CN102213918B - Positive type radiation-sensitive composition, inter-layer insulating film and forming method therefor - Google Patents

Positive type radiation-sensitive composition, inter-layer insulating film and forming method therefor Download PDF

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CN102213918B
CN102213918B CN201110081626.6A CN201110081626A CN102213918B CN 102213918 B CN102213918 B CN 102213918B CN 201110081626 A CN201110081626 A CN 201110081626A CN 102213918 B CN102213918 B CN 102213918B
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acid
ester
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alkyl
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CN102213918A (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
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

The invention relates to a positive-type radiation-sensitive composition, an inter-layer insulating film and a forming method therefore. The invention provides a positive-type radiation-sensitive composition for forming inter-layer insulating films. The inter-layer insulating film is excellent in heat resistance and transparency and high in coating evenness and smoothness. The composition can be coated at a high speed and is high in radiation sensitivity. The positive-type radiation-sensitive composition contains [A] identical or different polymer molecules containing group structural units represented as formula (1) and polymer containing the structural unit of epoxy groups; [B] photo-acid generating agent; [C] polymer having structural units containing fluorine and structural units containing silicon.

Description

Positive radiation line sensitive compositions, interlayer dielectric and forming method thereof
Technical field
The present invention relates to the method that forms of positive radiation line sensitive compositions, the interlayer dielectric being formed by said composition and this interlayer dielectric, this positive radiation line sensitive compositions is suitable as the material of the interlayer dielectric of display elements such as forming liquid crystal display cells (LCD), organic EL display element (OLED).
Background technology
The object insulating between the general wiring based on making layeredly to configure in display element and interlayer dielectric is set.Formation material as interlayer dielectric is widely used positive radiation line sensitive compositions, and this is few because obtain the process number of necessary pattern form, and to have enough planarizations be preferred.The positive radiation line sensitive compositions using while forming this interlayer dielectric requires good radioactive ray sensitivity and storage stability, and the interlayer dielectric obtaining requires excellent thermotolerance and the transparency etc.
Composition as above-mentioned positive radiation line sensitive compositions extensively adopts acrylic resin; a kind of eurymeric chemically amplified photo resist agent composition has for example been proposed in TOHKEMY 2004-4669 communique; it is characterized in that: there is crosslinking chemical, acid producing agent and a kind of resin; this resin itself is insoluble or is insoluble in aqueous alkali; can be due to the blocking group of sour effect cracking but have; after this blocking group fracture, can be dissolved in aqueous alkali.But the dielectric film adaptation being obtained by said composition is not enough, cannot meet the requirement of manufacturing high-quality liquid crystal display cells.In addition, in TOHKEMY 2004-264623 communique, proposed a kind of radiation sensitive resin composition, it is characterized in that: contain resin and acid producing agent, this resin has contained acetal and/or ketal structure and epoxy radicals, but the radioactive ray sensitivity of said composition is low, cannot meet the demands.
In addition, universal along with large frame TV in recent years, the size of the glass substrate using when it is manufactured also maximizes.Therefore, at interlayer dielectric, form the spin-coating method adopting in operation at present, be difficult to be coated with radiation-ray sensitive composition on large substrate.Therefore, can adopt the nozzle ejection radiation-ray sensitive composition from slit-shaped, the slit coating method being coated with at glass substrate to replace this spin-coating method.
In slot coated method, by vacuum suction, make substrate closely sealed to after on coating cloth deck specifically, coating nozzle is inswept on certain orientation, on substrate, form and film, after formation is filmed, by making to be accommodated in vacuum suction, by the support pin in hole, rise, substrate is picked up from coating cloth deck, the operation after being transported to.This slit coating method is compared with spin-coating method, can reduce the amount of the needed radiation-ray sensitive composition of coating, simultaneously can ejection radiation-ray sensitive composition limit, limit inswept on certain orientation, be coated with, so can also shorten the coating time, contribute to cut down the manufacturing cost of display element.
Yet, in this series of operation, likely in when coating, produce coating irregular, or on filming, produce the irregular of fine concavo-convex formation that the hole due to vacuum suction causes, due to above reason, become the obstacle of realizing as the desired height planarization of character of interlayer dielectric.
In this case, a kind of positive radiation line sensitive compositions is developed in strong hope, said composition can form as the thermotolerance of interlayer dielectric General Requirements and the transparency excellent, and there is the cured film that is not coated with irregular height planarization (film thickness uniformity), and said composition can high-speed coating, there is high radioactive ray sensitivity.
[prior art document]
[patent documentation]
[patent documentation 1] TOHKEMY 2004-4669 communique
[patent documentation 2] TOHKEMY 2004-264623 communique
Summary of the invention
The present invention proposes based on the problems referred to above, its object is to provide a kind of positive radiation line sensitive compositions, and the method that forms that the interlayer dielectric that formed by said composition and this interlayer dielectric are provided, said composition can form has excellent thermotolerance and the transparency, and there is the interlayer dielectric that is not coated with irregular height planarization (film thickness uniformity), and said composition can high-speed coating, there is very high radioactive ray sensitivity.
The present invention who proposes in order to address the above problem is a kind of positive radiation line sensitive compositions, and it contains:
[A] has the structural unit that comprises the group shown in following formula (1) and the polymkeric substance that contains the structural unit of epoxy radicals in same or different polymer molecules,
[B] light acid producing agent, and
[C] comprises the structural unit with fluorine and the multipolymer with the structural unit of silicon.
And then be a kind of positive radiation line sensitive compositions, [C] multipolymer that it comprises is the multipolymer at least having from the structural unit of following compound:
(c1) polymerizable compound shown in following formula (2),
(c2) polymerizable compound shown in following formula (3), and
(c3) there is the polymerizable compound of the group shown in following formula (4).
(in formula (1), R 1and R 2be hydrogen atom, alkyl, naphthenic base or aryl independently of one another, part or all of the hydrogen atom of these alkyl, naphthenic base or aryl can be substituted group replacement and (wherein, not comprise R 1and R 2not the situation of hydrogen atom).R 3be alkyl, naphthenic base, aralkyl, aryl or-M (R 3m) 3(M is Si, Ge or Sn to shown group, R 3malkyl), part or all of these hydrogen atom can be substituted group and replace.R 1and R 3can be connected to form cyclic ether.)
CH 2＝CR 4COO-C αH 2α-C βF 2β+1 (2)
(in formula (2), R 4hydrogen atom or methyl.α is 0～6 integer.β is 1～20 integer.)
CH 2＝CR 5COO-(C γH 2γ-O) a-R 6 (3)
(in formula (3), R 5hydrogen atom or methyl.R 6that carbon number is 1～12 alkyl.γ is 2 or 3.A is structural unit number, and its quantity mean value is 1～30.)
(in formula (4), R 7, R 8, R 9, R 10and R 11be the group shown in alkyl, phenyl or the following formula (5) of carbon number 1～20 independently of one another, b is 0～3 integer.)
(in formula (5), R 12, R 13and R 14be the alkyl or phenyl of carbon number 1～20 independently of one another, c is 0～3 integer.)
This positive radiation line sensitive compositions is due to except having [A] polymkeric substance and [B] light acid producing agent of above-mentioned ad hoc structure, [C] multipolymer also forming due to the polymerizable compound by having ad hoc structure plays as the function that reduces the surfactant that capillary performance is high, can form the harmonious character that meets well thermotolerance and the such General Requirements of the transparency, there is the interlayer dielectric without the irregular height planarization (film thickness uniformity) of coating.In addition, this positive radiation line sensitive compositions can high-speed coating, and has excellent radioactive ray sensitivity.
In this positive radiation line sensitive compositions, [C] multipolymer preferably further comprises from (c4) and has the structural unit that carbon number is the polymerizable compound of 1～8 non-substituted alkyl ester group.Thus, can improve the compatibility of [C] multipolymer to other composition or solvent, further improve the film thickness uniformity of the interlayer dielectric obtaining.
In this positive radiation line sensitive compositions, [C] multipolymer preferably further comprises the structural unit in a part from (c5) with more than two polymerizable compound of unsaturated link.Thus, film thickness uniformity and the intensity of the interlayer dielectric obtaining can be improved, the general character such as thermotolerance can also be improved.
In this positive radiation line sensitive resin composition, preferred compound (c1) is the polymerizable compound shown in following formula (6), and compound (c2) is the polymerizable compound shown in following formula (7),
[C] multipolymer preferably, by the total amount with respect to polymerizable compound (c1)～(c5), contains
The polymerizable compound of 25～35 quality % (c1),
The polymerizable compound of 20～30 quality % (c2),
The polymerizable compound of 15～20 quality % (c3),
The polymerizable compound of 25～35 quality % (c4), and
The composition of the polymerizable compound of 1～5 quality % (c5) forms.
CH 2＝CR 4COOC 2H 4C βF 2β+1 (6)
(in formula (6), R 4identical with the definition in above-mentioned formula (2).β is 1～8 integer.)
CH 2＝CR 5COO(C 2H 4O) aR 6 (7)
(in formula (7), R 5and R 6identical with the definition in above-mentioned formula (3) respectively, the quantity mean value that structural unit is counted a is 4～12.)
[C] multipolymer by this ad hoc structure plays the function that reduces the surfactant that performance is high as surface tension, even when its usage ratio is few, also the surface smoothness of filming can be improved, thereby the film thickness uniformity of the interlayer dielectric of formation can be further improved.
This positive radiation line sensitive compositions preferably further contains [D] closely sealed auxiliary agent.By using this closely sealed auxiliary agent, can further improve the cured film that the obtains adaptation to substrate.
This positive radiation line sensitive compositions preferably further contains [E] alkali compounds.Thus, can suitably control the sour diffusion being produced by light acid producing agent, improve the pattern development of positive radiation line sensitive compositions.
In addition, display element of the present invention comprises by the formation method of interlayer dielectric:
(1) on substrate, form the operation of filming of this positive radiation line sensitive compositions,
(2) at least a portion of filming forming in operation (1) is irradiated to the operation of radioactive ray,
(3) will in operation (2), irradiate the operation of the painting film development of radioactive ray, and
(4) operation to the heating of filming of developing in operation (3).
In the method, can high-speed coating, and use has the above-mentioned positive radiation line sensitive compositions of excellent radioactive ray sensitivity, by utilize radiation-sensitive exposure, develop, add thermosetting pattern, thereby can easily form the display element interlayer dielectric with fine and exquisite pattern.In addition, the interlayer dielectric forming like this has the character of General Requirements, and namely thermotolerance and the transparency are balancedly excellent, has without the irregular height planarization of coating simultaneously.
In this manual, " polymkeric substance " of [A] composition is in a polymer molecule, to have structural unit (1), but also is included in the implication having in the polymer molecule different with this polymer molecule containing the situation of the structural unit of epoxy radicals.
As above described in explanation, positive radiation line sensitive compositions of the present invention above-mentioned by containing [A], [B] and [C] composition, can form the character that can harmonious meet well thermotolerance and the such General Requirements of the transparency, there is the interlayer dielectric without the irregular height planarization of coating simultaneously.In addition, this positive radiation line sensitive compositions can high-speed coating, and shows excellent radioactive ray sensitivity.
Embodiment
Positive radiation line sensitive compositions of the present invention contains: in same or different polymer molecules, comprise that to have the structural unit of the group shown in following formula (1) (following, also referred to as " structural unit (1) ") and (following containing the polymkeric substance of the structural unit of epoxy radicals, also referred to as " polymkeric substance (A) "), the multipolymer that formed by the polymerizable compound with ad hoc structure of [B] light acid producing agent and [C] is (following, also referred to as " multipolymer [C] "), in addition, can also contain other optional member.
< polymkeric substance [A] >
Polymkeric substance [A] is the structural unit that has structural unit (1) and contain epoxy radicals in same or different polymer molecules, also can have other structural unit as required.To thering is structural unit (1) and there is no particular limitation containing the form of the polymkeric substance [A] of the structural unit of epoxy radicals, can list: (i) in same polymer molecule, have structural unit (1) and containing the structural unit of epoxy radicals the two, in polymkeric substance [A], there is a kind of situation of polymer molecule; (ii) in a polymer molecule, there is structural unit (1), in the polymer molecule different with it, there is the structural unit containing epoxy radicals, in polymkeric substance [A], have the situation of two kinds of polymer molecules; (iii) in a polymer molecule, have structural unit (1) and containing the structural unit of epoxy radicals the two, in the polymer molecule different with it, there is structural unit (1), all thering is the structural unit containing epoxy radicals in different polymer molecule with them, in polymkeric substance [A], there is the situation of three kinds of polymer molecules; (iv), except the polymer molecule of (i)～(iii) regulation, in polymkeric substance [A], further comprise the situation of other one or more polymer molecule etc.Any situation, can enjoy effect of the present invention.Below, to structural unit (1), describe successively containing structural unit and other structural unit of epoxy radicals.
< structural unit (1) >
In structural unit (1), group shown in above-mentioned formula (1) is (following with the group of decomposition polarization group in the presence of acid, also referred to as " sour decomposability group ") form exist, so acid being produced by light acid producing agent by irradiating radioactive ray, sour decomposability group is decomposed, thereby make the insoluble polymkeric substance of alkali [A] become alkali-soluble.Above-mentioned sour decomposability group has the more stable ethylidene ether structure of alkali or ketal structure, and they can decompose by sour effect.
