CN101788767B - Radiation sensitive linear resin composition and layer insulation film and manufacture method thereof - Google Patents

Radiation sensitive linear resin composition and layer insulation film and manufacture method thereof Download PDF

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CN101788767B
CN101788767B CN2010101041369A CN201010104136A CN101788767B CN 101788767 B CN101788767 B CN 101788767B CN 2010101041369 A CN2010101041369 A CN 2010101041369A CN 201010104136 A CN201010104136 A CN 201010104136A CN 101788767 B CN101788767 B CN 101788767B
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compound
resin composition
methyl
radiation sensitive
multipolymer
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CN101788767A (en
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花村政晓
长屋胜也
丸山拓之
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making

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Abstract

The invention relates to a radiation sensitive linear resin composition, a layer insulation film and a manufacture method thereof. The radiation sensitive linear resin composition also displays the excellent film thickness uniformity and has high ray sensibility even thought a slot mold coating method as the coating method. In a developing step, the development tolerance of a good pattern shape is still formed even though exceeding the best developing time. The layer insulation film has various excellent performances such as high heat endurance, high solvent resistance, high transmittance and low dielectric constant. The radiation sensitive linear resin composition comprises (A)alkali soluble resin, (B) 1,2-quinone-bi-azide compound and (C) special polymer with siloxane chain. The layer insulation film is formed by the radiation sensitive linear resin composition.

Description

Radiation sensitive linear resin composition and interlayer dielectric and manufacture method thereof
Technical field
The present invention relates to radiation sensitive linear resin composition and interlayer dielectric and manufacture method thereof.
Background technology
The electronic units such as thin film transistor (TFT) (hereinafter referred to as " TFT ") type liquid crystal display cells and magnetic head element, integrated circuit component, solid state image sensor element, usually in order to be insulated between the wiring of layered arrangement, arrange interlayer dielectric.Due to the material as forming interlayer dielectric, be preferably that to obtain the required operation of necessary pattern form few and have the material of height flatness, thereby radiation sensitive linear resin composition is widely used (referring to patent documentation 1 and patent documentation 2).
In above-mentioned electronic unit, TFT type liquid crystal display cells for example, form ELD owing to passing through on above-mentioned interlayer dielectric, form the operation of liquid crystal orientation film thereon again and manufacture, thereby interlayer dielectric forms in operation and will stand hot conditions in ELD, and stand when electrode pattern forms the resist layer stripper used, therefore, to it, must there is enough good tolerance.
The interlayer dielectric so made, in developing procedure when it forms, if development time is even exceed a little Best Times, also be easy to occur the developer solution infiltration and cause coming off between pattern and substrate, therefore, must strictly control development time, and be a problem in the yield rate aspect of goods very much.
In recent years, in TFT type liquid crystal display cells field, be in the trend of giant-screen, high brightness, high-precision refinement, quick responseization, slimming etc., as it, interlayer dielectric used forms and uses composition, requirement has high sensitive, and formed interlayer dielectric, require to have than in the past more superior low-k, the contour performance of high transmission rate.
Like this, when by radiation sensitive linear resin composition, forming interlayer dielectric, as composition, requirement has high sensitive, and, require in the developing procedure in forming operation, even when development time exceeds when fixed time, also coming off of pattern can not occur, and show good cohesive, and the interlayer dielectric formed by it has high-fire resistance, high solvent resistance, low-k, high transmission rate etc.But the radiation sensitive linear resin composition that meets this requirement so far or unknown.
And the requirement reduced along with trend and the production cost of large screen television in recent years, be in the impetus of maximization with base plate glass size used in the manufacture of the substrate of color filter.Therefore, in the working procedure of coating of the radiation sensitive linear resin composition carried out while on substrate, forming interlayer dielectric, before adopting, widely used spin-coating method is very difficult, and coating method replaces with the so-called slit die coating process applied by slit-like nozzle ejection composition.This slit die coating process, compare with spin-coating method, both had advantages of the amount that can reduce the required composition of coating, also is conducive to reduce the production cost of liquid crystal display cells.But, in this slit die coating process, under the adsorbed state of vacuum suction substrate, scan the coating mouth and applied with certain direction, then, the supporting pin remained in the hole that vacuum suction uses rises and, by substrate jack-up, it is transplanted on to subsequent processing from coating platform.Therefore, in a series of operation, the situation of the strip spot presented on the spot that the hole that there will be the upper generation of filming to be used by vacuum suction causes, the spot that supporting pin causes, coating mouth sweep directions etc., thus the obstacle of realizing height flatness as above become.
Prior art
[patent documentation]
[patent documentation 1] TOHKEMY 2001-354822 communique
[patent documentation 2] TOHKEMY 2001-343743 communique
Summary of the invention
The present invention In view of the foregoing makes, its objective is a kind of radiation sensitive linear resin composition is provided, even adopt the slit die coating process as coating method, also can demonstrate good thickness homogeneity, and there is high radiation-sensitive degree, in developing procedure, exceed even have the development nargin that optimum development time still can form good pattern form, and interlayer dielectric and manufacture method thereof that the various function admirables such as high-fire resistance, high solvent resistance, high transmission rate, low-k are provided.
Above object and advantages of the present invention, the first, by a kind of radiation sensitive linear resin composition, to be reached, it contains:
(A) alkali soluble resin;
(B) 1,2-quinone di-azido compound (hereinafter referred to as " compound (B) "); And
(C) contain (c1) following formula (1 0) compound (hereinafter referred to as " compound (c1) "), (c2) following general formula (2 of meaning 0) multipolymer (hereinafter referred to as " multipolymer (C) ") of polymerizable unsaturated compound of polymerizable unsaturated compound (hereinafter referred to as " compound (c3) ") of the compound (hereinafter referred to as " compound (c2) ") meaned and the group that (c3) there is following general formula (3) expression.
CH 2＝CR 1COO-C αH 2α-C βF 2β+1 (1 0)
Formula (1 0) in, R 1for hydrogen atom or methyl, the integer that α is 0～6, the integer that β is 1～20.
CH 2＝CR 2COO-(C γH 2γ-O) a-R 3 (2 0)
Formula (2 0) in, R 2for hydrogen atom or methyl, R 3for the carbon number alkyl that is 1～12, γ be 2 or 3, a be number of repeat unit, its mean values is 1～30.
Figure GSA00000009826700041
In formula (3), R 4, R 5, R 6, R 7and R 8the group that the alkyl that is 1～20 for carbon number independently of one another, phenyl or following general formula (4) mean, the integer that b is 0～3.
Figure GSA00000009826700042
In formula (4), R 9, R 10and R 11the alkyl or phenyl that is 1～20 for carbon number independently of one another, the integer that c is 0～3.
Above object and advantages of the present invention, the second, by the interlayer dielectric formed with above-mentioned radiation sensitive linear resin composition, reached.
Above object and advantages of the present invention, the 3rd, by the method that forms of the interlayer dielectric that comprises in the following order following operation, reached,
(1) above-mentioned radiation sensitive linear resin composition is coated in to the operation that on substrate, formation is filmed,
(2) operation of at least a portion useful to irradiation of rays of this being filmed,
(3) developing procedure, and
(4) heating process.
Above object and advantages of the present invention, the 4th, by the interlayer dielectric that adopts said method to form, reached.
