IRGACURE PAG 103) shown in above-claimed cpd (i)
B-2: (the sub-thiophene-2-yl of 5-octyl group sulfonyloxy imido grpup-5H-)-(2-aminomethyl phenyl) acetonitrile (CIBA speciality chemical system, IRGACURE PAG 108) shown in above-claimed cpd (ii)
B-3: (the sub-thiophene-2-yl of 5-tolysulfonyl oxygen base imido grpup-5H-)-(2-aminomethyl phenyl) acetonitrile (CIBA speciality chemical system, IRGACURE PAG 121) shown in above-claimed cpd (iv)
B-4: (the sub-thiophene-2-yl of camphor sulfonyloxy imido grpup-5H-)-(2-aminomethyl phenyl) acetonitrile (CIBA speciality chemical system, CGI 1380) shown in above-claimed cpd (iii)
B-5: (5-octyl group sulfonyloxy imido grpup)-(4-methoxyphenyl) acetonitrile (CIBA speciality chemical system, CGI 725) shown in above-claimed cpd (v)
B-6:4,7-bis--n-butoxy-1-naphthyl thiophane trifluoro-methanyl sulfonate
B-7: benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate
<[C] organic solvent >
(C1) organic solvent (being more than 0.1mmHg and lower than 1mmHg the vapor pressures of 20 ℃)
C-1-1: diethylene glycol ethyl-methyl ether (20 ℃, 0.75mmHg)
C-1-2: dipropylene glycol dimethyl ether (20 ℃, 0.38mmHg)
(C2) organic solvent (being below the above 20mmHg of 1mmHg the vapor pressures of 20 ℃)
C-2-1: diethylene glycol dimethyl ether (20 ℃, 1.3mmHg)
C-2-2: propylene glycol monomethyl ether (20 ℃, 3.75mmHg)
C-2-3: cyclohexanone (20 ℃, 3.4mmHg)
The solvent using in comparative example
Isosorbide-5-Nitrae-dioxs (20 ℃, 29mmHg)
Ethylene glycol (20 ℃, 0.08mmHg)
<[D] surfactant >
D-1: polysiloxane-based surfactant (eastern beautiful DOW CORNING シ リ コ mono-Application system, SH 8400 FLUID)
D-2: fluorine class surfactant (NEOS system, Ftergent FTX-218)
<[E] multifunctional (methyl) acrylate compounds >
E-1: ethylene glycol dimethacrylate
E-2: trimethylol-propane trimethacrylate
E-3: new penta tetrol tetraacrylate
<[F] antioxidant >
F-1:2,6-bis--tert-butyl group-4-cresols
F-2:4-metoxyphenol
<[G] epoxy compound >
G-1:2 bisphenol-A diepoxy propyl ether (4,4 '-isopropylidene biphenol and 1-are chloro-2, the bunching compound of 3-epoxy radicals propane)
G-2:3,4-epoxy radicals cyclohexyl methyl-3 ', 4 '-epoxy-cyclohexane carboxylate
<[H] closely sealed auxiliary agent >
H-1: γ-glycidoxypropyltrime,hoxysilane
H-2: β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane
H-3: γ-methacryloxypropyl trimethoxy silane
<[I] alkali compounds >
I-1:4-dimethyl amine yl pyridines
I-2:1,5-diazabicyclo [4,3,0]-5-nonene
[embodiment 1]
In the solution that contains polymkeric substance (A-1) (amount that is equivalent to polymkeric substance (A-1) 100 mass parts (solid constituent)), add 3 mass parts as (B-1) of [B] compound, add (C-1-1) of conduct (C1) organic solvent to reach desirable solid component concentration, mix 0.2 mass parts as (D-1) of [D] surfactant, with the membrane filter of aperture 0.2 μ m, filter, to modulate eurymeric radiation sensitive composition for jetting nozzle formula rubbing method.