In above-mentioned formula (1), as R 1and R 2shown alkyl, is preferably carbon number and is 1～30 straight chain and the alkyl of side chain, in this alkyl chain, can have oxygen atom, sulphur atom, nitrogen-atoms.Object lesson as abovementioned alkyl, can list such as the straight chain-like alkyl such as methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-octyl, dodecyl, n-tetradecane base, n-octadecane base, the branched alkyls such as isopropyl, isobutyl, the tert-butyl group, neopentyl, 2-hexyl, 3-hexyl.
In above-mentioned formula (1), as R 1and R 2shown naphthenic base, is preferably carbon number and is 3～20 naphthenic base, can be many rings, can in ring, have oxygen atom.As the object lesson of above-mentioned naphthenic base, can list such as cyclopropyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, bornyl, norborny, adamantyl etc.
In above-mentioned formula (1), as R 1and R 2shown aryl, the aryl that preferably carbon number is 6～14, can be monocycle, can be also the structure that monocycle connects, and can be also condensed ring.As the object lesson of above-mentioned aryl, can list such as phenyl, naphthyl etc.
Above-mentioned R 1and R 2part or all of hydrogen atom can be substituted group and replace.As this substituted radical, can list for example halogen atom, hydroxyl, nitro, cyano group, carboxyl, carbonyl, naphthenic base (as this naphthenic base, being applicable to using the explanation of above-mentioned naphthenic base), aryl (as this aryl, being applicable to using the explanation of above-mentioned aryl), alkoxy (is preferably carbon number and is 1～20 alkoxy, can list for example methoxyl, ethoxy, propoxyl group, n-butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy etc.), (acyl group that preferably carbon number is 2～20, can list for example acetyl group to acyl group, propiono, bytyry, isobutyryl etc.), (acyloxy that preferably carbon number is 2～10, can list for example acetoxyl group to acyloxy, propionyloxy, butyryl acyloxy, tertiary butyryl acyloxy, uncle's penta acyloxy etc.), (alkoxy carbonyl that preferably carbon number is 2～20, can list for example methoxycarbonyl to alkoxy carbonyl, ethoxy carbonyl, propoxycarbonyl etc.), (part or all group being replaced by halogen atom of the hydrogen atom of abovementioned alkyl or naphthenic base, can list for example perfluoro-methyl to haloalkyl, perfluor ethyl, perfluoro propyl, fluoro cyclopropyl, fluoro cyclobutyl etc.) etc.For ring texturees such as aryl, naphthenic base, can list abovementioned alkyl as further substituted radical.
In above-mentioned formula (1), R 3shown alkyl, naphthenic base and aryl can be used R 1and R 2in explanation.In above-mentioned formula (1), R 3shown aralkyl, preferably lists carbon number and is 7～20 aralkyl, can list such as benzyl, phenethyl, menaphthyl, naphthalene ethyl etc.In above-mentioned formula (1), as R 3-M (R 3m) 3shown group, can list such as TMS, trimethyl germyl etc.As replacing this R 3shown aralkyl or-M (R 3m) 3the substituted radical of part or all of the hydrogen atom of shown group, is applicable to adopting above-mentioned substituted radical.
R 1and R 3can be connected to form cyclic ether.As this cyclic ether, can list such as 2-epoxypropane base, 2-tetrahydrofuran base, 2-THP trtrahydropyranyl, 2-alkyl dioxin etc.Part or all of the hydrogen atom of this cyclic ether can be replaced by above-mentioned substituted radical.
Structural unit (1), by having the functional group that can have ethylidene ether structure or ketal structure on other carbon atom by being attached to, can have this ethylidene ether structure or ketal structure.
As above-mentioned, by being attached to the functional group can on other carbon atom with ethylidene ether structure, can list for example 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-cyclohexyl oxygen base oxethyl, 1-norborny oxygen base oxethyl, 1-bornyl oxygen base oxethyl, 1-phenyl oxygen base oxethyl, 1-(1-naphthyl oxygen base) ethoxy, 1-benzyl oxygen base oxethyl, 1-phenethyl oxygen base oxethyl, (cyclohexyl) (methoxyl) methoxyl, (cyclohexyl) (ethoxy) methoxyl, (cyclohexyl) (positive propoxy) methoxyl, (cyclohexyl) (isopropoxy) methoxyl, (cyclohexyl) (cyclohexyl oxygen base) methoxyl, (cyclohexyl) (phenoxy group) methoxyl, (cyclohexyl) (benzyl oxygen base) methoxyl, (phenyl) (methoxyl) methoxyl, (phenyl) (ethoxy) methoxyl, (phenyl) (positive propoxy) methoxyl, (phenyl) (isopropoxy) methoxyl, (phenyl) (cyclohexyl oxygen base) methoxyl, (phenyl) (phenoxy group) methoxyl, (phenyl) (benzyl oxygen base) methoxyl, (benzyl) (methoxyl) methoxyl, (benzyl) (ethoxy) methoxyl, (benzyl) (positive propoxy) methoxyl, (benzyl) (isopropoxy) methoxyl, (benzyl) (cyclohexyl oxygen base) methoxyl, (benzyl) (phenoxy group) methoxyl, (benzyl) (benzyl oxygen base) methoxyl, 2-tetrahydrofuran base oxygen base, 2-THP trtrahydropyranyl oxygen base, 1-TMS oxygen base oxethyl, 1-trimethyl germyl oxygen base oxethyl etc.
Among them, preferably list 1-ethoxy ethoxy, 1-cyclohexyl oxygen base oxethyl, 2-THP trtrahydropyranyl oxygen base, 1-positive propoxy ethoxy.
As above-mentioned, by being attached on other carbon atom, the functional group with ketal structure can be become, for example 1-methyl isophthalic acid-methoxy ethoxy can be listed, 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-cyclohexyl oxygen base oxethyl, 1-methyl isophthalic acid-norborny oxygen base oxethyl, 1-methyl isophthalic acid-bornyl oxygen base oxethyl, 1-methyl isophthalic acid-phenyl oxygen base oxethyl, 1-methyl isophthalic acid-(1-naphthyl oxygen base) ethoxy, 1-methyl isophthalic acid-benzyl oxygen base oxethyl, 1-methyl isophthalic acid-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-cyclohexyl oxygen base oxethyl, 1-cyclohexyl-1-phenoxy group ethoxy, 1-cyclohexyl-1-benzyl oxygen base oxethyl, 1-phenyl-1-methoxy ethoxy, 1-phenyl-1-ethoxy ethoxy, 1-phenyl-1-positive propoxy ethoxy, 1-phenyl-1-isopropoxy ethoxy, 1-phenyl-1-cyclohexyl oxygen base oxethyl, 1-phenyl-1-phenyl oxygen base oxethyl, 1-phenyl-1-benzyl oxygen base oxethyl, 1-benzyl-1-methoxy ethoxy, 1-benzyl-1-ethoxy ethoxy, 1-benzyl-1-positive propoxy ethoxy, 1-benzyl-1-isopropoxy ethoxy, 1-benzyl-1-cyclohexyl oxygen base oxethyl, 1-benzyl-1-phenyl oxygen base oxethyl, 1-benzyl-1-benzyl oxygen base oxethyl, 2-(2-methyl-tetrahydrofuran base) oxygen base, 2-(2-methyl-THP trtrahydropyranyl) oxygen base, 1-methoxyl-cyclopentyloxy, 1-methoxyl-cyclohexyl oxygen base etc.
Among them, preferably list 1-methyl isophthalic acid-methoxy ethoxy, 1-methyl isophthalic acid-cyclohexyl oxygen base oxethyl.
As the object lesson with the structural unit (1) of above-mentioned acetal or ketal structure, can list the structural unit shown in following formula (1-1) for example～(1-3).
(formula (1-1) and (1-3) in, R ' is hydrogen atom or methyl.R 1, R 2and R 3identical with the explanation of above-mentioned formula (1).)
As what the structural unit (1) shown in above-mentioned formula (1-1)～(1-3) was provided, there is free-radical polymerised monomer (following, also referred to as " containing the monomer of ethylidene ether structure "), for example can list:
(methyl) esters of acrylic acids such as (methyl) acrylic acid 1-alkoxy alkyl, (methyl) acrylic acid 1-(cycloalkyl oxy) Arrcostab, (methyl) acrylic acid 1-(halogenated alkoxy) Arrcostab, (methyl) acrylic acid 1-(aralkyl oxy) Arrcostab, (methyl) acrylic acid THP trtrahydropyranyl ester are containing the monomer of ethylidene ether structure;
2,3-bis-(1-(trialkylsilanyl oxygen base) alkoxy) carbonyl)-5-norbornane, 2,3-bis-(1-(trialkyl germyl oxygen base) alkoxy) carbonyl)-5-norbornane, 2,3-bis-(1-alkoxy alkoxy carbonyl)-5-norbornane, 2,3-bis-(1-(cycloalkyl oxy) alkoxy carbonyl)-5-norbornane, 2,3-bis-(1-(aralkyl oxy) the alkoxy carbonyl)-norborneol alkanes such as 5-norbornane are containing the monomer of ethylidene ether structure
The phenylethylenes such as 1-alkoxy alkoxystyrene, 1-(halogenated alkoxy) alkoxystyrene, 1-(aralkyl oxy) alkoxystyrene, THP trtrahydropyranyl oxygen base styrene are containing the monomer of ethylidene ether structure.
Among them, preferred (methyl) acrylic acid 1-alkoxy alkyl, (methyl) acrylic acid THP trtrahydropyranyl ester, 1-alkoxy alkoxystyrene, THP trtrahydropyranyl oxygen base styrene, more preferably (methyl) acrylic acid 1-alkoxy alkyl.
Object lesson as the monomer containing ethylidene ether structure of said structure unit (1) is provided, for example can list:
Methacrylic acid 1-ethoxyethyl group ester, methacrylic acid 1-methoxy 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-chloro ethoxy) ethyl ester, methacrylic acid 1-(2-ethylhexyl oxygen base) ethyl ester, methacrylic acid 1-positive propoxy ethyl ester, methacrylic acid 1-cyclohexyl oxygen base ethyl ester, methacrylic acid 1-(2-cyclohexyl ethoxy) ethyl ester, methacrylic acid 1-benzyl oxygen base ethyl ester, methacrylic acid 2-THP trtrahydropyranyl ester,
Acrylic acid 1-ethoxyethyl group ester, acrylic acid 1-methoxy 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-chloro ethoxy) ethyl ester, acrylic acid 1-(2-ethylhexyl oxygen base) ethyl ester, acrylic acid 1-positive propoxy ethyl ester, acrylic acid 1-cyclohexyl oxygen base ethyl ester, acrylic acid 1-(2-cyclohexyl ethoxy) ethyl ester, acrylic acid 1-benzyl oxygen base ethyl ester, acrylic acid 2-THP trtrahydropyranyl ester,
2,3-bis-(1-(TMS oxygen base) ethoxy) carbonyl)-5-norbornane, 2,3-bis-(1-(trimethyl germyl oxygen base) ethoxy) carbonyl)-5-norbornane, 2,3-bis-(1-methoxy ethoxy carbonyl)-5-norbornane, 2,3-bis-(1-(cyclohexyl oxygen base) ethoxy carbonyl)-5-norbornane, 2,3-bis-(1-(benzyl oxygen base) ethoxy carbonyl)-5-norbornane
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-chloro ethoxy) ethoxybenzene ethene, to or m-1-(2-ethylhexyl oxygen base) ethoxybenzene ethene, to or m-1-positive propoxy ethoxybenzene ethene, to or m-1-cyclohexyl oxygen base oxethyl styrene, to or m-1-(2-cyclohexyl ethoxy) ethoxybenzene ethene, to or m-1-benzyl oxygen base oxethyl styrene etc.
Said structure unit (1) can be used a kind of or combine two or more uses.
Provide said structure unit (1) containing in the monomer of ethylidene ether structure, preferable methyl acrylic acid 1-ethoxyethyl group ester, methacrylic acid 1-n-butoxy ethyl ester, methacrylic acid 2-THP trtrahydropyranyl ester, methacrylic acid 1-benzyl oxygen base ethyl ester.
What said structure unit (1) was provided can use market sale containing the monomer of ethylidene ether structure, also can use known method synthetic.For example, provide the monomer containing ethylidene ether structure of the structural unit (1) shown in above-mentioned formula (1-1) as shown in following, by under the existence of acid catalyst, to make (methyl) acrylic acid and vinyl ether reaction synthetic.
(in formula, R ', R 1and R 3respectively with above-mentioned formula (1-1) in R ', R 1and R 3correspondence, R 21and R 22with-CH (R 21) (R 22) mode and the R in above-mentioned formula (1-1) 2corresponding.)