If employing the present invention, can provide a kind of radiation sensitive linear resin composition, even adopt the slit die coating process as coating method, also can demonstrate good thickness homogeneity, and there is high radiation-sensitive degree, in developing procedure, exceed even have the development nargin that optimum development time still can form good pattern form, and interlayer dielectric and the manufacture method thereof of the various function admirables such as high-fire resistance, high solvent resistance, high transmission rate, low-k can be provided.
Embodiment
Below, the present invention is specifically described.
<(A) alkali soluble resin >
As (A) alkali soluble resin contained in radiation sensitive linear resin composition of the present invention, so long as the alkali soluble resin that has solubility for developer solution used in following developing procedure (preferred bases developer solution) has no particular limits.As this (A) alkali soluble resin, preferably there is at least one the alkali soluble resin be selected from the group that carboxyl and acid anhydride form, can be applicable to using and for example contain the multipolymer (hereinafter referred to as " multipolymer (A) ") of monomer that (a1) is selected from least one (hereinafter referred to as " compound (a1) ") in the group that unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides form and (a2) has the polymerizable unsaturated compound (hereinafter referred to as " compound (a2) ") of epoxy radicals.
The multipolymer of the monomer that multipolymer (A) can be comprised of above-claimed cpd (a 1) and compound (a2), can be also perhaps the multipolymer that also contains the monomer of (a3) their polymerizable unsaturated compounds (hereinafter referred to as " compound a 3 ") in addition except above-claimed cpd (a1) and compound (a2), and be preferably the latter.
Multipolymer (A) can by by monomer as above preferably in solvent, preferably under the existence of polymerization initiator, carry out free radical polymerization and prepare.
[compound (a1)]
In the multipolymer used in the present invention (A), based on by compound (a1), (a2) and (a3) total amount of derivative repetitive, preferably contain 5～40 quality %, particularly preferably contain 5～25 quality % by the derivative Component units of compound (a1).When the ratio of this Component units is 5～40 quality %, can obtain the balanced radiation sensitive linear resin composition in the various performance higher levels ground such as radiation-sensitive degree, developability and storage stability.
Compound (a1) is at least one being selected from the group that unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides form, and can enumerate such as the acid anhydrides of monocarboxylic acid, dicarboxylic acid, dicarboxylic acid, the list of polybasic carboxylic acid [(methyl) acryloxyalkyl] ester, two ends and have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl, the polycyclic compound with carboxyl and acid anhydrides thereof etc.
As its object lesson, monocarboxylic acid can be enumerated such as acrylic acid, methacrylic acid, crotonic acid etc.;
Dicarboxylic acid can be enumerated such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc.;
The acid anhydrides of dicarboxylic acid can be enumerated such as above-mentioned dicarboxylic acid and the acid anhydrides of illustrative compound etc.;
The list of polybasic carboxylic acid [(methyl) acryloxyalkyl] ester can be enumerated such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester etc.;
Two ends have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl can enumerate list (methyl) acrylate such as ω-carboxyl polycaprolactone etc.;
Polycyclic compound and acid anhydrides thereof with carboxyl can be enumerated for example 5-carboxyl two ring [2.2.1] hept-2-ene"s, 5,6-dicarboxyl two ring [2.2.1] hept-2-ene"s, 5-carboxyl-5-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl two ring [2.2.1] hept-2-ene"s, 5-carboxyl-6-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl two ring [2.2.1] hept-2-ene"s, 5,6-dicarboxyl two ring [2.2.1] hept-2-ene" acid anhydrides etc.
In the middle of them, preferably use the acid anhydrides of monocarboxylic acid, dicarboxylic acid, from copolymerization, for dissolubility and the easy acquired aspect consideration of aqueous alkali, particularly preferably use acrylic acid, methacrylic acid, maleic anhydride.These compounds (a1) can be used alone or in combination.
(compound (a2))
The multipolymer used in the present invention (A), based on by compound (a1), (a2) and (a3) total amount of derivative repetitive, preferably contain 10～80 quality %, particularly preferably contain 30～80 quality % by the derivative Component units of compound (a2).When the ratio of this Component units is 10～80 quality %, can obtain the thermotolerance of interlayer dielectric and the balanced radiation sensitive linear resin composition in storage stability higher level ground of solvent resistance and radiation sensitive linear resin composition.
Compound (a2) is the polymerizable unsaturated compound with epoxy radicals.Here, as epoxy radicals, can enumerate epoxy ethyl (thering is 1,2-epoxy radicals structure), oxa-cyclobutyl (thering is 1,3-epoxy radicals structure) etc.
As the polymerizable unsaturated compound with epoxy ethyl, can enumerate for example glycidyl acrylate, glycidyl methacrylate, the α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, acrylic acid 3, 4-epoxy radicals butyl ester, methacrylic acid 3, 4-epoxy radicals butyl ester, acrylic acid 6, 7-epoxy radicals heptyl ester, methacrylic acid 6, 7-epoxy radicals heptyl ester, α-ethylacrylate 6, 7-epoxy radicals heptyl ester, adjacent vinyl benzyl glycidyl ether, between the vinyl benzyl glycidyl ether, to the vinyl benzyl glycidyl ether, methacrylic acid-3, 4-epoxy radicals cyclohexyl ester etc.Wherein, preferable methyl glycidyl acrylate, methacrylic acid 6,7-epoxy radicals heptyl ester, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether, methacrylic acid 3,4-epoxy radicals cyclohexyl ester etc.;
As the unsaturated compound with oxa-cyclobutyl, can enumerate for example 3-(acryloyl-oxy ylmethyl) oxetanes, 3-(acryloyl-oxy ylmethyl)-2-methyl oxetanes, 3-(acryloyl-oxy ylmethyl)-3-Ethyloxetane, 3-(acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 3-(2-acryloxy ethyl) oxetanes, 3-(2-acryloxy ethyl)-2-Ethyloxetane, 3-(2-acryloxy ethyl)-3-Ethyloxetane, 3-(2-acryloxy ethyl)-2-phenyl oxetanes, 3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-2-methyl oxetanes, 3-(methacryloxy methyl)-3-Ethyloxetane, 3-(methacryloxy methyl)-2-phenyl oxetanes, 3-(2-methacryloxyethyl) oxetanes, 3-(2-methacryloxyethyl)-2-Ethyloxetane, 3-(2-methacryloxyethyl)-3-Ethyloxetane, 3-(2-methacryloxyethyl)-2-phenyl oxetanes etc.
These compounds (a2) can be used alone or in combination.
[compound (a3)]
The multipolymer used in the present invention (A), based on by compound (a1), (a2) and (a3) total amount of derivative repetitive, preferably contain 1～50 quality %, particularly preferably contain 5～50 quality % by the derivative Component units of compound (a3).When the ratio of this Component units is 1～50 quality %, can obtain the thermotolerance of formed interlayer dielectric and solvent resistance and the radiation sensitive linear resin composition balanced radiation sensitive linear resin composition in developability higher level ground for aqueous alkali.
Compound (a3) so long as have free-radical polymerised unsaturated compound, has no particular limits it.As compound (a3), can enumerate for example alkyl methacrylate, alkyl acrylate, methacrylic acid cycloalkyl ester, the methacrylate with hydroxyl, acrylic acid cycloalkyl ester, aryl methacrylate, acrylic acid aryl ester, unsaturated dicarboxylic diester, two ring unsaturated compounds, maleimide compound, unsaturated aromatics, conjugated diolefine;
Unsaturated compound with phenol hydroxyl of following formula (I) expression;
Unsaturated compound with skeleton of tetrahydrofuran skeleton, furans skeleton, oxinane skeleton, pyrans skeleton or following formula (II) expression; And other unsaturated compounds.