[embodiment 2～16 and comparative example 1～4]
Except the kind of each composition and combined amount are as recording in table 1, operate similarly to Example 1 and modulate each composition.Moreover the numerical value of [C] organic solvent in table 1 is (C1) organic solvent and (C2) the quality % ratio of organic solvent.Again, the meaning of "-" in table 1 is not used this composition.
< evaluates >
Use each composition of modulating, implement following evaluation.In table 1, merge and show result.
[viscosity (mPas)]
Use E type viscosity meter (eastern machine industry system, VISCONIC ELD.R), be determined at the viscosity (mPas) of the said composition of 25 ℃.
[solid component concentration (quality %)]
Smart each composition of scale 0.3g in aluminum dish, adds after about 1g diethylene glycol dimethyl ether, with 175 ℃, on hot plate, is dried 60 minutes, and the quality before and after dry is tried to achieve the solid component concentration (quality %) in each composition.
[outward appearance of filming]
On the chromium film forming glass of 550 * 650mm, (chemical industry system is answered in Tokyo, each composition that TR632105-CL) coating is modulated to use slit mould coating machine, drying under reduced pressure, to till 0.5Torr, then, forms and films with 100 ℃ of prebake conditions 2 minutes on hot plate, again with 2,000J/m 2exposure expose, thus, above chromium film forming glass, form the film that thickness is 4 μ m.Under sodium vapor lamp, this outward appearance of filming with visual inspection.Now, investigation is filmed in all muscle shape uneven (coating direction or with its direction of intersecting in formed one or more straight line uneven), the appearance situation of vaporific inequality (cloud form is uneven), pin trace uneven (formed point-like is uneven on substrate anchor).Using the situation of almost not seeing above-mentioned any inequality as " A " (being judged as good), using the situation of seeing a little any one as " B " (being judged as defective a little), situation about will clear see is as good " C " (being judged as defective).
[film thickness uniformity (%)]
Use determining film thickness device (large Japanese SCREEN system, Lambda Ace), measure as the thickness of filming on the chromium film forming glass of above-mentioned made.Film thickness uniformity, for measuring the thickness of 9 measuring points, is calculated by following formula.9 measuring points are using the short-axis direction of substrate as X, using long axis direction as Y, now (X[mm], Y[mm]) be (275,20), (275,30), (275,60), (275,100), (275,325), (275,550), (275,590), (275,620), (275,630).By film thickness uniformity, for the situation judgement surpassing below 1.80% and 2% is good a little, by film thickness uniformity, be that situation below 1.80% is judged as well.
Film thickness uniformity (%)={ FT (X, Y) max-FT (X, Y) min} * 100/{2 * FT (X, Y) avg.}
In above-mentioned formula, FT (X, Y) max is the maximal value in the thickness of 9 measuring points, and FT (X, Y) min is the minimum value in the thickness of 9 measuring points, and FT (X, Y) avg. is the mean value in the thickness of 9 measuring points.
[high-speed coating (mm/sec.)]
On the alkali-free glass substrate of 550 * 650mm, use slit mould coating machine, coating condition is: the distance of substrate and nozzle is that the thickness after 150 μ m, exposure is 2.5 μ m, thus from nozzle ejection coating fluid, the translational speed of nozzle is changed in the scope of 120mm/sec.～220mm/sec., try to achieve the maximal rate that the muscle shape inequality due to disconnected liquid does not occur.Now, good even if the situation that muscle shape inequality do not occurred the speed more than 180mm/sec. to is yet judged as high-speed coating.