Content as the structural unit (1) in polymkeric substance [A], so long as polymkeric substance [A] demonstrates alkali-soluble by acid, given play to the desirable thermotolerance of cured film, just there is no particular limitation, in the situation that in a polymer molecule, contain structural unit (1) with containing the structural unit of epoxy radicals the two, with respect to the whole structural unit containing in polymkeric substance [A], in monomer add than, more than being preferably 5 quality %, below 70 quality %, more preferably more than 10 quality %, below 60 quality %, more than being particularly preferably 20 quality %, below 50 quality %.
On the other hand, in single polymer molecule, there is structural unit (1), and in the situation that there is the structural unit containing epoxy radicals in other single polymer molecule, as the content with the structural unit (1) in the single polymer molecule of structural unit (1), with respect to the whole structural unit containing in this polymer molecule, in monomer add than, more than being preferably 40 quality %, below 99 quality %, more preferably 50 quality % above, below 98 quality %, be particularly preferably 55 quality % above, below 95 quality %.
< is containing the structural unit > of epoxy radicals
Polymkeric substance [A], when having said structure unit (1), also has the structural unit containing epoxy radicals.Structural unit containing epoxy radicals is from the structural unit with the free-radical polymerised monomer containing epoxy radicals.As this epoxy radicals, can list Oxyranyle (1,2-epoxy construction), epoxypropane base (1,3-epoxy construction).Polymkeric substance [A], by have the structural unit containing Oxyranyle or epoxypropane base etc. in molecule, can improve the hardness of the cured film being obtained by this positive radiation line sensitive compositions, further improves thermotolerance.
Object lesson as the monomer containing epoxy radicals of the above-mentioned structural unit containing epoxy radicals is provided, for example can list:
Acrylic acid glycidyl esters, methyl propenoic acid glycidyl base ester, acrylic acid 3,4-epoxy butyl ester, methacrylic acid 3,4-epoxy butyl ester, acrylic acid 3-methyl-3,4-epoxy butyl ester, methacrylic acid 3-ethyl-3,4-epoxy butyl ester, acrylic acid 5,6-epoxy hexyl ester, methacrylic acid 5,6-epoxy hexyl ester, methacrylic acid 5-methyl-5,6-epoxy hexyl ester, methacrylic acid 5-ethyl-5,6-epoxy hexyl ester, acrylic acid 6,7-epoxy heptyl ester, methacrylic acid 6,7-epoxy heptyl ester
Methacrylic acid 3, 4-epoxycyclohexyl ester, methacrylic acid 3, 4-epoxycyclohexyl methyl ester, methacrylic acid 3, 4-epoxycyclohexyl ethyl ester, methacrylic acid 3, 4-epoxycyclohexyl propyl diester, methacrylic acid 3, 4-epoxycyclohexyl butyl ester, methacrylic acid 3, 4-epoxycyclohexyl hexyl ester, acrylic acid 3, 4-epoxycyclohexyl ester, acrylic acid 3, 4-epoxycyclohexyl methyl ester, acrylic acid 3, 4-epoxycyclohexyl ethyl ester, acrylic acid 3, 4-epoxycyclohexyl propyl diester, acrylic acid 3, 4-epoxycyclohexyl butyl ester, acrylic acid 3, 4-epoxycyclohexyl hexyl esters etc. are containing (methyl) acrylic compounds of Oxyranyle,
Adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether, Alpha-Methyl-adjacent vinyl benzyl glycidyl ether, an Alpha-Methyl-vinyl benzyl glycidyl ether, Alpha-Methyl-to vinyl benzyl glycidyl ethers such as vinyl benzyl glycidyl ethers;
Adjacent ethenylphenyl glycidyl ether, an ethenylphenyl glycidyl ether, to ethenylphenyl glycidyl ethers such as ethenylphenyl glycidyl ethers;
3-(acryloyl-oxy ylmethyl) epoxypropane, 3-(acryloyl-oxy ylmethyl)-3-methyl epoxypropane, 3-(acryloyl-oxy ylmethyl)-3-ethyl epoxypropane, 3-(acryloyl-oxy ylmethyl)-3-benzyl ring Ethylene Oxide, 3-(2-acryloxy ethyl) epoxypropane, 3-(2-acryloxy ethyl)-3-ethyl epoxypropane, 3-(2-acryloxy ethyl)-3-ethyl epoxypropane, 3-(2-acryloxy ethyl)-3-benzyl ring Ethylene Oxide
3-(methacryloxy methyl) epoxypropane, 3-(methacryloxy methyl)-3-methyl epoxypropane, 3-(methacryloxy methyl)-3-ethyl epoxypropane, 3-(methacryloxy methyl)-3-benzyl ring Ethylene Oxide, 3-(2-methacryloxyethyl) epoxypropane, 3-(2-methacryloxyethyl)-3-ethyl epoxypropane, 3-(2-methacryloxyethyl)-3-ethyl epoxypropane, 3-(2-methacryloxyethyl)-3-benzyl ring Ethylene Oxide
2-(acryloyl-oxy ylmethyl) epoxypropane, 2-(acryloyl-oxy ylmethyl)-2-methyl epoxypropane, 2-(acryloyl-oxy ylmethyl)-2-ethyl epoxypropane, 2-(acryloyl-oxy ylmethyl)-2-benzyl ring Ethylene Oxide, 2-(2-acryloxy ethyl) epoxypropane, 2-(2-acryloxy ethyl)-2-ethyl epoxypropane, 2-(2-acryloxy ethyl)-2-ethyl epoxypropane, 2-(2-acryloxy ethyl)-2-benzyl ring Ethylene Oxide
2-(methacryloxy methyl) epoxypropane, 2-(methacryloxy methyl)-2-methyl epoxypropane, 2-(methacryloxy methyl)-2-ethyl epoxypropane, 2-(methacryloxy methyl)-2-benzyl ring Ethylene Oxide, 2-(2-methacryloxyethyl) epoxypropane, 2-(2-methacryloxyethyl)-2-ethyl epoxypropane, 2-(2-methacryloxyethyl)-2-ethyl epoxypropane, (methyl) acrylic compounds that 2-(2-methacryloxyethyl)-2-benzyl ring Ethylene Oxide etc. contains epoxypropane base etc.The above-mentioned structural unit two or more uses alone or in combination containing epoxy radicals.
Above-mentioned containing in the monomer of epoxy radicals, viewpoint from the developability of the copolyreaction with other free radical polymerization monomer and positive radiation line sensitive compositions, preferable methyl acrylic acid glycidyl esters, methacrylic acid 2-methyl glycidyl esters, methacrylic acid 3,4-epoxycyclohexyl ester, methacrylic acid 3,4-epoxycyclohexyl methyl ester, 3-(methacryloxy methyl)-3-methyl epoxypropane, 3-(methacryloxy methyl)-3-ethyl epoxypropane.
Content as the structural unit containing epoxy radicals in polymkeric substance [A], so long as can give play to the desirable thermotolerance of interlayer dielectric, just there is no particular limitation, in the situation that contain structural unit (1) and the structural unit that contains epoxy radicals in a polymer molecule, with respect to the whole structural unit containing in polymkeric substance [A], in monomer add than, more than being preferably 10 quality %, below 60 quality %, more preferably 15 quality % above, below 55 quality %, be particularly preferably 20 quality % above, below 50 quality %.
On the other hand, in a polymer molecule, there is structural unit (1), and in the situation that there is the structural unit containing epoxy radicals in other polymer molecule, with respect to the entire infrastructure unit containing in other polymer molecule having containing the structural unit of epoxy radicals, content as the structural unit containing epoxy radicals, in monomer add than, more than being preferably 20 quality %, below 80 quality %, more preferably 30 quality % above, below 70 quality %, be particularly preferably 35 quality % above, below 65 quality %.
Other structural unit of < >
As the free radical polymerization monomer that other structural unit is provided, can list free radical polymerization monomer having carboxyl or derivatives thereof, hydroxyl etc.
As the above-mentioned free radical polymerization monomer with carboxyl or derivatives thereof, can list the monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-acryloxy ethyl succinic acid, 2-methacryloxyethyl succinic acid, 2-acryloxy ethyl hexahydrophthalic acid, 2-methacryloxy hexahydrophthalic acid;
The dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The acid anhydrides of above-mentioned dicarboxylic acids etc.
As the above-mentioned example with the free radical polymerization monomer of hydroxyl, can list:
The acrylic acid hydroxyalkyl acrylates such as acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxy-propyl ester, acrylic acid 4-hydroxybutyl ester, acrylic acid 4-hydroxymethyl cyclohexyl methyl ester;
The methacrylic acid hydroxyl Arrcostabs such as methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3-hydroxy-propyl ester, methacrylic acid 4-hydroxybutyl ester, methacrylic acid 5-hydroxyl amyl group ester, methacrylic acid 6-hydroxyl hexyl ester, methacrylic acid 4-hydroxymethyl-cyclohexyl methyl ester etc.
These have in the free radical polymerization monomer of hydroxyl, from the stable on heating viewpoint of the copolyreaction with other free radical polymerization monomer and the interlayer dielectric that obtains, preferably acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxy-propyl ester, acrylic acid 4-hydroxybutyl ester, methacrylic acid 2-hydroxyethyl ester, methacrylic acid 4-hydroxybutyl ester, acrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, methacrylic acid 4-hydroxymethyl-cyclohexyl methyl ester.
As the example of other free radical polymerization monomer, can list:
The alkyl acrylate such as methyl acrylate, isopropyl acrylate;
The alkyl methacrylates such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, the secondary butyl ester of methacrylic acid, Tert-butyl Methacrylate;
Cyclohexyl acrylate, acrylic acid 2-methyl cyclohexyl, acrylic acid three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester, acrylic acid 2-(three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base oxygen base) the acrylate ring type Arrcostab such as ethyl ester, isobornyl acrylate;
Cyclohexyl methacrylate, methacrylic acid 2-methyl cyclohexyl, methacrylic acid three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester, methacrylic acid 2-(three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base oxygen base) the methacrylic acid ester ring type Arrcostab such as ethyl ester, IBOMA;
Acrylic acid aryl ester and the acrylic acid aralkyl esters such as phenyl acrylate, acrylic acid benzyl ester;
The aryl ester of methacrylic acid and the aralkyl esters of methacrylic acid such as methacrylic acid phenylester, methacrylic acid benzyl ester;
The dicarboxylic acids dialkyls such as diethyl maleate, DEF, diethyl itaconate;
The methacrylate of 5 yuan of heterocycles and the methacrylate of unsaturated 6 yuan of heterocycles that methacrylic acid tetrahydro furfuryl ester, methacrylic acid tetrahydrofuran base ester, methacrylic acid oxinane-2-methyl ester etc. contain 1 oxygen atom;
4-methacryloxy methyl-2-methyl-2-ethyl-1,3-dioxolanes, 4-methacryloxy methyl-2-methyl-2-isobutyl-1, unsaturated 5 yuan of heterocyclic methyl acrylate that 3-dioxolanes, 4-methacryloxy methyl-2-cyclohexyl-DOX etc. contain two oxygen atoms;
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 acrylate of unsaturated 5 yuan of heterocycles that 3-dioxolanes etc. contains two oxygen atoms,
Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, to vinyl aromatic compounds such as methoxy styrene, 4-isopropenyl phenols;
The maleimide that the N-positions such as 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 replace;
1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene equiconjugate dienes compound;
Other unsaturated compounds such as vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate.
From with there is the copolyreaction of free radical polymerization monomer of above-mentioned reactive functional group group and the aspect of the developability of this positive radiation line sensitive compositions, in these other free radical polymerization monomers, optimization styrene, 4-isopropenyl phenol, methacrylic acid three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester, methacrylic acid tetrahydro furfuryl ester, 1,3-butadiene, 4-acryloyl-oxy ylmethyl-2-methyl-2-ethyl-DOX, N-N-cyclohexylmaleimide, N-phenylmaleimide, methacrylic acid benzyl ester etc.
The matter average molecular weight of the polystyrene conversion that the GPC (gel permeation chromatography) of polymkeric substance [A] obtains (following, also referred to as " Mw ") 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 polymkeric substance [A], be above-mentioned scope, can improve radioactive ray sensitivity and the alkali-developable of this positive radiation line sensitive compositions.
In addition, the number-average molecular weight of the polystyrene conversion that the GPC (gel permeation chromatography) of polymkeric substance [A] obtains (following, also referred to as " Mn ") is preferably 2.0 * 10 3～1.0 * 10 5, more preferably 5.0 * 10 3～5.0 * 10 4.By making the Mn of multipolymer, be above-mentioned scope, the solidification reactivity in the time of can improving the curing of coating of this positive radiation line sensitive compositions.
In addition, the molecular weight distribution " Mw/Mn " of polymkeric substance [A] is preferably below 3.0, more preferably below 2.6.By making the Mw/Mn of polymkeric substance [A], be below 3.0, can improve the developability of the interlayer dielectric obtaining.This positive radiation line sensitive compositions that contains polymkeric substance [A] is when developing, and generation development is residual, can easily form desirable pattern form.