Figure GSA00000009826700091
In formula (I), R ifor hydrogen atom or carbon number be 1～4 alkyl, R iI～R vIidentical or different, be hydrogen atom, hydroxyl or the carbon number alkyl that is 1～4, B be singly-bound ,-COO-or-CONH-, the integer that m is 0～3, wherein, R iI～R vIin at least one is hydroxyl.
Figure GSA00000009826700092
In formula (II), R vIIfor hydrogen atom or methyl.
As their object lesson, as alkyl methacrylate, can enumerate such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, methacrylic acid n-butyl, methacrylic acid sec-butyl ester, methacrylic acid tertiary butyl ester, methacrylic acid 2-ethylhexyl, methacrylic acid isodecyl ester, methacrylic acid dodecyl ester, methacrylic acid tridecyl ester, methacrylic acid n-octadecane base ester etc.;
As alkyl acrylate, can enumerate such as methyl acrylate, isopropyl acrylate etc.;
As the methacrylic acid cycloalkyl ester, can enumerate for example methacrylic acid cyclohexyl ester, methacrylic acid 2-methylcyclohexyl ester, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base oxygen base ethyl ester, IBOMA etc.;
As the methacrylate with hydroxyl, can enumerate for example methacrylic acid hydroxyl methyl esters, 2-hydroxyethyl methacrylate, methacrylic acid 3-hydroxy propyl ester, methacrylic acid 4-hydroxyl butyl ester, diglycol monotertiary methacrylate, methacrylic acid 2,3-dihydroxy propyl ester, 2-methacryloxyethyl glucosides, methacrylic acid 4-hydroxy phenyl ester etc.;
As the acrylic acid cycloalkyl ester, can enumerate for example acrylic acid cyclohexyl ester, acrylic acid 2-methylcyclohexyl ester, acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, acrylic acid three rings [5.2.1.0 2,6] decane-8-base oxygen base ethyl ester, isobornyl acrylate etc.;
As aryl methacrylate, can enumerate such as methacrylic acid phenylester, methacrylic acid benzyl ester etc.;
As the acrylic acid aryl ester, can enumerate such as phenyl acrylate, acrylic acid benzyl ester etc.;
As the unsaturated dicarboxylic diester, can enumerate such as diethyl maleate, DEF, diethyl itaconate etc.;
As two ring unsaturated compounds, can enumerate for example two ring [2.2.1] hept-2-ene"s, 5-methyl bicyclic [2.2.1] hept-2-ene", 5-ethyl two ring [2.2.1] hept-2-ene"s, 5-methoxyl two ring [2.2.1] hept-2-ene"s, 5-ethoxy two ring [2.2.1] hept-2-ene"s, 5,6-dimethoxy two ring [2.2.1] hept-2-ene"s etc.;
As maleimide compound, can enumerate such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-(4-hydroxy phenyl) maleimide, N-(4-hydroxybenzyl) maleimide, N-succinimido-3-dimaleoyl imino benzoic ether, N-succinimido-4-dimaleoyl imino butyric ester, N-succinimido-6-dimaleoyl imino capronate, N-succinimido-3-dimaleoyl imino propionic ester, N-(9-acridinyl) maleimide etc.;
As unsaturated aromatics, can enumerate such as styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene etc.;
As conjugated diolefine, can enumerate for example 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.;
As the unsaturated compound with phenol skeleton that above-mentioned formula (I) means, can enumerate the compound that means separately such as following formula (I-1)～(I-5) etc.;
Figure GSA00000009826700111
Respectively do for oneself 1～3 integer of n in formula (I-1) and formula (I-3), the R in formula (I-1)～(I-5) i, R iI, R iII, R iV, R vand R vIdefinition, separately with identical in above-mentioned formula (I).
As the unsaturated compound with tetrahydrofuran skeleton, can enumerate such as (methyl) acrylic acid tetrahydro furfuryl ester, 2-(methyl) acryloxy-propionic acid tetrahydro furfuryl ester, 3-(methyl) acryloxy tetrahydrofuran-2-ketone etc.;
As the unsaturated compound with furans skeleton, can enumerate such as 2-methyl-5-(3-furyl)-1-penten-3-one, (methyl) acrylic acid furfuryl group ester, 1-furans-2-butyl-3-alkene-2-ketone, 1-furans-2-butyl-3-methoxyl-3-alkene-2-ketone, 6-(2-furyl)-2-methyl isophthalic acid-hexene-3-one, 6-furans-2-base-own-1-alkene-3-ketone, (methyl) acrylic acid 2-furans-2-base-1-methyl-ethyl ester, 6-(2-furyl)-6-methyl isophthalic acid-teracrylic acid-one etc.;
As the unsaturated compound with oxinane skeleton, can enumerate for example (methyl) acrylic acid (oxinane-2-yl) methyl ester, 2,6-dimethyl-8-(oxinane-2-base oxygen base)-Xin-1-alkene-3-ketone, 2-(methyl) acrylic acid oxinane-2-base ester, 1-(oxinane-2-oxygen base)-butyl-3-alkene-2-ketone etc.; As the unsaturated compound with pyrans skeleton, can enumerate for example 4-(Isosorbide-5-Nitrae-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyrone, 4-(1,5-dioxa-6-oxo-7-octenyl)-6-methyl-2-pyrone etc.;
As the unsaturated compound with skeleton that above-mentioned formula (II) means, can enumerate such as the degree of polymerization polyethyleneglycol (methyl) acrylate that is 2～10, polypropylene glycol list (methyl) acrylate that the degree of polymerization is 2～10 etc.;
As other unsaturated compounds, can enumerate such as vinyl cyanide, methacrylonitrile, acrylamide, Methacrylamide etc.
In the middle of them, preferably use alkyl methacrylate, the methacrylic acid cycloalkyl ester, the acrylic acid cycloalkyl ester, maleimide compound, unsaturated aromatics, unsaturated compound with phenol hydroxyl of above-mentioned formula (I) expression, there is the tetrahydrofuran skeleton, the furans skeleton, the oxinane skeleton, the unsaturated compound of the skeleton that pyrans skeleton or above-mentioned formula (II) mean, from copolyreaction with for the dissolubility aspect of aqueous alkali, consider, particularly preferably use and be selected from styrene, the methacrylic acid tertiary butyl ester, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, to methoxy styrene, acrylic acid 2-methylcyclohexyl ester, N-phenylmaleimide, the N-N-cyclohexylmaleimide, (methyl) acrylic acid tetrahydro furfuryl ester, single (methyl) acrylate of polyglycol (n=2～～10), 3-(methyl) acryloxy tetrahydrofuran-2-ketone, (methyl) acrylic acid 4-hydroxybenzyl ester, (methyl) acrylic acid 4-hydroxy phenyl ester, o-hydroxy ethene, 4-Vinyl phenol, at least one in the group that Alpha-Methyl-4-Vinyl phenol forms.
These compounds (a3) can be used alone or in combination.