[radiation-sensitive degree (J/m 2)]
On the chromium film forming glass of 550 * 650mm, be coated with hexamethyldisilazane, 60 ℃ of heating 1 minute.(chemical industry system is answered in Tokyo to use slit mould coating machine, TR632105-CL), on chromium film forming glass after this hexamethyldisilazane is processed, be coated with each composition, to arrive pressure setting at 100Pa, after vacuum goes down to desolventize, carry out 2 minutes prebake conditions in 90 ℃ again, form thus filming of thickness 3.0 μ m.Then, use exposure machine (CANON system, MPA-600FA), line sky by having 60 μ m is than the photomask of the pattern of (10 to 1), for filming, take exposure as variable, after useful to irradiation of rays, in the tetramethylammonium hydroxide aqueous solution of the concentration shown in table 1, at 25 ℃, based on containing liquid method, develop.When the concentration of using tetramethylammonium hydroxide is the developer solution of 0.40 quality %, development time is 80 seconds, while using the developer solution of 2.38 quality %, is 50 seconds.Then, with ultrapure water, carry out 1 minute flowing water and clean, then, based on dry, on the chromium film forming glass substrate after HMDS processes, form pattern.Now, investigation is dissolved necessary exposure completely by the gap pattern of 6 μ m.This value is 500J/m 2when following, judgement susceptibility is good.
[transmittance (%)]
Use spin coater, after each modulated composition is coated on glass substrate, 90 ℃ of prebake conditions 2 minutes and form filming of thickness 3.0 μ m on hot plate.For filming with exposure 700J/m 2after exposing, in clean baking oven, with 220 ℃ of heating 1 hour, obtain cured film.Secondly, use spectrophotometer (Hitachi's system, 150-20 type Double Beam) to be determined at the transmittance of wavelength 400nm.Using measured value (%) as transmittance, it is better that value more approaches 100% transmittance, the situation lower than 90% is judged as to the transparency defective.
[the heat-resisting transparency (%)]
The substrate of measuring in evaluation for above-mentioned transmittance, further in clean baking oven in 250 ℃ of heating 1 hour, similarly measure after the light transmittance before and after heating with the evaluation of above-mentioned transmittance, based on following formula, calculate the heat-resisting transparency (%).It is better that this value more approaches 0% heat-resisting transparency, and it is defective that the situation over 4% is judged as the heat-resisting transparency.
Transmittance after transmittance-heating before the heat-resisting transparency (%)=heating
By the result of table 1, can know and use the embodiment 1～16 of said composition to compare with the composition of comparative example 1～4, can form and there is filming of high ray susceptibility and excellent film thickness uniformity, and can high-speed coating, the outward appearance of filming is also good.
Moreover, combination have (C1) organic solvent with (C2) organic solvent as the embodiment 3～16 of [C] organic solvent, compare with only using the embodiment 1 and 2 of (C1) organic solvent, known film thickness uniformity is further excellent.Again, with respect to (C1) organic solvent and (C2) total amount of organic solvent to make the content of (C2) organic solvent be the embodiment 3～11 below 50 quality %, with with respect to (C1) organic solvent and (C2) total amount of organic solvent to make the content of (C2) organic solvent be that the embodiment 12 of 70 quality % compares, known outward appearance, film thickness uniformity filming is excellent especially.
On the other hand, the embodiment 13～16 of [E] multifunctional (methyl) acrylate compounds, [F] antioxidant and [G] epoxy compound of the suitable component that contains said composition, compare with the embodiment 1～12 that does not contain these compositions, known further excellent at transmittance and the heat-resisting transparency.
[utilizability in industry]
Jetting nozzle formula rubbing method of the present invention is to have high radiation-sensitive degree with eurymeric radiation sensitive composition, and can form the display element interlayer dielectric with height flatness (film thickness uniformity) without crawling, further and can high-speed coating.Therefore, said composition is to be suitable as the material that display elements such as forming liquid crystal display cells, organic EL display element is used with interlayer dielectric.