The manufacture method > of < polymkeric substance [A]
Polymkeric substance [A] can by containing the monomer of ethylidene ether structure, containing the monomer of epoxy radicals, the free-radical polymerized manufacture of the monomer of other structural unit is provided.In being manufactured on same polymer molecule, comprise structural unit (1) and during containing the two polymkeric substance [A] of the structural unit of epoxy radicals, use and at least comprise containing the monomer of ethylidene ether structure with containing the potpourri of the monomer of epoxy radicals, copolymerization.On the other hand, in being manufactured on a polymer molecule, there is structural unit (1), and while thering is the polymkeric substance [A] containing the structural unit of epoxy radicals in the polymer molecule different with it, make at least to comprise the polymerism solution free radical polymerization containing the monomer of ethylidene ether structure, obtain the thering is structural unit polymer molecule of (1), make in addition at least to comprise the polymerism solution free radical polymerization containing epoxy radicals monomer, obtain thering is the polymer molecule containing the structural unit of epoxy radicals, finally both are mixed to form to polymkeric substance [A].
Solvent as using in manufacturing the polyreaction of polymkeric substance [A], can list such as alcohols, ethers, glycol ethers, ethylene glycol alkyl acetates, diethylene glycol alkyl ether, propylene-glycol monoalky lether, propylene-glycol monoalky lether acetic acid esters, propylene-glycol monoalky lether propionic ester, aromatic hydrocarbons, ketone, other ester class etc.
As these solvents, can list respectively:
As alcohols, be such as methyl alcohol, ethanol, phenmethylol, 2-phenylethanol, 3-phenyl-1-propanol etc.;
As ethers, be such as tetrahydrofuran etc.;
As glycol ethers, be such as ethylene glycol monomethyl ether, ethylene glycol monomethyl ether etc.;
As ethylene glycol alkyl ether acetic acid esters, be such as methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol monomethyl ether acetate etc.;
As diethylene glycol alkyl ether, be such as diethylene glycol monomethyl ether, TC, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether etc.;
As propylene-glycol monoalky lether, be such as 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, be such as 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, be such as 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 be such as toluene, dimethylbenzene etc.;
As ketone, be such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone etc.;
As other ester class, it is methyl acetate for example, 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, the ester classes such as 3-butoxy butyl propionate.
In these solvents, preferred ethylene glycol alkyl ether acetic acid esters, diethylene glycol alkyl ether, propylene-glycol monoalky lether, propylene-glycol monoalky lether acetic acid esters, methoxyacetic acid butyl ester, particularly preferably diethylene glycol dimethyl ether, diethylene glycol ethyl-methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, methoxyacetic acid butyl ester.
As manufacturing the polymerization initiator using in the polyreaction of polymkeric substance [A], can use generally as known those of radical polymerization initiator.As radical polymerization initiator, for example can list:
2,2 '-azoisobutyronitrile, 2,2 '-azo two-(2,4-methyl pentane nitrile), 2,2 '-azo two-azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles);
The organic peroxides such as benzoyl peroxide, lauroyl peroxide, peroxidating neopentanoic acid tertiary butyl ester, 1,1 '-bis-(tert-butyl hydroperoxide) cyclohexane, and hydrogen peroxide.
When using superoxide as radical polymerization initiator, superoxide can be formed together with reductive agent to oxidation-reduction type initiating agent.
In the polyreaction for the manufacture of polymkeric substance [A], can use molecular weight regulator Molecular regulator amount.Object lesson as molecular weight regulator can list:
The halogenated hydrocarbon such as chloroform, carbon tetrabromide;
The thio-alcohols such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary lauryl mercaptan, mercaptoacetic acid;
The xanthate classes such as sulfuration dimethyl yellow ortho esters, dithiodiisopropyl xanthate;
Terpinolene, α-methylstyrenedimer etc.
<[B] light acid producing agent >
[B] light acid producing agent is by irradiating the acidic compound of radioactive ray.Here, as radioactive ray, can use such as luminous ray, ultraviolet ray, far ultraviolet, electron beam, X ray etc.This positive radiation line sensitive compositions, by containing [B] light acid producing agent, can have been given play to the radioactive ray sensitivity characteristic of eurymeric.[B] light acid producing agent is so long as for example, by irradiating the compound of radioactive ray generation acid (, carboxylic acid, sulfonic acid etc.), and just there is no particular limitation.As [B] light acid producing agent in this positive radiation line sensitive compositions, contain the light acid producing agent form that form can be the such compound of aftermentioned, also can be the sour form that produces group of light combining with a part for polymkeric substance [A] or other polymkeric substance, can also be these two kinds of forms.As [B] light acid producing agent, list typically oxime sulfonates compound, can list diphenyl iodnium, triphenyl sulfonium salt, sulfonium salt, benzothiazolium salt, ammonium salt, phosphonium salt and thiophane salt etc. salt or, sulfimine compound and quinone di-azido compound.
< oxime sulfonates compound >
As above-mentioned oxime sulfonates compound, preferably contain the compound of the oxime sulfonates base shown in following formula (8).
In above-mentioned formula (8), R b1being can substituted straight chain shape, the alkyl of a chain, ring-type or can substituted aryl.As R b1alkyl be preferably the alkyl that carbon number is 1～10 straight chain shape or a chain.R b1the alkyl alkoxy that can is 1～10 by carbon number or alicyclic group (comprise the alicyclic group that 7,7-dimethyl-2-oxo norborny etc. comprises bridged bond, preferably bicyclic alkyl etc.) replace.As R b1the preferred carbon number of aryl be 6～11 aryl, more preferably phenyl or naphthyl.R b1aryl can be 1～5 by carbon number alkyl, alkoxy or halogen atom replace.
The above-claimed cpd that contains the oxime sulfonates base shown in above-mentioned formula (8) is the oxime sulfonates compound shown in following formula (9) more preferably.
In above-mentioned formula (9), R b1with the R in above-mentioned formula (8) b1the definition of explanation identical.X is alkyl, alkoxy or halogen atom.M is 0～3 integer.M is 2 or 3 o'clock, and a plurality of X can be identical, also can be different.As the alkyl of X, being preferably carbon number is 1～4 straight chain shape or the alkyl of a chain.
As the alkoxy of X, being preferably carbon number is 1～4 straight chain shape or the alkoxy of a chain.Halogen atom as X is preferably chlorine atom or fluorine atom.M is preferably 0 or 1.Particularly, in above-mentioned formula (9), the position of substitution that preferably m is 1, X is methyl, X is the compound at ortho position.
As the object lesson of oxime sulfonates compound, can list compound (i), compound (ii), compound (iii), compound (iv) and the compound (v) etc. that such as following formula (i)～(v), represent respectively.
They can distinguish two or more uses alone or in combination, also can and be used in combination as other light acid producing agent of [B] composition.As above-claimed cpd (i)～(v) can be obtained by commercial goods.
< salt >
In above-mentioned salt, example as diphenyl iodnium, can list diphenyl iodine tetrafluoroborate, diphenyl iodine hexafluorophosphate, diphenyl iodine hexafluoro arsenate, diphenyl iodine fluoroform sulphonate, diphenyl iodine trifluoroacetate, the iodo-tosilate of diphenyl, diphenyl iodine butyl three (2, 6-difluoro-benzene base) borate, 4-methoxyphenyl-phenyl-iodide tetrafluoroborate, two (4-tert-butyl-phenyl) iodine tetrafluoroborate, two (4-tert-butyl-phenyl) iodine hexafluoro arsenate, two (4-tert-butyl-phenyl) iodine fluoroform sulphonate, two (4-tert-butyl-phenyl) iodine trifluoroacetate, two (4-tert-butyl-phenyl) iodo-tosilate, two (4-tert-butyl-phenyl) iodine camsilate etc.
Example as triphenyl sulfonium salt, can list triphenylsulfonium fluoroform sulphonate, triphenylsulfonium camsilate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-tosilate, triphenylsulfonium butyl three (2,6-difluoro-benzene base) borate etc.
As the example of sulfonium salt, can list the benzyl sulfonium salt of alkyl sulfonium salt, benzyl sulfonium salt, dibenzyl sulfonium salt, replacement etc.
As these sulfonium salts, can list respectively:
As alkyl sulfonium salt, be such as 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro stibate, 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, dimethyl-4-(benzyloxycarbonyl group oxygen base) phenyl sulfonium hexafluoro stibate, dimethyl-4-(benzoyloxy) phenyl sulfonium hexafluoro stibate, dimethyl-4-(benzoyl oxygen base) phenyl sulfonium hexafluoro arsenate, dimethyl-3-chloro-4-acetoxyl group phenyl sulfonium hexafluoro stibate etc.;
As benzyl sulfonium salt, be such as benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro stibate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro phosphate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro stibate, benzyl-4-methoxybenzene ylmethyl sulfonium hexafluoro stibate, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro stibate, benzyl-3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro arsenate, 4-methoxy-benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro phosphate etc.;
As dibenzyl sulfonium salt, be such as dibenzyl-4-hydroxy phenyl sulfonium hexafluoro stibate, dibenzyl-4-hydroxy phenyl sulfonium hexafluoro phosphate, 4-acetoxyl group phenyl dibenzyl sulfonium hexafluoro stibate, dibenzyl-4-methoxyphenyl sulfonium hexafluoro stibate, dibenzyl-3-chloro-4-hydroxy phenyl sulfonium hexafluoro arsenate, dibenzyl-3-methyl-4-hydroxyl-5-tert-butyl-phenyl sulfonium hexafluoro stibate, benzyl-4-methoxy-benzyl-4-hydroxy phenyl sulfonium hexafluoro phosphate etc.;
As the benzyl sulfonium salt replacing be for example to chloro benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro stibate, to nitrobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro stibate, to chloro benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro phosphate, to nitrobenzyl-3-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro stibate, 3,5-dichloro-benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro stibate, adjacent chloro benzyl-3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro stibate etc.
As the example of benzothiazolium salt, can list 3-benzyl benzothiazole hexafluoro stibate, 3-benzyl benzothiazole hexafluoro phosphate, 3-benzyl benzothiazole tetrafluoroborate, 3-(to methoxy-benzyl) benzothiazole hexafluoro stibate, 3-benzyl-2-methyl-thio-benzothiazole hexafluoro stibate, 3-benzyl-5-chloro benzo thiazole hexafluoro stibate etc.
Example as thiophane salt, can list 1-(4-n-butoxy naphthalene-1-yl) thiophane three fluoro mesylates, the positive fourth sulfonate of 1-(4-n-butoxy naphthalene-1-yl) thiophane nine fluoro, 1-(4-n-butoxy naphthalene-1-yl) thiophane-1, 1, 2, 2-tetrafluoro generation-2-(norbornane-2-yl) esilate, 1-(4-n-butoxy naphthalene-1-yl) thiophane-2-(5-tert-butoxycarbonyl oxygen base two ring [2.2.1] heptan-2-yls)-1, 1, 2, 2-tetrafluoro is for esilate, 1-(4-n-butoxy naphthalene-1-yl) thiophane-2-(6-tert-butoxycarbonyl oxygen base two ring [2.2.1] heptan-2-yls)-1, 1, 2, 2-tetrafluoro is for esilate, 1-(4, 7-dibutoxy-1-naphthyl) thiophane fluoroform sulphonate etc.
In these salt, the viewpoint from the adaptation of the radioactive ray sensitivity of this raising positive radiation line sensitive compositions and the solidfied material that obtains, is applicable to using triphenyl sulfonium salt, sulfonium salt, benzothiazolium salt, tetrahydro-thiazoles salt, sulfimine compound.Among them, particularly preferably use triphenylsulfonium fluoroform sulphonate, triphenylsulfonium camsilate, 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, 3-benzyl benzothiazole hexafluoro antimonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, 1-(4-n-butoxy naphthalene-1-yl) thiophane fluoroform sulphonate, 1-(4, 7-dibutoxy-1-naphthyl) thiophane fluoroform sulphonate.