As the preferred object lesson of the multipolymer used in the present invention (A), can enumerate for example methacrylic acid/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/acrylic acid 2-methylcyclohexyl ester/glycidyl methacrylate/styrol copolymer, methacrylic acid/methacrylic acid tetrahydro furfuryl ester/glycidyl methacrylate/N-N-cyclohexylmaleimide/lauryl methacrylate/Alpha-Methyl-p-hydroxy styrenes multipolymer, styrene/methacrylic acid/glycidyl methacrylate/methacrylic acid (3-Ethyloxetane-3-base ester)/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester copolymer etc.
To the multipolymer (A) used in the present invention, adopt the weight-average molecular weight (hereinafter referred to as " Mw ") of the polystyrene conversion of gel permeation chromatography to be preferably 2 * 10 3～1 * 10 5, more preferably 5 * 10 3～5 * 10 4.If Mw less than 2 * 10 3, there will be the imperfect situation of development nargin, thereby the declines such as residual film ratio that gained is filmed occur, and the situation of the variation such as pattern form of gained interlayer dielectric, thermotolerance.On the other hand, if surpass 1 * 10 5, there will be susceptibility to descend, thus the situation of pattern form variation.In addition, molecular weight distribution (hereinafter referred to as " Mw/Mn ", wherein above-mentioned Mn is the number-average molecular weight by the polystyrene conversion of gel permeation chromatography to multipolymer (A)) is preferably below 5.0, more preferably below 3.0.If Mw/Mn surpasses 5.0, there will be the situation of the pattern form variation of gained interlayer dielectric.
The radiation sensitive linear resin composition that contains multipolymer as above (A) can not produce and develop residually when developing, and can easily form predetermined pattern form.
Solvent used in preparation as multipolymer (A), can enumerate such as diglycol dialkyl ether, propylene glycol alkyl ether acetic acid ester, propylene glycol alkyl ether propionic ester, ketone, alkoxyl propionic ester etc.
The concrete example as it, as the diglycol dialkyl ether, can enumerate such as diethylene glycol dimethyl ether, diethyl carbitol, diglycol ethyl-methyl ether etc.;
As propylene glycol alkyl ether acetic acid ester, can enumerate such as propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol propyl ether acetic acid esters etc.;
As alkoxyl propionic ester, can enumerate such as 3-methoxy methyl propionate etc.
Wherein, preferably diglycol dialkyl ether, propylene glycol alkyl ether acetic acid ester, alkoxyl propionic ester, particularly preferably used diethylene glycol dimethyl ether, diglycol ethyl-methyl ether, propylene-glycol ethyl ether acetic acid esters, propylene glycol methyl ether acetate, 3-methoxy methyl propionate.
Polymerization initiator used in preparation as multipolymer (A), can be used the known polymerization initiator as radical polymerization initiator usually.For example can enumerate 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).
In the preparation of multipolymer (A), the molecular weight regulator that can also use the Molecular regulator amount to use.As its object lesson, can enumerate the mercaptan such as positive hexyl mercaptan, n-octyl mercaptan, n-dodecane mercaptan, tertiary dodecyl mercaptans, mercaptoacetic acid; The xanthan such as dimethyl yellow essence sulfide (ジ メ チ Le キ サ Application ト ゲ Application ス Le Off イ De), diisopropyl xanthan element disulfide (ジ イ ソ プ ロ ピ Le キ サ Application ト ゲ Application ジ ス Le Off イ De) element (キ サ Application ト ゲ Application); Terpinolene, α-methylstyrenedimer etc.
<compound (B) >
Compound (B) used in the present invention is can produce 1 of carboxylic acid by useful to irradiation of rays, the 2-quinone di-azido compound, can use phenoloid or alcohol compound (hereinafter referred to as " parent nucleus ") and 1, the condensation product of 2-naphthoquinones two nitrine sulfonic acid halides.
As above-mentioned parent nucleus, can enumerate such as trihydroxy benzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxy benzophenone, (polyhydroxy phenyl) alkane etc.
As its object lesson, as the trihydroxy benzophenone, for example can enumerate 2,3,4-trihydroxy benzophenone, 2,4,6-trihydroxy benzophenone etc.;
As tetrahydroxybenzophenone, can enumerate 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,3,4,3 '-tetrahydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl ketone, 2,3,4,4 '-tetrahydroxy-3 '-methoxyl benzophenone etc.;
As pentahydroxybenzophenone, for example can enumerate 2,3,4,2 ', 6 '-pentahydroxybenzophenone etc.;
As the hexahydroxy benzophenone, for example can enumerate 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone etc.;
As (polyhydroxy phenyl) alkane, for example can enumerate two (2, the 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] bis-phenol, two (2, 5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane, 3, 3, 3 ', 3 '-tetramethyl-1, 1 '-spirobiindene-5, 6, 7, 5 ', 6 ', 7 '-six alcohol, 2, 2, 4-trimethyl-7, 2 ', 4 '-trihydroxy flavane etc.,
In addition, can also suitably use and change the ester bond of above illustrative parent nucleus into after amido link 1,2-naphthoquinones two nitrine sulfonamidess, for example 2,3,4-trihydroxy benzophenone-1,2-naphthoquinones two nitrine-4-sulfonamide etc.
In these parent nucleus, preferably 2,3,4,4 '-tetrahydroxybenzophenone, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol.
As 1,2-naphthoquinones, two nitrine sulfonic acid halides, preferably 1,2-naphthoquinones two nitrine sulfonic acid chlorides.As its object lesson, can enumerate 1,2-naphthoquinones, two nitrine-4-sulfonic acid chloride and 1,2-naphthoquinones, two nitrine-5-sulfonic acid chloride.Wherein, preferably use 1,2-naphthoquinones, two nitrine-5-sulfonic acid chloride.
In condensation reaction, with respect to the hydroxyl value in parent nucleus, can use preferably be equivalent to 30～85 % by mole, more preferably be equivalent to 50～70 % by mole 1,2-naphthoquinones two nitrine sulfonic acid halides.
Condensation reaction can adopt known method to carry out.
These compounds (B) can be separately or two or more be used in combination.
The usage rate of compound (B), with respect to 100 mass parts (A) alkali soluble resin, be preferably 5～100 mass parts, more preferably 10～50 mass parts.When this ratio is 5～100 mass parts, the part of useful to irradiation of rays is not with illuminated portion is not large for the difference of the solubleness of the aqueous alkali as developer solution, thereby makes pattern good, and the thermotolerance of gained interlayer dielectric and solvent resistance are also good.
<multipolymer (C) >
Multipolymer in the present invention (C), it is the multipolymer of the polymerizable unsaturated compound that contains above-claimed cpd (c1), compound (c2) and compound (c3), at interlayer dielectric of the present invention, form in the resin combination of use, reduce the high surfactant of performance and play a role as surface tension, even use with little ratio, also can improve the surface smoothness of filming, thereby, can significantly improve the thickness homogeneity of formed interlayer dielectric.
Multipolymer (C), preferably except above-claimed cpd (c1), compound (c2) and compound (c3) also contain the multipolymer of the polymerizable unsaturated compound of the polymerizable unsaturated compound (hereinafter referred to as " compound (c4) ") that (c4) have the alkyl that carbon number is 1～8 in addition, more preferably except above-claimed cpd (c1), compound (c2), compound (c3) and compound (c4) also contain the multipolymer of the polymerizable unsaturated compound of the polymerizable unsaturated compound (hereinafter referred to as " compound (c5) ") that has two above unsaturated links in (c5) a part in addition, be particularly preferably by above-claimed cpd (c1), compound (c2), compound (c3), the multipolymer of the polymerization physical property unsaturated compound that compound (c4) and compound (c5) form.