Claims (9)

1. an eurymeric radiation sensitive composition for jetting nozzle formula rubbing method, it contains:
[A] in same or different polymer molecules, have polymkeric substance containing the structural unit (I) of the group shown in following formula (1) and structural unit containing epoxy radicals,
At least one compound of selecting in the group that [B] is comprised of oxime sulfonates compound and salt compound,
[C] organic solvent and
[E] multifunctional (methyl) acrylate compounds
Wherein, the solid component concentration of said composition is below the above 30 quality % of 10 quality %, the viscosity of 25 ℃, is below the above 12mPas of 2.0mPas, and,
As [C] organic solvent, at least containing (C1) is more than 0.1mmHg and lower than the organic solvent of 1mmHg the vapor pressure of 20 ℃, wherein (C1) organic solvent is at least one organic solvent of selecting the group who forms from diethylene glycol ethyl-methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, phenmethylol, DPGME
In formula (1), R 1and R 2be hydrogen atom, alkyl, naphthenic base or aryl independently of one another; Wherein, part or all hydrogen atom that abovementioned alkyl, naphthenic base or aryl have can be substituted; There is not R again, 1and R 2it is the situation of hydrogen atom simultaneously; R 3for alkyl, naphthenic base, aralkyl, aryl or-M (R 3m) 3shown group, part or all hydrogen atom that wherein these groups have can be substituted; M is Si, Ge or Sn; R 3mfor alkyl; Wherein, R 1with R 3can connect, can form cyclic ether with together with the carbon atom of institute's bond.
2. eurymeric radiation sensitive composition for jetting nozzle formula rubbing method as claimed in claim 1, wherein further to contain (C2) be the organic solvent below the above 20mmHg of 1mmHg the vapor pressure of 20 ℃ to [C] organic solvent,
With respect to (C1) organic solvent and (C2) total amount of organic solvent, (C2) content of organic solvent is below the above 90 quality % of 10 quality %.
3. eurymeric radiation sensitive composition for jetting nozzle formula rubbing method as claimed in claim 1, wherein further to contain (C2) be the organic solvent below the above 20mmHg of 1mmHg the vapor pressure of 20 ℃ to [C] organic solvent,
With respect to (C1) organic solvent and (C2) total amount of organic solvent, (C2) content of organic solvent is below the above 50 quality % of 10 quality %.
4. eurymeric radiation sensitive composition for jetting nozzle formula rubbing method as claimed in claim 1, it further contains at least one surfactant of selecting in the group that [D] be comprised of fluorine class surfactant and polysiloxane-based surfactant,
With respect to [A] polymkeric substance 100 mass parts, the content of [D] surfactant is below above 2 mass parts of 0.01 mass parts.
5. eurymeric radiation sensitive composition for jetting nozzle formula rubbing method as claimed in claim 1, it further contains [F] antioxidant.
6. eurymeric radiation sensitive composition for jetting nozzle formula rubbing method as claimed in claim 1, it further contains [G] and in 1 molecule, has the compound of more than 2 epoxy radicals.
7. eurymeric radiation sensitive composition for jetting nozzle formula rubbing method as claimed in claim 2, wherein (C2) organic solvent at least one organic solvent for selecting in the group who is formed by diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol list propyl ether acetic acid esters, propylene glycol monomethyl ether, cyclohexanone, n-butyl acetate, methyl isobutyl ketone, 3-methoxy methyl propionate.
8. a display element interlayer dielectric, it is formed with eurymeric radiation sensitive composition by jetting nozzle formula rubbing method claimed in claim 1.
9. the formation method of interlayer dielectric for display element, it has:
(1) jetting nozzle and substrate are relatively moved on one side, on one side jetting nozzle formula rubbing method claimed in claim 1 is coated on substrate with eurymeric radiation sensitive composition, form the operation of filming,
(2) operation to above-mentioned formed at least a portion useful to irradiation of rays of filming,
(3) by the operation of the painting film development after above-mentioned radiation exposure, and
(4) by the operation of the heating of filming after above-mentioned development.
CN201180021053.6A 2010-04-28 2011-03-22 Positive Radiation-sensitive Composition For Discharge Nozzle Coating Method, Interlayer Insulating Film For Display Element, And Formation Method For Same Active CN102870045B (en)

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