< sulfimine compound >
Example as sulfimine compound is N-(trimethyl fluoride sulfonyl oxygen base) succinimide (trade name " SI-105 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(camphor sulfonyloxy) succinimide (trade name " SI-106 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(4-aminomethyl phenyl sulfonyloxy) succinimide (trade name " SI-101 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(2-trifluoromethyl sulfonyloxy) succinimide, N-(4-difluorophenyl sulfonyloxy) succinimide, N-(trimethyl fluoride sulfonyl oxygen base) phthalimide, N-(camphor sulfonyloxy) phthalimide, N-(2-trifluoromethyl sulfonyloxy) phthalimide, N-(2-difluorophenyl sulfonyloxy) phthalimide, N-(trimethyl fluoride sulfonyl oxygen base) diphenyl maleimide (trade name " PI-105 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(camphor sulfonyloxy) diphenyl maleimide, N-(4-aminomethyl phenyl sulfonyloxy) diphenyl maleimide, N-(2-trifluoromethyl sulfonyloxy) diphenyl maleimide, N-(4-difluorophenyl sulfonyloxy) diphenyl maleimide, N-(4-difluorophenyl sulfonyloxy) diphenyl maleimide, N-(phenyl sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboximide (trade name " NDI-100 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(4-aminomethyl phenyl sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboximide (trade name " NDI-101 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(trifluoro-methanesulfonyl oxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboximide (trade name " NDI-105 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(nine fluoro fourth sulfonyloxies) two ring [2.2.1] heptan-5-alkene-2,3-dicarboximide (trade name " NDI-109 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(camphor sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboximide (trade name " NDI-106 " (body ど り chemistry (Co., Ltd.) is manufactured)), 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) two ring [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) two ring [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-difluorophenyl sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(4-difluorophenyl sulfonyloxy)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(trimethyl fluoride sulfonyl oxygen base) two ring [2.2.1] heptane-5,6-oxygen base-2,3-dicarboximide, N-(camphor sulfonyloxy) two ring [2.2.1] heptane-5,6-oxygen base-2,3-dicarboximide, N-(4-aminomethyl phenyl sulfonyloxy) two ring [2.2.1] heptane-5,6-oxygen base-2,3-dicarboximide, N-(2-trifluoromethyl sulfonyloxy) two ring [2.2.1] heptane-5,6-oxygen base-2,3-dicarboximide, N-(4-difluorophenyl sulfonyloxy) two ring [2.2.1] heptane-5,6-oxygen base-2,3-dicarboximide, N-(trimethyl fluoride sulfonyl oxygen base) naphthyl dicarboximide (trade name " NAI-105 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(camphor sulfonyloxy) naphthyl dicarboximide (trade name " NAI-106 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(4-aminomethyl phenyl sulfonyloxy) naphthyl dicarboximide (trade name " NAI-101 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(phenyl sulfonyloxy) naphthyl dicarboximide (trade name " NAI-100 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(2-trifluoromethyl sulfonyloxy) naphthyl dicarboximide, N-(4-difluorophenyl sulfonyloxy) naphthyl dicarboximide, N-(five fluoro ethyl sulfonyloxies) naphthyl dicarboximide, N-(seven fluoro sulfonyl propyl oxygen bases) naphthyl dicarboximide, N-(nine fluoro butyl sulfonyloxies) naphthyl dicarboximide (trade name " NAI-109 " (body ど り chemistry (Co., Ltd.) is manufactured)), N-(ethyl sulfonyloxy) naphthyl dicarboximide, N-(sulfonyl propyl oxygen base) naphthyl dicarboximide, N-(butyl sulfonyloxy) naphthyl dicarboximide (trade name " NAI-1004 " (body ど り chemistry (Co., Ltd.) is manufactured)), 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.
< quinone di-azido compound >
Quinone di-azido compound is by irradiating radioactive ray, to produce the compound of carboxylic acid.As quinone di-azido compound, can use the condensation product of phenol or alcohol compound (following, to be called " parent nucleus ") and 1,2-naphthoquinones, two nitrine sulfonic acid halides.
As above-mentioned parent nucleus, can list for example trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxy benzophenone, (polyhydroxy phenyl) alkane, other parent nucleus.
As these parent nucleus, can list:
As trihydroxybenzophenone, be for example 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone etc.;
Tetrahydroxybenzophenone is BP-2,2,3 for example, 4,3 '-tetrahydroxybenzophenone, 2,3,4,4'-Tetrahydroxybenzophenone, 2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl ketone, 2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone etc.;
As pentahydroxybenzophenone, be for example 2,3,4,2 ', 6 '-pentahydroxybenzophenone etc.;
As hexahydroxy benzophenone, be for example 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone etc.;
As (polyhydroxy phenyl) alkane, be for example 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-bis-(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] xenol, 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 '-six alcohol, 2, 2, 4-trimethyl-7, 2 ', 4 '-trihydroxy flavane etc.,
As other parent nucleus, be 2-methyl-2-(2 for example, 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, 4,6-bis-{ 1-(4-hydroxy phenyl)-1-Methylethyl }-1,3-dihydroxy benzenes.
In these parent nucleus, preferred 2,3,4,4'-Tetrahydroxybenzophenone, 1,1,1-tri-(p-hydroxybenzene) ethane, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] xenol.
In addition, as 1,2-naphthoquinones, two nitrine sulfonic acid halides, preferably 1,2-naphthoquinones two nitrine sulfonic acid chlorides.As the object lesson of 1,2-naphthoquinones, two nitrine sulfonic acid chlorides, can list 1,2-naphthoquinones, two nitrine-4-sulfonic acid chloride and 1,2-naphthoquinones, two nitrine-5-sulfonic acid chloride.Wherein, particularly preferably use 1,2-naphthoquinones, two nitrine-5-sulfonic acid chloride.
As phenoloid or alcohol compound and 1, the suitable example of the condensation product of 2-naphthoquinones two nitrine sulfonic acid halides, can list 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 xenol and 1,2-naphthoquinones, two nitrine-5-sulfonic acid chloride.
In phenoloid or alcohol compound (parent nucleus) and 1, in the condensation reaction of 2-naphthoquinones two nitrine sulfonic acid carboxylic acid halides, with respect to the OH radix amount in phenoloid or alcohol compound, use be equivalent to be preferably 30～85mol%, more preferably 50～70mol% 1,2-naphthoquinones two nitrine sulfonic acid halides.Condensation reaction is undertaken by known method.
In addition, as quinone di-azido compound, be also applicable to use 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-triamido BP-1,2-naphthoquinones two nitrine-4-sulfonamide etc.These [B] compositions can be used separately or combine two or more uses.
The content of [B] light acid producing agent in this positive radiation line sensitive compositions, is preferably 1～20 mass parts with respect to 100 mass parts polymkeric substance [A], more preferably 1～10 mass parts.By making the content of [B] composition, be above-mentioned scope, can make the illuminated portion of radioactive ray and non-irradiated part become large to the poor of the solubleness of the aqueous alkali as developer solution, pattern functional, and also the solvent resistance of the interlayer dielectric obtaining is also good.
< multipolymer [C] >
Multipolymer [C] composition is to comprise have the structural unit of fluorine and have the multipolymer of the structural unit of silicon, and then is the multipolymer at least comprising from the structural unit of the polymerizable compound with ad hoc structure (c1), polymerizable compound (c2) and polymerizable compound (c3).In this positive radiation line sensitive compositions, multipolymer [C] plays the function as the high surfactant of the performance of surface tension reduction, even while using this material with less ratio, also can significantly improve the profile pattern of the interlayer dielectric of formation.
In this positive radiation line sensitive compositions, multipolymer [C] preferably further has the structural unit from (c4) with the polymerizable unsaturated compound that carbon number is 1～8 unsubstituted alkyl ester group (following, also referred to as " polymerizable compound (c4) "); There is in addition and then more preferably the structural unit in a part from (c5) with the polymerizable unsaturated compound (following, also referred to as " polymerizable compound (c5) ") of more than two unsaturated link; Particularly preferably by the composition that contains above-mentioned polymerizable compound (c1), polymerizable compound (c2), polymerizable compound (c3), polymerizable compound (c4) and polymerizable compound (c5), formed.
Group-C in above-mentioned formula (2) αh 2 α-be the alkylidene of methylene or alkyl methylene or straight chain shape or a chain.Group-C αh 2 α-be non-when symmetrical, its closure is not limit.Group-C αh 2 α-carbon number α be preferably 2～4.As group-C αh 2 α-object lesson, for example can list 1,2-ethylidene, 1,2-propylidene, 1,3-propylidene, Isosorbide-5-Nitrae-butylidene etc.; Among them, preferably 1,2-ethylidene or 1,3-propylidene, particularly preferably 1,2-ethylidene.
Group-C in above-mentioned formula (2) βf 2 β+1it is the fluoro-alkyl of straight chain shape or a chain.Group-C βf 2 β+1carbon number β be 1～20, be preferably 1～12, more preferably 1～8, be particularly preferably 2～8.Group-C βf 2 β+1be preferably the fluoro-alkyl of straight chain shape.
As the polymerizable compound in the present invention (c1), be preferably the compound shown in above-mentioned formula (6).As the object lesson of compound (c1), can list compound that following formula (c1-1)～(c1-8) represents respectively etc.
CH 2＝CHCOOC 2H 4C 8F 17 (c1-1)
CH 2＝C(CH 3)COOC 2H 4C 8F 17 (c1-2)
CH 2＝CH COOC 2H 4C 6F 13 (c1-3)
CH 2＝C(CH 3)COOC 2H 4C 6F 13 (c1-4)
CH 2＝CHCOOC 2H 4C 4F 9 (c1-5)
CH 2＝C(CH 3)COOC 2H 4C 4F 9 (c1-6)
CH 2＝CHCOOC 2H 4C 2F 5 (c1-7)
CH 2＝C(CH 3)COOC 2H 4C 2F 5 (c1-8)
Group-C in above-mentioned formula (3) γh 2 γ-be the alkylidene of straight chain shape or a chain.Group-C γh 2 γwhen-right and wrong are symmetrical, its closure is not limit.As group-C γh 2 γ-object lesson, for example can list 1,2-ethylidene and 1,2-propylidene, preferably 1,2-ethylidene.
Compound (c2) is used with the potpourri of the different compound of the value of the number of repeat unit a in above-mentioned formula (3).Several averages of a are 1～30, are preferably 2～20, are particularly preferably 4～12.In compound (c2), be to be respectively 2 o'clock at γ, (methyl) acrylic acid and reacting ethylene oxide are synthesized, at γ, be 3 o'clock, make (methyl) acrylic acid and propylene oxide reaction synthetic.Now, with respect to 1mol (methyl) acrylic acid, the oxirane of importing or the molal quantity of epoxypropane are according to the value of a and different.This value can be by trying to achieve the number-average molecular weight of the polystyrene conversion of gel permeation chromatography for compound (c2), from with respect to 1mol (methyl) acrylic acid, the molal quantity that the oxirane importing or epoxypropane add, calculates the value of above-mentioned number-average molecular weight of trying to achieve and tries to achieve.
As compound (c2), be applicable to using commercial goods.Example as this commercial goods, can enumerate NK-エ ス テ Le M-40G, NK-エ ス テ Le M-90G, AM-90G that the middle village chemical industry (Co., Ltd.) that makes new advances is manufactured, Block レ Application マ mono-PME-200, PME-400, the PME-550 etc. of day oil (Co., Ltd.) manufacture.
In above-mentioned formula (4), there are respectively a plurality of R in above-claimed cpd (c3) 8and R 9time, each R 8can be the same or different, each R 9can be the same or different.In addition, in above-mentioned formula (5), there are respectively a plurality of R 13and R 14time, each R 13can be the same or different, each R 14can be the same or different.In addition, as compound (c3), preferably in above-mentioned formula (4), R 7, R 8and R 9respectively that carbon number is 1～20 alkyl or phenyl, and R 10and R 11it is respectively the polymerizable unsaturated compound with the group shown in above-mentioned formula (5).
As compound (c3), preferably can use the compound shown in following formula (c3-1).
(in formula (c3-1), R sithe group shown in above-mentioned formula (4), R 15be hydrogen atom or methyl, d is 1～3 integer.)
As the object lesson of compound (c3-1), can list following formula (c3-1-1), (c3-1-2) and the compound that (c3-1-3) represents respectively etc.
(in formula (c3-1-1), Me is methyl, and r, s and t are respectively 0～3 integers.)
(in formula (c3-1-2), similarly definition in Me and r, s and t and above-mentioned formula (c3-1-1).)
(in formula (c3-1-3), similarly definition in Me and r, s and t and above-mentioned formula (c3-1-1), Ph is phenyl.)
As compound (c4), can list such as having carbon number is (methyl) alkyl acrylate of 1～8 unsubstituted alkyl ester group etc.As the object lesson of compound (c4), can list methacrylic acid n-butyl, methyl methacrylate, 2-ethylhexyl acrylate etc.
As compound (c5), the compound of the two terminal methyl group acroleic acid esterifications that can list such as BDO, the degree of polymerization polyglycol that is 1～20, the polypropylene glycol that the degree of polymerization is 1～20 etc.As compound (c5), be applicable to using commercial goods.As the example of this commercial goods, can enumerate NK-エ ス テ Le 1G, NK-エ ス テ Le 2G, NK-エ ス テ Le 3G, NK-エ ス テ Le 4G, NK-エ ス テ Le 9G, NK-エ ス テ Le 14G etc. that the middle village chemical industry (Co., Ltd.) that makes new advances is manufactured.
Multipolymer [C] is when having the above-mentioned this structural unit from polymerizable compound (c1), polymerizable compound (c2) and polymerizable compound (c3), each polymerizable compound with respect to the usage ratio of the total amount of these polymerizable compounds is: polymerizable compound (c1) is 10～55 quality %, polymerizable compound (c2) is 10～50 quality %, and polymerizable compound (c3) is 5～45 quality %.
Multipolymer [C] is when the structural unit further having from polymerizable compound (c4), each polymerizable compound with respect to the usage ratio of the total amount of these polymerizable unsaturated compounds is: polymerizable compound (c1) is 20～50 quality %, polymerizable compound (c2) is 15～40 quality %, and polymerizable compound (c3) is that 10～30 quality %, polymerizable compound are 20～35 quality %.
Multipolymer [C] is when the structural unit further having from polymerizable compound (c5), each polymerizable compound with respect to the usage ratio of the total amount of these polymerizable unsaturated compounds is: polymerizable compound (c1) is 25～35 quality %, polymerizable compound (c2) is 20～30 quality %, polymerizable compound (c3) is that 15～20 quality %, polymerizable compound are 25～35 quality %, and polymerizable compound (c5) is 1～5 quality %.Be used to form the compound (c1) of multipolymer [C]～(c5) can use separately respectively, also can mix multiple use.