Above-mentioned formula (1 0) in group-C αh 2 α-be methylene, alkyl methylene or straight chain shape or a chain alkylidene, as group-C αh 2 αduring-left-right asymmetry, it doesn't matter for its bonding position.Group-C αh 2 α-carbon number α be preferably 2～4.As group-C αh 2 α-object lesson, for example can enumerate 1,2-ethylidene, 1,2-propylidene, 1,3-propylidene, Isosorbide-5-Nitrae-butylidene etc., wherein preferably 1,2-ethylidene or 1,3-propylidene, particularly preferably 1,2-ethylidene.
Above-mentioned formula (1 0) in group C βf 2 β+1for straight chain shape or a chain fluoro alkylidene, its carbon number β is 1～20, is preferably 4～12, is particularly preferably 8.Group C βf 2 β+1be preferably straight chain shape fluoro alkylidene.
As the compound in the present invention (c1), be preferably the compound that following formula (1) means,
CH 2＝CR 1COO-CH 2CH 2C 8F 17 (1)
In formula (1), R 1with above-mentioned formula (1 0) in the definition identical.
As its object lesson, the compound that can enumerate following formula (c1-1) and (c1-2) mean separately.
CH 2＝CHCOOCH 2CH 2(CF 2) 7CF 3 (c1-1)
CH 2＝C(CH 3)COOCH 2CH 2(CF 2) 7CF 3 (c1-2)
Above-mentioned formula (2 0) in group-C γh 2 γ-be the alkylidene of straight chain shape or a chain.As group-C γh 2 γduring-left-right asymmetry, it doesn't matter for its bonding position.As group-C γh 2 γ-object lesson, for example can enumerate 1,2-ethylidene and 1,2-propylidene, be preferably 1,2-ethylidene.
Compound (c2) can be used above-mentioned general formula (2 0) in the potpourri of the different compound of the value of number of repeat unit a.The mean values of a is 1～30, is preferably 2～20, is particularly preferably 4～12.The value of this can be by compound (c2), adopting the number-average molecular weight of the polystyrene conversion of gel permeation chromatography to obtain by calculating.
As the compound in the present invention (c2), be preferably the compound that following formula (2) means.
CH 2＝CR 2COO-(C 2H 4O) aR 3 (2)
In formula (2), R 2and R 3respectively with above-mentioned formula (2 0) in definition identical, the mean values of number of repeat unit a is 4～12.
As this compound (c2), can apply commercially available product, as its example, can enumerate NK-エ ス テ Le M-40G, M-90G, AM-90G that for example Xin Zhong village chemical industry (strain) is produced; Block レ Application マ mono-PME-200, PME-400, PME-550 etc. that day oil (strain) is produced.
In above-mentioned general formula (3), work as R 5and R 6there is separately when a plurality of each R 5can be identical, also can be different, each R 6can be identical, also can be different.In addition, in above-mentioned general formula (4), work as R 10and R 11there is separately when a plurality of each R 10can be identical, also can be different, each R 11can be identical, also can be different.
As above-claimed cpd (c3), the R in preferred above-mentioned formula (3) 4, R 5and R 6the alkyl or phenyl that the carbon number of respectively doing for oneself is 1～20, and R 7and R 8the polymerizable unsaturated compound that there is separately the group of above-mentioned formula (4) expression.As compound (c3), be preferably the compound that following general formula (c3-1) means.
Figure GSA00000009826700191
In formula (c3-1), R sifor the group that above-mentioned general formula (3) means, R 12for hydrogen atom or methyl, the integer that d is 1～3.As the example more specifically of compound (c3), can enumerate the compound that following general formula (c3-1-1)～(c3-1-3) means separately,
Figure GSA00000009826700201
Figure GSA00000009826700211
In above formula, Me is methyl, and Ph is phenyl, respectively do for oneself 0～3 integer of r, s and t.
As above-claimed cpd (c4), can enumerate (methyl) alkyl acrylate that for example there is the alkyl that carbon number is 1～8, particularly, can enumerate such as methyl methacrylate, 2-ethylhexyl acrylate etc.As the object lesson of above-claimed cpd (c5), can enumerate the compound that two ends of butylene glycol for example carry out methacrylated, can enumerate the degree of polymerization polyglycol that is 1～20, polypropylene glycol that the degree of polymerization is 1～20 etc.As above-claimed cpd (c5), can apply commercially available product, as its object lesson, can enumerate the NK エ ス テ Le 1G, the NK エ ス テ Le 2G that produce such as Xin Zhong village chemical industry (strain) society, NK エ ス テ Le 3G, NK エ ス テ Le 4G, NK エ ス テ Le 9G, NK エ ス テ Le 14G, NK エ ス テ Le 23G etc.
The multipolymer that multipolymer in the present invention (C) is the polymerizable unsaturated compound that contains compound as above (c1), compound (c2) and compound (c3).Here, with respect to the total amount of polymerizable unsaturated compound, the usage rate of each compound, for compound (c1), be 10～55 % by weight, for compound (c2), being 10～50 % by weight, for compound (c3), is 5～45 % by weight.
Multipolymer (C) is preferably the multipolymer that also contains the polymerizable unsaturated compound of compound (c4) except compound (c1), compound (c2) and compound (c3).Now, total amount with respect to polymerizable unsaturated compound, the usage rate of each compound, for compound (c1), is 20～50 % by weight, for compound (c2), being 15～40 % by weight, for compound (c3), is 10～30 % by weight, for compound (c4), be 20～35 % by weight.Multipolymer (C), more preferably except compound (c1), compound (c2), compound (c3), compound (c4), also containing the multipolymer of the polymerizable unsaturated compound of compound (c5), is particularly preferably the multipolymer of the polymerizable unsaturated compound that is comprised of compound (c1), compound (c2), compound (c3), compound (c4) and compound (c5).Now, with respect to the total amount of polymerizable unsaturated compound, the usage rate of each compound, for compound (c1), being 25～35 % by weight, for compound (c2), is 20～30 % by weight, for compound (c3), being 15～20 % by weight, for compound (c4), is 25～35 % by weight, and, for compound (c5), be 1～5 % by weight.
The weight-average molecular weight (Mw) of multipolymer (C) is preferably 5000～25000, and more preferably 10000～25000, be particularly preferably 15000～25000.The molecular weight distribution mw/mn of multipolymer (C) is preferably 1～10, and more preferably 2～4.
Preparation method about this multipolymer (C), have no particular limits, can be according to the flowcollector aggregation scheme FlowCollector of known method such as radical polymerization, cationic polymerization, anionic polymerization etc., adopt solution polymerization process, mass polymerization, emulsion polymerization etc. to be prepared, and in solution radical polymerization due to easy, thereby industrial be preferred.
Polymerization initiator used when preparing multipolymer (C), can enumerate superoxide such as benzoyl peroxide, peroxidating two acyls; The azo-compounds such as azoisobutyronitrile, phenylazo triphenyl methane etc.
The preparation of multipolymer (C) can be carried out under solvent existence or non-existent arbitrary condition, from operational point of view, preferably under the existence of solvent, carries out.As above-mentioned solvent, can enumerate Arrcostab, polar solvent, ether, propylene glycol and ester thereof, halogenated hydrocarbons, aromatic hydrocarbon such as alcohol, ketone, ester, monocarboxylic acid, fluoridize inert fluid (Off Star イ Na one ト リ キ Star De) etc.As above-mentioned alcohol, can enumerate such as ethanol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, the tert-butyl alcohol etc.;
As above-mentioned ketone, can enumerate such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methylamino ketone etc.; As above-mentioned ester, can enumerate such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate etc.;
As the Arrcostab of above-mentioned monocarboxylic acid, can enumerate such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid propyl ester, butyl 2-hydroxypropanoate, 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester etc.;
As above-mentioned polar solvent, can enumerate such as dimethyl formamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE etc.;
As above-mentioned ether, can enumerate such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, tetrahydrofuran, dioxane etc.; As above-mentioned propylene glycol and ester thereof, can enumerate such as propylene glycol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetic acid esters etc.;
As above-mentioned halogenated hydrocarbons, for example can enumerate 1,1,1-trichloroethanes, chloroform etc.;
As above-mentioned aromatic hydrocarbon, can enumerate such as benzene,toluene,xylene etc.; As the above-mentioned inert fluid of fluoridizing, can enumerate such as PFO, perfluor tri-n-butyl amine etc., use their central any one all can.
When preparing multipolymer (C), can also further as required, use the chain-transferring agents such as dodecyl mercaptans, 2 mercapto ethanol, ethyl thioglycolate, mercaptoacetic acid monooctyl ester.
In radiation sensitive linear resin composition of the present invention, the usage rate of multipolymer (C), with respect to 100 mass parts (A) alkali soluble resin, be preferably 0.01～3 mass parts, more preferably 0.05～2 mass parts.Here, if the usage rate of multipolymer (C) is 0.01～3 mass parts, adopt the slit die coating process to be applied and the thick homogeneity of the mould of filming that forms is good.If this value surpasses 3 mass parts, there will be films, and the situation of film be full of cracks easily occurs, and there will be the injured situation of thickness homogeneity of formed interlayer dielectric.
<other compositions >
Radiation sensitive linear resin composition of the present invention contains multipolymer as above (A), compound (B) and multipolymer (C) as essential composition, and as required, can also further contain epoxy resin (hereinafter referred to as " (F) composition ") in addition of polymerizable compound (hereinafter referred to as " (E) composition ") that (D) thermal sensitivity acid-producing cpd, (E) contain at least 1 ethene unsaturated double-bond, (F) multipolymer (A), (G) bonding agent, (H) radical scavenger etc.
[(D) thermal sensitivity acid-producing cpd]
Above-mentioned (D) thermal sensitivity acid-producing cpd is that it can be to be contained in radiation sensitive linear resin composition of the present invention in order to improve thermotolerance and hardness by heating acidic compound.As its object lesson, can enumerate the salt such as sulfonium salt, benzothiazolium salt, ammonium salt, phosphonium salt.
As the object lesson of above-mentioned sulfonium salt, can enumerate the benzyl sulfonium salt of alkyl sulfonium salt, benzyl sulfonium salt, dibenzyl sulfonium salt, replacement etc.
Wherein, preferably use sulfonium salt and benzothiazolium salt, particularly preferably use 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, 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 sulfonium hexafluoro antimonate, 3-benzyl benzothiazole hexafluoro antimonate.
As their commercially available product, can enumerate サ Application エ イ De SI-L85, サ Application エ イ De SI-L110, サ Application エ イ De SI-L 145, サ Application エ イ De SI-L150, サ Application エ イ De SI-L160 (three new chemical industry (strain) are produced) etc.
(D) usage rate of thermal sensitivity acid-producing cpd, with respect to 100 mass parts (A) alkali soluble resin, be preferably 0.1～10 mass parts, more preferably 0.5～5 mass parts.When this consumption is 0.1～10 mass parts, can not separate out precipitate in the formation operation of filming, can form the interlayer dielectric with good hardness.
[(E) composition]
As the polymerizable compound with at least one ethene unsaturated double-bond of above-mentioned (E) composition, can use (methyl) acrylate above such as simple function (methyl) acrylate, difunctionality (methyl) acrylate, trifunctional etc.
As above-mentioned simple function (methyl) acrylate, can enumerate such as 2-(methyl) acryloxy ethyl-2-hydroxypropyl butyric ester etc.As its commercially available product, can enumerate for example ア ロ ニ Star Network ス M-101, ア ロ ニ Star Network ス M-111, ア ロ ニ Star Network ス M-114 (the Shang You East of Yi Asia synthetic (strain) produces); KAYARAD TC-110S, KAYARADTC-120S (above by Japanese chemical drug (strain) production); PVC ス コ mono-ト 158, PVC ス コ mono-ト 2311 (above by Osaka You Machine chemical industry (strain) production) etc.
As above-mentioned difunctionality (methyl) acrylate, can enumerate for example ethylene glycol bisthioglycolate (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, two (phenoxetol) fluorenes two (methyl) acrylate etc.As their commercially available product, can enumerate for example ア ロ ニ Star Network ス M-210, ア ロ ニ Star Network ス M-240, ア ロ ニ Star Network ス M-6200 (the Shang You East of Yi Asia synthetic (strain) produces); KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (above by Japanese chemical drug (strain) production); PVC ス コ mono-ト 260, PVC ス コ mono-ト 312, PVC ス コ mono-ト 335HP (above by Osaka You Machine chemical industry (strain) production) etc.
As (methyl) acrylate more than above-mentioned trifunctional, can enumerate such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, three ((methyl) acryloxy ethyl) phosphonate ester, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.As its commercially available product, can enumerate for example ア ロ ニ Star Network ス M-309, ア ロ ニ Star Network ス M-400, ア ロ ニ Star Network ス M-405, ア ロ ニ Star Network ス M-450, ア ロ ニ Star Network ス M-7100, ア ロ ニ Star Network ス M-8030, ア ロ ニ Star Network ス M-8060, (the Shang You East of Yi Asia synthetic (strain) produces); KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (above by Japanese chemical drug (strain) production); PVC ス コ mono-ト 295, PVC ス コ mono-ト 300, PVC ス コ mono-ト 360, PVC ス コ mono-ト GPT, PVC ス コ mono-ト 3PA, PVC ス コ mono-ト 400 (above by Osaka You Machine chemical industry (strain) production) etc.
In the middle of them, preferably use (methyl) acrylate that 3 officials can be above, wherein particularly preferably trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate.
These simple functions, difunctionality or above (methyl) acrylate of 3 officials energy can be used alone or in combination.(E) usage rate of composition, with respect to 100 mass parts (A) alkali soluble resin, be preferably below 50 mass parts, more preferably 1～50 mass parts, more preferably 3～30 mass parts.When the usage rate of (E) composition is 1～50 mass parts, can further improve the thermotolerance of gained interlayer dielectric and skin hardness etc.
[(F) composition]
Multipolymer (A) epoxy resin in addition as above-mentioned (F) composition, it is the resin with epoxy radicals (preferably epoxy ethyl), and as long as the not impact of its compatibility on other compositions contained in radiation sensitive linear resin composition of the present invention, not restriction.As preferred (F) composition, can enumerate such as bisphenol A type epoxy resin, phenol phenol aldehyde type epoxy resin, cresols phenol aldehyde type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl group amine type epoxy resin, hetero ring type epoxy resin, with glycidyl methacrylate (be total to) polymerization and must resin etc.Wherein, particularly preferably bisphenol A type epoxy resin, cresols phenol aldehyde type epoxy resin, glycidyl ester type epoxy resin etc.