The matter average molecular weight (Mw) of multipolymer [C] is 5,000～25,000, be preferably 10,000～25,000, and be particularly preferably 15,000～25,000.The molecular weight distribution (Mw/Mn) (Mw is with respect to the ratio of number-average molecular weight Mn) of multipolymer [C] is preferably 1～10, and more preferably 2～4.
There is no particular limitation for the manufacture method of multipolymer [C], can be by known method, and such as based on polymerization mechanism such as radical polymerization, cationic polymerization, anionic polymerizations, by manufactures such as solution polymerization process, mass polymerization, emulsion polymerizations.In these manufacture methods, because the radical polymerization in solution is simple, industrial be preferred.
The polymerization initiator using during as manufacture multipolymer [C], can list superoxide such as benzoyl peroxide, diacyl peroxide; 2, the azo-compounds such as 2 '-azoisobutyronitrile, phenylazo triphenyl methane etc.
The manufacture of multipolymer [C] can be carried out under any situation under the existence of solvent or not, but from workability aspect, preferably under the existence of solvent, carries out.As above-mentioned solvent, can list such as alcohol, ketone, monocarboxylic Arrcostab, ether, propylene glycol and ester thereof, halogenated hydrocarbons, aromatic hydrocarbons, fluoridize inert fluid, other polar solvent etc.
Example as these solvents is:
As above-mentioned alcohol, can list such as ethanol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, the tert-butyl alcohol etc.;
As above-mentioned ketone, can list such as acetone, MEK, methyl isobutyl ketone, methylamino ketone etc.;
As above-mentioned monocarboxylic Arrcostab, can list such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, Acetylformic acid methyl esters, ethyl 2-oxopropanoate, Acetylformic acid propyl ester, Acetylformic acid butyl ester, 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester etc.;
As above-mentioned ether, can list such as methyl cellosolve, cellosolve, butyl cellosolve, butyl card and finish alcohol, ethyl cellosolve acetate, tetrahydrofuran, diox etc.;
As above-mentioned propylene glycol and ester thereof, can list such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol single-butyl ether acetic acid esters etc.;
As above-mentioned halogenated hydrocarbons, for example can list 1,1,1-trichloroethanes, chloroform etc.;
As above-mentioned aromatic hydrocarbons, can list such as benzene,toluene,xylene etc.;
As the above-mentioned inert fluid of fluoridizing, can list such as PFO, perfluor tri-n-butyl amine etc.;
As above-mentioned other polar solvent, can list such as dimethyl formamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE etc.
These solvents can be used separately a kind of, two or more suitable mixing can be used.
While manufacturing multipolymer [C], as required, can further use the chain-transferring agents such as lauryl mercaptan, 2 mercapto ethanol, ethyl thioacetate, thioacetic acid monooctyl ester.
The usage ratio of the multipolymer [C] in this positive radiation line sensitive compositions is with respect to 100 mass parts [A] composition, is preferably 0.01～3 mass parts, more preferably 0.05～2 mass parts.By using [C] composition with this ratio, can form the interlayer dielectric having without the irregular height planarization of coating.
Other optional member of < >
Positive radiation line sensitive compositions of the present invention, except above-mentioned [A]～[C] composition, in not damaging the scope of desirable effect, can contain other optional members such as [D] closely sealed auxiliary agent, [E] alkali compounds as required.
<[D] closely sealed auxiliary agent >
In this positive radiation line sensitive compositions, can use for improving the closely sealed auxiliary agent as the inorganics of substrate and close-burning [D] composition of dielectric film, silicon compounds such as silicon, monox, silicon nitride of the described inorganics as substrate, the metals such as gold, copper, aluminium.As this closely sealed auxiliary agent, preferably use functional silanes coupling agent.As the example of functional silanes coupling agent, can list there is carboxyl, the silane coupling agent of methacryl, isocyanate group, epoxy radicals (optimization ethylene oxide base), mercapto isoreactivity substituted radical etc.
Object lesson as functional silanes coupling agent, can list trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl alkyl-dialkoxysilanes, γ-chloro propyl trialkoxy silane, γ-sulfydryl propyl trialkoxy silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc.Among them, preferred γ-glycidoxypropyl alkyl-dialkoxysilanes, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-methacryloxypropyl trimethoxy silane.
In this positive radiation line sensitive compositions, with respect to 100 mass parts polymkeric substance [A], this closely sealed auxiliary agent is preferably with more than 0.5 mass parts, below 20 mass parts, and more preferably, amount 10 mass parts below above with 1 mass parts used.By making the amount of closely sealed auxiliary agent, be above-mentioned scope, can improve the adaptation of interlayer dielectric and the substrate of formation.
<[E] alkali compounds >
As alkali compounds, any choice for use in the alkali compounds that can use from chemically amplified photo resist agent.As alkali compounds, can list such as fatty amine, aromatic amine, heterocyclic amine, quaternary ammonium hydroxide, carboxylic acid quaternary ammonium salt etc.By contain alkali compounds in this positive radiation line sensitive compositions, can suitably control the sour diffusion that exposes and produced by light acid producing agent, can form good pattern development.
As fatty amine, can list such as trimethylamine, diethylamine, triethylamine, di-n-propyl amine, three n-pro-pyl amine, two n-pentyl amine, three n-pentyl amine, diethanolamine, triethanolamine, dicyclohexyl amine, dicyclohexyl methyl amine etc.
As aromatic amine, can list such as aniline, benzyl amine, DMA, diphenylamine etc.
As heterocyclic amine, can list for example pyridine, 2-picoline, 4-picoline, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl 4-phenyl pyridine, 4-dimethylaminopyridine, imidazoles, benzimidazole, 4-methylimidazole, 2-Phenylbenzimidazole, 2, 4, 5-triphenyl imidazoles, nicotine, nicotinic acid, niacinamide, quinoline, 8-Oxoquinoline, pyrazine, pyrazoles, pyridazine, purine, pyrrolidine, piperidines, piperazine, morpholine, 4-methyl morpholine, 1, 5-diazabicylo [4, 3, 0]-5-nonene, 1, 8-diazabicylo [5, 3, 0]-7-hendecene etc.
As quaternary ammonium hydroxide, can list such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, the positive fourth ammonium of hydroxide four, hydroxide four own ammonium etc. just.
As carboxylic acid quaternary ammonium salt, can list such as tetramethyl ammonium acetate, tetramethylbenzene ammonium formate, tetra-n-butyl ammonium acetate, tetra-n-butyl ammonium benzoate etc.
The content of the alkali compounds in this positive radiation line sensitive compositions, with respect to 100 mass parts polymkeric substance [A], is preferably 0.001～1 mass parts, more preferably 0.005～0.2 mass parts.By making the content of alkali compounds, be above-mentioned scope, pattern development is good.
< positive radiation line sensitive compositions >
Positive radiation line sensitive compositions of the present invention is mixed with by the multipolymer that above-mentioned [A] polymkeric substance, [B] light acid producing agent, [C] are formed by the monomer of ad hoc structure and the optional member using as required.Conventionally, preferably preparation under the state of dissolving or dispersion, use in suitable [F] solvent of positive radiation line sensitive compositions.For example, in solvent, by [A], [B] and [C] composition and optional member are mixed with the ratio of regulation, can prepare positive radiation line sensitive compositions.
<[F] solvent >
As [F] solvent that can use in the preparation of this positive radiation line sensitive compositions, be applicable to using each composition is dissolved equably or disperseed, and the solvent of each composition reaction of getting along well.As this solvent, can list such as alcohols, ethers, diethylene glycol alkyl ether, ethylene glycol alkyl ether acetate esters, propylene-glycol monoalky lether class, propylene-glycol monoalky lether acetate esters, propylene-glycol monoalky lether propionic acid ester, aromatic hydrocarbon based, ketone, ester class etc.
As these solvents, can list respectively:
As alcohols, be such as phenmethylol, diacetone alcohol etc.;
As ethers, be such as dialkyl ethers such as tetrahydrofuran and Di Iso Propyl Ether, di-n-butyl ether, two n-pentyl ethers, diisoamyl ether, di-n-hexyl ether etc.;
As diethylene glycol alkyl ether, be such as diethylene glycol monomethyl ether, TC, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether etc.;
As ethylene glycol alkyl ether acetate esters, be such as methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol monomethyl ether acetate etc.;
As propylene-glycol monoalky lether class, be such as propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, propylene glycol single-butyl ether etc.;
As propylene-glycol monoalky lether acetate esters, be such as 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 acid ester, be such as 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 be such as toluene, dimethylbenzene etc.;
As ketone, be such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-HEPTANONE, 4-hydroxy-4-methyl-2-pentanone etc.;
As ester class, it is methyl acetate for example, ethyl acetate, propyl acetate, isopropyl 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 etc.
In these solvents, from dissolubility or excellent dispersion, with the non-reacted of each composition and the viewpoint that forms the easiness film set out, the ethers such as preferred dialkyl ether, diethylene glycol alkyl ether, ethylene glycol alkyl ether acetate esters, propylene-glycol monoalky lether class, propylene-glycol monoalky lether acetate esters, ketone and ester class, diethylene glycol diethyl ether particularly preferably, diethylene glycol ethyl-methyl ether, methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, cyclohexanone, propyl acetate, isopropyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester.These solvents can be used alone or as a mixture.
In addition, in these solvents, the ethers such as dialkyl ether such as preferred Di Iso Propyl Ether, di-n-butyl ether, two n-pentyl ethers, diisoamyl ether, di-n-hexyl ether, most preferably diisoamyl ether.By using this solvent, while being coated with radiation-ray sensitive composition by slot coated method on large-size glass substrate, can shorten the drying process time, can further improve coating (suppressing coating irregular) simultaneously.
Except above-mentioned solvent, as required, use together with can also finishing the high boiling solvents such as alcohol acetic ester with benzylisoeugenol, hexyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether, acetonyl acetone, isophorone, caproic acid, capric acid, 1-octanol, 1 nonyl alcohol, benzylalcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetic acid esters, card.
When positive radiation line sensitive compositions is prepared with solution or dispersion liquid state, occupy composition beyond [F] solvent in solution (namely, the total amount of [A], [B] and [C] composition and other optional member) ratio, can set arbitrarily according to application target and desirable thickness etc., be preferably 5～50 quality %, more preferably 10～40 quality %, 15～35 quality % more preferably.
The formation > of < interlayer dielectric
Then,, to using above-mentioned positive radiation line sensitive compositions, the method that forms interlayer dielectric on substrate describes.The method comprises the following operation that following order is recorded.
(1) on substrate, form the operation of filming of this positive radiation line sensitive compositions,
(2) at least a portion of filming forming in operation (1) is irradiated to the operation of radioactive ray,
(3) will in operation (2), irradiate the operation of the painting film development of radioactive ray, and
(4) operation to the heating of filming of developing in operation (3).
< (1) forms the operation > filming of this positive radiation line sensitive compositions on substrate
In the operation of above-mentioned (1), by the solution of this positive radiation line sensitive compositions or dispersed liquid coating to after on substrate, preferably by heating (prebake) applicator surface except desolventizing, formation is filmed.As the example of operable substrate, can list glass, quartz, silicon, resin etc.As the object lesson of resin, can list the ring-opening polymerization polymer of polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, cyclic olefin and hydride thereof etc.
As the coating process of composition solution or dispersion liquid, there is no particular limitation, can adopt suitable methods such as spray-on process, rolling method, method of spin coating (spin-coating method), slit die rubbing method, excellent rubbing method.In these coating processes, preferred spin-coating method or slit die rubbing method, particularly preferably slit die rubbing method.The condition of prebake according to the kind of each composition, blending ratio etc. and different, is preferably carried out about 1～10 minute at 70～120 ℃.
< (2) irradiates the operation > of radioactive ray at least a portion of filming
In the operation of above-mentioned (2), by least a portion of the filming exposure forming.In this case, when a part of filming is exposed, conventionally by thering is the photomask exposure of predetermined pattern.The radioactive ray that use during as exposure, suitable is the radioactive ray that light acid producing agent is used.In these radioactive ray, optimal wavelength, at the radioactive ray of the scope of 190～450nm, particularly preferably contains the ultraviolet radioactive ray of 365nm.
Exposure in this operation is the value obtaining by the intensity under the wavelength 365nm of illuminometer (OAI model 356, OAI Optical Associates Inc. manufactures) mensuration radioactive ray, is preferably 500～6,000J/m 2, more preferably 1500～1,800J/m 2.
< (3) developing procedure >
In the operation of above-mentioned (3), by by the painting film development after exposure, remove unwanted part (illuminated portions of radioactive ray), form the pattern of regulation.As the developer solution using in developing procedure, the aqueous solution of preferred bases (alkali compounds).As the example of alkali, can list the inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, the quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide etc.