(F) usage rate of composition, with respect to 100 mass parts (A) alkali soluble resin, be preferably below 30 mass parts, more preferably 1～30 mass parts.Contain (F) composition by the ratio with 1～30 mass parts, can further improve the thermotolerance of interlayer dielectric and skin hardness etc.
In addition, multipolymer (A) also can be called " epoxy resin ", but multipolymer (A) have aspect alkali-soluble different from (F) composition.(F) composition is that alkali is insoluble.
[(G) bonding agent]
In radiation sensitive linear resin composition of the present invention, for the cohesive of further raising with substrate, can also use (G) bonding agent.As this (G) bonding agent, preferably use the functional silanes coupling agent, can enumerate for example there is carboxyl, methacryl, isocyanate group, epoxy radicals (preferably epoxy ethyl) the substituent functional silanes coupling agent of isoreactivity.Particularly, can enumerate for example trimethoxy silane yl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanates propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc.
This (G) bonding agent, with respect to 100 mass parts (A) alkali soluble resin, preferably with below 20 mass parts, more preferably 1～20 mass parts, further preferably the amount of 3～15 mass parts is used.When the usage rate of (G) bonding agent is 1～20 mass parts, best with the cohesive of substrate.
[(H) radical scavenger]
Above-mentioned (H) radical scavenger, can be in order further to improve the storage stability of gained radiation sensitive linear resin composition, the thickness that simultaneously makes formed interlayer dielectric more homogeneous purpose and use.As this (H) radical scavenger, can use such as hindered phenol compound, hindered amine compound, phosphonate ester, sulfur atom-containing compound (wherein except alkyl phosphonic acid ester compound) etc.
As its object lesson, as above-mentioned hindered phenol compound, [3-(3 for example can to enumerate pentaerythrite four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], [3-(3 for sulphur diethylene two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, 1, 3, 5-trimethyl-2, 4, 6-tri-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, N, N '-hexane-1, [3-(3 for 6-bis-bases two, 5-bis--tert-butyl-hydroxy phenyl propionic acid acid amides)], 3, 3 ', 3 ", 5 ', 5 "-five tert-butyl groups-α, α ', α "-(sym-trimethyl benzene-2, 4-tri-bases) three paracresol, 4, 6-bis-(hot sulfenyl methyl)-orthoresol, 4, 6-bis-(dodecane sulfenyl methyl)-orthoresol, ethylene (oxygen ethylidene) two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic ester], [3-(3 for hexylidene two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 1, 3, 5-tri-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-1, 3, 5-triazine-2, 4, 6-(1H, 3H, 5H)-triketone, 1, 3, 5-tri-[(the 4-tert-butyl group-3-hydroxyl-2, the 6-xylyl) methyl]-1, 3, 5-triazine-2, 4, 6-(1H, 3H, 5H)-triketone, 2, 6-di-t-butyl-4-(4, 6-bis-(hot sulfenyl)-1, 3, 5-triazine-2-base amine) phenol, 1, 3, 5-tri-(3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl) isocyanuric acid etc.
As its commercially available product, can enumerate for example ア デ カ ス タ Block AO-20, ア デ カ ス タ Block AO-30, ア デ カ ス タ Block AO-40, ア デ カ ス タ Block AO-50, ア デ カ ス タ Block AO-60, ア デ カ ス タ Block AO-70, ア デ カ ス タ Block AO-80, ア デ カ ス タ Block AO-330 (above by (strain) ADEKA production); SumilizerGM, sumilizer GS, sumilizer MDP-S, sumilizer BBM-S, sumilizerWX-R, sumilizer GA-80 (above by Sumitomo Chemical (strain) production); IRGANOX1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX1425WL, IRGANOX 1520L, IRGANOX 245, IRGANOX 259, IRGANOX 3114, IRGANOX 565, IRGAMOD 295 (above by チ バ ジ ヤ パ Application (strain) production); ヨ シ ノ Star Network ス BHT, ヨ シ ノ Star Network ス BB, ヨ シ ノ Star Network ス 2246G, ヨ シ ノ Star Network ス 425, ヨ シ ノ Star Network ス 250, ヨ シ ノ Star Network ス 930, ヨ シ ノ Star Network ス S S, ヨ シ ノ Star Network ス TT, ヨ シ ノ Star Network ス 917, ヨ シ ノ Star Network ス 314 (above by (strain) エ mono-ピ mono-ア イ コ mono-Port レ mono-シ ヨ Application production) etc.
As above-mentioned hindered amine compound, for example can enumerate four (2, 2, 6, 6-tetramethyl-4-piperidyl) 1, 2, 3, 4-butane tetracarboxylic acid esters, two (1-octyloxy-2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) [[3, 5-bis-(1, the 1-dimethyl ethyl)-4-hydroxy phenyl] methyl] the butylmalonic acid ester etc., as its commercially available product, can enumerate for example ア デ カ ス タ Block LA-52, ア デ カ ス タ Block LA-57, ア デ カ ス タ Block LA-62, ア デ カ ス タ Block LA-67, ア デ カ ス タ Block LA-63P, ア デ カ ス タ Block LA-68LD, ア デ カ ス タ Block LA-77, ア デ カ ス タ Block LA-82, ア デ カ ス タ Block LA-87 (above by (strain) ADEKA production), sumilizer9A (being produced by Sumitomo Chemical (strain)),
CHIMASSORB 119FL, CHIMASSORB 2020FDL, CHIMASSORB944FDL, TINUVIN 622LD, TINUVIN 123, TINUVIN 144, TINUVIN765, TINUVIN 770DF (above by the production of チ バ ス ペ シ ヤ Le テ イ mono-ゲ ミ カ Le ズ society) etc.
As the abovementioned alkyl phosphonate compound, for example can enumerate butylidene two { the 2-tert-butyl group-5-methyl-to phenylene }-P, P, P, P-tetra--tridecyl two (phosphine), two (octadecyl) pentaerythritol diphosphites, 2,2 '-methylene two (4,6-, bis--tert-butyl group-1-phenyl oxygen base) (2-ethyl hexyl oxy) phosphorus, three (2,4-, bis--tert-butyl-phenyl) phosphite ester, 3,9-bis-(2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetra-oxa-s-3,9-bis-phospha spiral shell [5.5] undecanes etc., as its commercially available product, can enumerate for example ア デ カ ス タ Block PEP-4C, ア デ カ ス タ Block PEP-8, ア デ カ ス タ Block PEP-8W, ア デ カ ス タ Block PEP-24G, ア デ カ ス タ Block PEP-36, ア デ カ ス タ Block HP-10, ア デ カ ス タ Block 2112, ア デ カ ス タ Block 260, ア デ カ ス タ Block 522A, ア デ カ ス タ Block 1178, ア デ カ ス タ Block 1500, ア デ カ ス タ Block C, ア デ カ ス タ Block 135A, ア デ カ ス タ Block 3010, ア デ カ ス タ Block TPP (above by (strain) ADEKA production), IRGAFOS 168 (above by the production of チ バ ス ペ シ ヤ Le テ イ mono-ゲ ミ カ Le ズ society) etc.