In addition, in this aqueous alkali, can also add in right amount water-miscible organic solvent or the surfactants such as methyl alcohol, ethanol.From obtaining the viewpoint of suitable developability, more than the concentration of the alkali in aqueous alkali is preferably 0.1 quality %, below 5 quality %.As developing method, can utilize suitable methods such as containing liquid method, infusion process, vibrations infusion process, shower method.Development time according to the composition of positive radiation line sensitive compositions and different, is preferably about 10～180 seconds.After this development treatment, for example carry out after flowing water washing in 30～90 seconds, for example air-dry by pressurized air or compressed nitrogen, can form desirable pattern.
< (4) heating process >
In the operation of above-mentioned (4), use the heating arrangements such as hot plate, baking oven, to forming the film heating of pattern, promote the curing reaction of above-mentioned [A] composition and [C] composition, can obtain solidfied material.Heating-up temperature in this operation is for example 120～250 ℃.Heat time according to the kind of firing equipment and different, for example, while carrying out heating process on hot plate, carries out 5～30 minutes; While carrying out heating process in baking oven, it is 30～90 minutes.Can also use interim baking process carrying out more than twice heating process etc.Like this, can form the pattern-like film corresponding to needed interlayer dielectric at substrate surface.
< interlayer dielectric >
The thickness of the interlayer dielectric forming is like this preferably 0.1～8 μ m, more preferably 0.1～6 μ m, more preferably 0.1～4 μ m.
The interlayer dielectric being formed by positive radiation line sensitive compositions of the present invention also, as shown in following embodiment, can harmonious meet thermotolerance and the transparency character of General Requirements so well, has without the irregular height planarization of coating simultaneously.Therefore, this interlayer dielectric is suitable as the purposes use of display element.
[embodiment]
Below, represent synthesis example, embodiment, the present invention is described more specifically, but the present invention is not subject to the restriction of following examples.
Hereinafter, the gel permeation chromatography (GPC) that the matter average molecular weight (Mw) of polymkeric substance and number-average molecular weight (Mn) are undertaken by following condition is measured.
Device: GPC-101 (clear and electrician (Co., Ltd.) manufactures)
Post: combination GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804
Mobile phase: tetrahydrofuran
Column temperature: 40 ℃
Flow velocity: 1.0mL/ minute
Sample solution concentration: 1.0 quality %
Sample injection rate IR: 100 μ L
Detecting device: differential refraction rate meter
Standard substance: monodisperse polystyrene
The synthesis example > of < polymkeric substance (A)
[synthesis example 1]
In thering is the flask of condenser pipe and stirrer, add 7 mass parts 2,2 '-azo two (2,4-methyl pentane nitrile), 200 mass parts diethylene glycol ethyl-methyl ethers.Then, add 5 mass parts methacrylic acids, 40 mass parts methacrylic acid 1-ethoxyethyl group esters, 5 mass parts styrene, 40 mass parts methyl propenoic acid glycidyl base esters, 10 mass parts methacrylic acid 2-hydroxyethyl esters and 3 mass parts α-methylstyrenedimers, after nitrogen replacement, start slowly to stir.The temperature of solution is risen to 70 ℃, keep this temperature 5 hours, obtain the polymer solution that contains polymkeric substance (A-1).The matter average molecular weight (Mw) of the polystyrene conversion of polymkeric substance (A-1) is 9,000.The solid component concentration of the polymer solution obtaining here in addition, (refers to that the quality of the polymkeric substance containing in polymer solution occupies the ratio of the all-mass of polymer solution.Identical below) be 32.1 quality %.
[synthesis example 2]
In thering is the flask of condenser pipe and stirrer, add 7 mass parts 2,2 '-azo two (2,4-methyl pentane nitrile), 200 mass parts diethylene glycol ethyl-methyl ethers.Then, add 5 mass parts methacrylic acids, 40 mass parts methacrylic acid tetrahydrochysene-2H-pyrans-2-base esters, 5 mass parts styrene, 40 mass parts methyl propenoic acid glycidyl base esters, 10 mass parts methacrylic acid 2-hydroxyethyl esters and 3 mass parts α-methylstyrenedimers, after nitrogen replacement, start slowly to stir.The temperature of solution is risen to 70 ℃, keep this temperature 5 hours, obtain the polymer solution that contains polymkeric substance (A-2).The matter average molecular weight (Mw) of the polystyrene conversion of polymkeric substance (A-2) is 9,000.The solid component concentration of the polymer solution obtaining here in addition, is 31.3 quality %.
[synthesis example 3]
In thering is the flask of condenser pipe and stirrer, add 7 mass parts 2,2 '-azo two (2 Methylpropionic acid methyl esters), 200 mass parts propylene glycol monomethyl ether.Then, add 67 mass parts methacrylic acid 1-n-butoxy ethyl esters, 23 mass parts methacrylic acid benzyl esters, 10 mass parts methacrylic acids, after nitrogen replacement, start slowly to stir.The temperature of solution is risen to 80 ℃, this temperature is kept 6 hours, obtain the polymer solution that contains polymkeric substance (a-1).The matter average molecular weight (Mw) of the polystyrene conversion of polymkeric substance (a-1) is 9,000.The solid component concentration of the polymer solution obtaining here in addition, is 30.3 quality %.
[synthesis example 4]
In thering is the flask of condenser pipe and stirrer, add 7 mass parts 2,2 '-azo two (2 Methylpropionic acid methyl esters), 200 mass parts propylene glycol monomethyl ether.Then, add 90 mass parts methacrylic acid 1-benzyloxy ethyl esters, 6 mass parts methacrylic acid 2-hydroxyethyl esters, 4 mass parts methacrylic acids, after nitrogen replacement, start slowly to stir the temperature of solution is risen to 80 ℃, this temperature is kept 6 hours, obtain the polymer solution that contains polymkeric substance (a-2).The matter average molecular weight (Mw) of the polystyrene conversion of polymkeric substance (a-2) is 9,000.The solid component concentration of the polymer solution obtaining here in addition, is 31.2 quality %.
[synthesis example 5]
In thering is the flask of condenser pipe and stirrer, add 7 mass parts 2,2 '-azo two (2 Methylpropionic acid methyl esters), 200 mass parts propylene glycol monomethyl ether.Then, add 85 mass parts methacrylic acid tetrahydrochysene-2H-pyrans-2-base esters, 7 mass parts methacrylic acid 2-hydroxyethyl esters, 8 mass parts methacrylic acids, after nitrogen replacement, start slowly to stir.The temperature of solution is risen to 80 ℃, this temperature is kept 6 hours, obtain the polymer solution that contains polymkeric substance (a-3).The matter average molecular weight (Mw) of the polystyrene conversion of polymkeric substance (a-3) is 10,000.The solid component concentration of the polymer solution obtaining here in addition, is 29.2 quality %.
[synthesis example 6]
In thering is the flask of condenser pipe and stirrer, add 7 mass parts 2,2 '-azo two (2,4-methyl pentane nitrile), 200 mass parts diethylene glycol ethyl-methyl ethers.Then, add 52 mass parts methyl propenoic acid glycidyl base esters, 48 mass parts methacrylic acid benzyl esters, after nitrogen replacement, start slowly to stir.The temperature of solution is risen to 80 ℃, this temperature is kept 6 hours, obtain the polymer solution that contains polymkeric substance (aa-1).The matter average molecular weight (Mw) of the polystyrene conversion of polymkeric substance (aa-1) is 10,000.The solid component concentration of the polymer solution obtaining here in addition, is 32.3 quality %.
[synthesis example 7]
In thering is the flask of condenser pipe and stirrer, add 7 mass parts 2,2 '-azo two (2,4-methyl pentane nitrile), 200 mass parts diethylene glycol ethyl-methyl ethers.Then, add 45 mass parts methacrylic acids 3,4-epoxycyclohexyl methyl ester, 45 mass parts methacrylic acid benzyl esters, 10 mass parts methacrylic acids, after nitrogen replacement, start slowly to stir.The temperature of solution is risen to 80 ℃, this temperature is kept 6 hours, obtain the polymer solution that contains polymkeric substance (aa-2).The matter average molecular weight (Mw) of the polystyrene conversion of polymkeric substance (aa-2) is 10,000.The solid component concentration of the polymer solution obtaining here in addition, is 33.2 quality %.
[synthesis example 8]
In thering is the flask of condenser pipe and stirrer, add 7 mass parts 2,2 '-azo two (2,4-methyl pentane nitrile), 200 mass parts diethylene glycol ethyl-methyl ethers.Then, add 35 mass parts methacrylic acid 1-n-butoxy ethyl esters, 35 mass parts methacrylic acid benzyl esters, 30 mass parts glycidyl methacrylate, after nitrogen replacement, start slowly to stir.The temperature of solution is risen to 80 ℃, this temperature is kept 6 hours, obtain the polymer solution that contains polymkeric substance (aa-3).The matter average molecular weight (Mw) of the polystyrene conversion of polymkeric substance (aa-3) is 10,000.The solid component concentration of the polymer solution obtaining here in addition, is 32.3 quality %.
The synthetic > of < multipolymer [C]
[synthesis example 9]
With stirring apparatus, in the glass flask of condenser and thermometer, add 28.4 mass parts as the compound shown in the above-mentioned formula (c1-1) of (c1) compound, " the NK-エ ス テ Le M-90G " that 20.7 mass parts are manufactured as (c2) compound Xin Zhong village chemistry (Co., Ltd.), 18.1 mass parts are as the compound shown in the following formula (c3-1-1-1) of (c3) compound, 5.9 mass parts methyl methacrylates and 23.5 mass parts 2-ethylhexyl acrylates as (c4) compound, 3.4 mass parts are as the compound 1 of (c5), the compound of two terminal methyl group acroleic acid esterifications of 4-butylene glycol and as 414 mass parts isopropyl alcohols of solvent, in nitrogen stream, under refluxing, add 0.7 mass parts as 2 of polymerization initiator, after 2 '-azoisobutyronitrile (AIBN) and the lauryl mercaptan of 4 mass parts as chain-transferring agent, at 75 ℃, reflux and within 8 hours, carry out copolymerization, obtain the solution that contains multipolymer (C-1).Afterwards, use evaporator, under the heating condition below 70 ℃, except desolventizing, isolate multipolymer (C-1).The number-average molecular weight Mn of the multipolymer obtaining (C-1) is 2,800, and matter average molecular weight Mw is 5,300, and molecular weight distribution (Mw/Mn) is 1.9.
(in formula, Me is methyl.)
[synthesis example 10]
Except making addition as the lauryl mercaptan of chain-transferring agent, be 1 mass parts, and above-mentioned synthesis example 3 similarly obtain multipolymer (C-2).The number-average molecular weight Mn of the multipolymer obtaining (C-2) is 4,700, and matter average molecular weight Mw is 11,000, and molecular weight distribution (Mw/Mn) is 2.3.
[synthesis example 11]
Except not being used as the lauryl mercaptan of chain-transferring agent, the temperature and time that makes copolymerization is respectively beyond 73 ℃ and 10 hours, and above-mentioned synthesis example 3 similarly, obtains multipolymer (C-3).The number-average molecular weight Mn of the multipolymer obtaining (C-3) is 5,600, and matter average molecular weight Mw is 21,000, and molecular weight distribution (Mw/Mn) is 3.8.
[synthesis example 12]
With stirring apparatus, in the glass flask of condenser and thermometer, add 31.8 mass parts as the compound shown in the above-mentioned formula (c1-3) of (c1) compound, " the NK-エ ス テ Le M-90G " that 31.6 mass parts are manufactured as (c2) compound Xin Zhong village chemistry (Co., Ltd.), 29.0 mass parts are as compound and the 414 mass parts isopropyl alcohols shown in the above-mentioned formula (c3-1-1-1) of (c3) compound, in nitrogen stream, under refluxing, add 0.7 mass parts as the AIBN of polymerization initiator, after the lauryl mercaptan of 4 mass parts as chain-transferring agent, at 75 ℃, reflux and within 8 hours, carry out copolymerization, obtain the solution that contains multipolymer (C-4).Afterwards, use evaporator, under the heating condition below 70 ℃, except desolventizing, isolate separately multipolymer (C-4).The number-average molecular weight Mn of the multipolymer obtaining (C-4) is 3,500, and matter average molecular weight Mw is 7,000.And molecular weight distribution (Mw/Mn) is 2.0.
[synthesis example 13]
With stirring apparatus, in the glass flask of condenser and thermometer, add 24.2 mass parts as the compound shown in the above-mentioned formula (c1-5) of (c1) compound, " the NK-エ ス テ Le M-90G " that 20.7 mass parts are manufactured as (c2) compound Xin Zhong village chemistry (Co., Ltd.), 21.5 mass parts are as the compound shown in the above-mentioned formula (c3-1-1-1) of (c3) compound, 29.4 mass parts are as n-BMA and the 414 mass parts isopropyl alcohols of (c4) compound, in nitrogen stream, under refluxing, add 0.7 mass parts as the AIBN of polymerization initiator, after the lauryl mercaptan of 4 mass parts as chain-transferring agent, at 75 ℃, reflux and within 8 hours, carry out copolymerization, obtain the solution that contains multipolymer (C-5).Afterwards, use evaporator, under the heating condition below 70 ℃, except desolventizing, isolate multipolymer (C-5).The number-average molecular weight Mn of the multipolymer obtaining (C-5) is 3,500, and matter average molecular weight Mw is 6,000.And molecular weight distribution (Mw/Mn) is 1.7.
[synthesis example 14]
With stirring apparatus, in the glass flask of condenser and thermometer, add 16.6 mass parts as the compound shown in the above-mentioned formula (c1-7) of (c1) compound, " the NK-エ ス テ Le M-90G " that 20.7 mass parts are manufactured as (c2) compound Xin Zhong village chemistry (Co., Ltd.), 21.5 mass parts are as the compound shown in the above-mentioned formula (c3-1-1-1) of (c3) compound, 29.4 mass parts are as n-BMA and the 414 mass parts isopropyl alcohols of (c4) compound, in nitrogen stream, under refluxing, add 0.7 mass parts as the AIBN of polymerization initiator, after the lauryl mercaptan of 4 mass parts as chain-transferring agent, at 75 ℃, reflux and within 8 hours, carry out copolymerization, obtain the solution that contains multipolymer (C-5).Afterwards, use evaporator, under the heating condition below 70 ℃, except desolventizing, isolate multipolymer (C-5).The number-average molecular weight Mn of the multipolymer obtaining (C-5) is 4,000, and matter average molecular weight Mw is 7,000.And molecular weight distribution (Mw/Mn) is 1.8.
The preparation > of < positive radiation line sensitive compositions
[embodiment 1]
In the solution that contains polymkeric substance (A-1) obtaining in synthesis example 1 (amount that is equivalent to 100 mass parts hydrolytic condensate (A-1) (solid constituent)), mix the multipolymer (C-1) that 3 mass parts obtain as the synthesis example 9 of [C] composition as the IRGACURE PAG 103 of [B] composition (チ バ ス ペ シ ヤ リ テ イ mono-ケミカル ズ company manufactures), 0.50 mass parts, then add as the diethylene glycol ethyl-methyl ether of solvent so that after solid component concentration is 25 quality %, membrane filter by bore 0.2 μ m filters, and prepares positive radiation line sensitive compositions (S-1).
[embodiment 2～12 and comparative example 1～5]
Except each composition kind with measuring as described in Table 1, and embodiment 1 similarly prepares positive radiation line sensitive compositions.In addition, the composition using in each embodiment and comparative example is as follows.
(light acid producing agent: B composition)
B-1: above-claimed cpd (i) (" IRGACURE PAG 103 " that チ バ ス ペ シ ヤ リ テ イ mono-ケミカル ズ company manufactures)
B-2: above-claimed cpd (ii) (" IRGACURE PAG 108 " that チ バ ス ペ シ ヤ リ テ イ mono-ケミカル ズ company manufactures)
B-3: above-claimed cpd (iii) (" C GI 1380 " that チ バ ス ペ シ ヤ リ テ イ mono-ケミカル ズ company manufactures)
B-4: above-claimed cpd (iv) (" IRGACURE PAG 121 " that チ バ ス ペ シ ヤ リ テ イ mono-ケミカル ズ company manufactures)
B-5: above-claimed cpd (v) (" CGI 725 " that チ バ ス ペ シ ヤ リ テ イ mono-ケミカル ズ company manufactures)
(surfactant)
C-1 (comparative example 1): " SH-193 " that organosilicone surfactants (East レ ダ ウ コ mono-ニ Application グ シ リ コ mono-Application (Co., Ltd.) is manufactured)
C-2 (comparative example 2): fluorochemical surfactant (" Off ロ ラ mono-De F-430 " that (Co., Ltd.) ス リYiエム company manufactures)
(closely sealed auxiliary agent: D composition)
D-1: γ-glycidoxypropyltrimewasxysilane
D-2: β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane
D-3: γ-methacryloxypropyl trimethoxy silane
(alkali compounds: E composition)
E-1:4-dimethyl aminopyridine
E-2:1,5-diazabicylo [4,3,0]-5-nonene
< evaluation of physical property >
Use the as above various positive radiation line sensitive compositions of preparation, evaluate as follows said composition and as filming or the various character of interlayer dielectric.
(1) ocular estimate of filming
The radiation-ray sensitive composition that uses slit die formula spreader (model " TR632105-CL " that Tokyo answers chemical industry (Co., Ltd.) to manufacture) as above to prepare in the coating on glass of the formation chromium film of 550 * 650mm, extreme pressure is set as to 100Pa, under vacuum, remove after desolventizing, and then carry out 2 minutes prebake at 90 ℃, form filming of thickness 3.0 μ m.Under sodium vapor lamp, this outward appearance of filming by visual inspection.Now, what film integral was produced is vaporific irregular as " vaporific irregular ", using from prebake stove approach the irregular as " selling irregular " of pin (プ ロ キ シ ピ Application), study it and occur situation.Nearly all do not find that these irregular situations are evaluated as " zero (well) ", find that on a small quantity these irregular situations are arbitrarily evaluated as " △ (slightly well) ", the situation being clear that is evaluated as " * (bad) ".Evaluation result represents in table 1.
(2) evaluation of film thickness uniformity (consistance)
Use probe contact analyzer (AS200 that KLA Tencor company manufactures) to measure the thickness of filming on glass of the formation chromium film of as above manufacturing.As consistance, from the thickness of 9 measuring points, calculate.9 described measuring points are that the short-axis direction of hypothesis substrate is X, long axis direction is Y, and (X[mm], Y[mm]) is (275,20), (275,30), (275,60), (275,100), (275,325), (275,550), (275,590), (275,620), (275,630).
Conforming calculating formula represents by following formula.The FT of following formula (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.Consistance is 2% when following, can judge that film thickness uniformity is good.Evaluation result represents in table 1.
(conforming calculating formula)
Consistance (%)={ FT (X, Y) max-FT (X, Y) min} * 100/{2 * FT (X, Y) avg.}
(3) evaluation of high-speed coating
On the alkali-free glass substrate of 550mm * 650mm, use the coating of slot coated device, coating condition be the distance (GAP) of substrate and nozzle be 150 μ m, exposure after thickness be 2.5 μ m, from nozzle ejection coating fluid, the translational speed of nozzle is to change in 120mm/s～220mm/s, tries to achieve and does not produce the irregular maximal rate of liquid cut-out generation strip.Now, even under the speed more than 180mm/s, do not produce the irregular situation of strip yet, can be judged as and can adapt to high-speed coating.Evaluation result represents in table 1.
(4) the radioactive ray sensitivity of radiation-ray sensitive composition is evaluated
Coating hexamethyldisilazane on glass (HMDS) at the formation chromium film of 550 * 650mm heats 1 minute (HMDS processing) at 60 ℃.Use slit die spreader " TR632105-CL ", the radiation-ray sensitive composition that the coating on glass of the formation chromium film after this HMDS processes is as above prepared, by the pressure setting reaching, be 100Pa, under vacuum, remove after desolventizing, and then carry out 2 minutes prebake at 90 ℃, form filming of thickness 3.0 μ m.Then, the MPA-600FA exposure machine that uses キ ヤ ノ Application (Co., Ltd.) to manufacture, by thering is the line sky of 60 μ m than the mask of the pattern of (10 pairs 1), take to the exposure of filming as variable, irradiate after radioactive ray, in the tetramethyl ammonium hydroxide aqueous solution of the concentration of recording at table 1, at 25 ℃, by containing liquid method, develop.Here, development time is when to use the concentration of tetramethylammonium hydroxide be the developer solution of 0.40 quality % to be 80 seconds, while using the developer solution of 2.38 quality %, is 50 seconds.Then, by ultrapure water, carry out 1 minute flowing water and wash, by dry, on the substrate of the formation chromium film after HMDS processes, form pattern afterwards.Now, research is dissolved necessary exposure completely by the space pattern of 6 μ m.This value is represented in table 1 as radioactive ray sensitivity.This value is 500J/m 2when following, think that sensitivity is good.
(5) the stable on heating evaluation of interlayer dielectric
With the situation of above-mentioned [evaluation of the solvent resistance of interlayer dielectric] similarly, in the formation cured film on glass that forms chromium film.Measure the thickness (T2) of the cured film obtaining here.Then, the glass substrate of formation chromium film that forms this cured film in clean baking oven, append heating after 1 hour at 240 ℃, is measured to the thickness (t2) of cured film again, by following formula, calculate the Thickness Variation rate that heating causes of appending.This value is 5% when following, thinks that thermotolerance is good.Evaluation result represents in table 1.
(calculating formula of Thickness Variation rate)
Thickness Variation rate (%)=| t2-T2|/T2} * 100
(6) the transparent evaluation of interlayer dielectric
Except using the glass substrate (NH テ Network ノ グ ラ ス (Co., Ltd.) company manufacture " NA35 ") of 550 * 650mm to replace forming the glass substrate of chromium film, with the situation of above-mentioned [evaluation of the solvent resistance of interlayer dielectric] similarly, on glass substrate, form cured film.Use spectrophotometer " 150-20 type ダ Block Le PVC one system ((the) Li System of Co., Ltd. does manufacturing) ", using and there is no the glass substrate of cured film as with reference to side, under the wavelength of the scope of 400～800nm, measure the light penetration of the glass substrate of the cured film with formation.The value of minimum light penetration now represents in table 1.This value is 90% when above, thinks that the transparency is good.
As shown in the result of table 1, can know that the positive radiation line sensitive compositions that contains [A], [B] and the embodiment 1～12 of [C] composition compares with the positive radiation line sensitive compositions containing the comparative example 1～3 of [C] composition not, even high-speed coating, aspect the planarization of the irregular and interlayer dielectric of coating in coating in outward appearance, also more excellent.In addition, the positive radiation line sensitive compositions of these embodiment, when having high radioactive ray sensitivity, can also form the interlayer dielectric of the character that can fully meet thermotolerance and the such General Requirements of the transparency.
Industrial applicibility
Positive radiation line sensitive compositions of the present invention as mentioned above, can high-speed coating, has high radioactive ray sensitivity, can form except having enough thermotolerance and the transparency, also has the cured film of excellent planarization.Therefore, this positive radiation line sensitive compositions is suitable for forming the interlayer dielectric that display element is used.

Claims (6)

1. a positive radiation line sensitive compositions, said composition comprises:
[A] has the structural unit that comprises the group shown in following formula (1) and the polymkeric substance that contains the structural unit of epoxy radicals in same or different polymer molecules,
[B] light acid producing agent, and
The multipolymer that the composition that [C] comprises following compound by the total amount with respect to polymerizable compound (c1)～(c5) forms, described compound is:
Polymerizable compound shown in (c1) following formula (6) of 25～35 quality %,
Polymerizable compound shown in (c2) following formula (7) of 20～30 quality %,
(c3) of 15～20 quality % has the polymerizable compound of the group shown in following formula (4),
(c4) of 25～35 quality % has the polymerizable compound that carbon number is 1～8 non-substituted alkyl ester group, and
(c5) of 1～5 quality % has the polymerizable compound of more than two unsaturated link in a part;
In formula (1), R 1and R 2be hydrogen atom, alkyl, naphthenic base or aryl independently of one another, part or all of the hydrogen atom of these alkyl, naphthenic base or aryl can be substituted group and replace, and still, do not comprise R 1and R 2all the situation of hydrogen atom, R 3be alkyl, naphthenic base, aralkyl or aryl, part or all of these hydrogen atom can be substituted group and replace, R 1and R 3can be connected to form cyclic ether, wherein said substituted radical is selected from halogen atom, hydroxyl, nitro, cyano group, carboxyl, carbonyl, naphthenic base, aryl, alkoxy, acyl group, acyloxy, alkoxy carbonyl and haloalkyl;
In formula (4), R 7, R 8, R 9, R 10and R 11be the group shown in alkyl, phenyl or the following formula (5) of carbon number 1～20 independently of one another, b is 0～3 integer,
In formula (5), R 12, R 13and R 14be the alkyl or phenyl of carbon number 1～20 independently of one another, c is 0～3 integer,
CH 2=CR 4COOC 2H 4C βF 2β+1 (6)
In formula (6), R 4be hydrogen atom or methyl, β is 1～8 integer,
CH 2＝CR 5COO(C 2H 4O) aR 6 (7)
In formula (7), R 5hydrogen atom or methyl, R 6be that carbon number is 1～12 alkyl, the quantity mean value that structural unit is counted a is 4～12.
2. the positive radiation line sensitive compositions of recording according to claim 1, wherein further contains [D] closely sealed auxiliary agent.
3. the positive radiation line sensitive compositions of recording according to claim 1, wherein further contains [E] alkali compounds.
4. the positive radiation line sensitive compositions of recording according to claim 1, it is used to form the interlayer dielectric of display element.
5. the formation method of interlayer dielectric for display element, the method comprises:
(1) on substrate, form the operation of filming of the positive radiation line sensitive compositions that claim 4 records,
(2) at least a portion of filming forming in operation (1) is irradiated to the operation of radioactive ray,
(3) will in operation (2), irradiate the operation of the painting film development of radioactive ray, and
(4) operation to the heating of filming of developing in operation (3).
6. the interlayer dielectric of the display element that the positive radiation line sensitive compositions of being recorded by claim 4 forms.
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