Compound as above-mentioned sulfur atom-containing, for example can enumerate pentaerythrite four (3-dodecyl thiopropionate), two (propionic acid-n-tridecane base) thioether, [3-(3 for sulphur diethylene two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] etc., in addition, can also use thioether.As the commercially available product of thioether, can enumerate for example ア デ カ ス タ Block AO-412S, ア デ カ ス タ Block AO-503 (above by (strain) ADEKA production); Sumilizer TPL-R, sumilizer TPM, sumilizer TPS, sumilizer TP-D, sumilizerMB (above by Sumitomo Chemical (strain) production); IRGANOX PS800FD, IRGANOXPS802FD, IRGANOX 1035 (above by the production of チ バ ス ペ シ ヤ Le テ イ mono-ゲ ミ カ Le ズ society); DLTP, DSTP, DMTP, DTTP (above by (strain) エ mono-ピ mono-ア イ コ mono-Port レ mono-シ ヨ Application production) etc.
This (H) radical scavenger can be used alone or in combination of two or more.
(H) radical scavenger, can be with respect to 100 mass parts (A) alkali soluble resin, with the ratio below 15 weight portions, use, by the scope with 0.01～15 mass parts, and then use with the scope of 1～10 mass parts, in the situation that can not damage the radiation sensitive of gained radiation sensitive linear resin composition, the effect of performance (H) radical scavenger, be therefore preferred effectively.
<radiation sensitive linear resin composition >
Radiation sensitive linear resin composition of the present invention can be by by above-mentioned (A) alkali soluble resin, compound (B) and multipolymer (C), or (A) alkali soluble resin, compound (B) and multipolymer (C) and other compositions as above mix equably and modulate.Radiation sensitive linear resin composition of the present invention, preferably used with the solution state be dissolved in suitable solvent.For example, by (A) alkali soluble resin, compound (B) and multipolymer (C) and optional other compositions that add are mixed with certain ratio, can modulate the radiation sensitive linear resin composition of solution state.
Operable solvent in modulation as radiation sensitive linear resin composition of the present invention, use can be dissolved each composition in (A) alkali soluble resin, compound (B) and multipolymer (C) and optional other compositions that mix equably, and the solvent do not reacted with each composition.
As such solvent, can enumerate with as can be for the preparation of the solvent of above-mentioned multipolymer (A) illustrative same solvent.
In this solvent, from the dissolubility of each composition, with the reactivity of each composition, form the easiness equal angles of filming and consider, preferably use alcohol, glycol ether, ethylene glycol alkyl ether acetic acid esters, ester and diglycol.Wherein, can particularly preferably use benzylalcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetic acid esters, diethylene glycol monoethyl ether acetate, diethyl carbitol, diglycol ethyl-methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, methoxy methyl propionate, ethoxyl ethyl propionate.
In order to improve the inner evenness of thickness, can also be together with above-mentioned solvent the coupling high boiling solvent.As high boiling solvent that can coupling, can enumerate for example N-METHYLFORMAMIDE, N, dinethylformamide, N-methyl formyl aniline, N-methylacetamide, DMA, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), benzylisoeugenol, hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetic acid esters etc.Wherein, preferred 1-METHYLPYRROLIDONE, gamma-butyrolacton, DMA.
As the solvent of radiation sensitive linear resin composition of the present invention, when the coupling high boiling solvent, its consumption, with respect to whole solvents, can be preferably 1～40 quality %, more preferably 3～30 quality %.When the consumption of high boiling solvent is 1～40 quality %, the thickness homogeneity of filming is good, and pattern is also good.
When radiation sensitive linear resin composition of the present invention is mixed with to solution state, the shared ratio of composition beyond desolventizing in solution (i.e. the total amount of (A) alkali soluble resin, compound (B) and multipolymer (C) and optional other compositions that add), can at random set according to application target and required film thickness value etc., be preferably 5～50 quality %, more preferably 10～40 quality %, more preferably 15～35 quality %.
So the composition solution of preparation can also resupply use after the filtrations such as millipore filter that be 0.2 μ m left and right with aperture.
The formation method of<interlayer dielectric >
Then, the method that forms interlayer dielectric with radiation sensitive linear resin composition of the present invention is described.The formation method characteristic of interlayer dielectric of the present invention is to comprise in the following order following operation.
(1) form the operation that radiation sensitive linear resin composition of the present invention is filmed on substrate,
(2) operation of at least a portion useful to irradiation of rays of this being filmed,
(3) developing procedure, and
(4) heating process.
[(1) forms the operation that radiation sensitive linear resin composition of the present invention is filmed on substrate]
In the operation of above-mentioned (1), radiation sensitive linear resin composition of the present invention is coated on to substrate surface, preferably by carrying out prebake, except desolventizing forms, film, then make curing of coating by curing after carrying out.
As the kind of the substrate that can use in the formation of interlayer dielectric, the substrate that can enumerate glass substrate for example, silicon chip and form various metals on their surfaces.
Coating method as resin combination solution, it is had no particular limits, suitable methods such as spraying process, rolling method, method of spin coating (spin-coating method), slit die coating process, excellent painting method, ink-jet method be can adopt, spin-coating method, slit die coating process particularly preferably used.Particularly, when adopting the slit die coating process, can bring into play to greatest extent advantageous effects of the present invention, be therefore preferred.
As prebake and after the condition of curing, according to the kind of each composition, usage rate etc., suitably set respectively.Prebake can for example carry out for example under the condition about 1～15 minute, carrying out under 70～90 ℃.After cure suitable heating arrangements such as can adopting heating plate, cleaning oven and carry out.As after the temperature of curing, preferably 120～250 ℃.As after cure the time, when using heating plate as heating arrangement, preferably carry out 5～30 minutes, when adopting cleaning oven as heating arrangement, preferably carry out 30～90 minutes.
The thickness of filming so formed, be preferably 0.1～8 μ m, more preferably 0.1～6 μ m, more preferably 0.1～4 μ m.
[operation of at least a portion useful to irradiation of rays that film to this (2)]
In the operation of above-mentioned (2), to formed, film, by the mask useful to irradiation of rays with predetermined pattern.As operable ray now, can enumerate such as ultraviolet ray, far ultraviolet etc.
As above-mentioned ultraviolet ray, can enumerate such as g line (wavelength 436nm), i line (wavelength 365nm) etc.As far ultraviolet, can enumerate such as KrF excimer laser etc.In the middle of them, preferably ultraviolet ray, wherein particularly preferably contain the ray that is selected from least one bright line in the group that g line and i line form.
Exposure as ray, be preferably 1500～3000J/m 2.In addition, if use radiation sensitive linear resin composition of the present invention, even there is this radiation exposure of working as, be 2000J/m 2when following, also can form required pattern, even even be worth for 1700J/m when this 2when following, also can form the advantage of required pattern.
[(3) developing procedure]
Then in the operation of (3), by filming after adopting developer solution to above-mentioned useful to irradiation of rays, developed, removed the radiation exposure part, formed pattern.
As the developer solution used in developing procedure, can use the aqueous solution of alkali (alkali compounds) such as NaOH, potassium hydroxide, sodium carbonate, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide.In addition, can also the aqueous solution of the water-miscible organic solvent such as appropriate methyl alcohol, ethanol or surfactant will be added in above-mentioned aqueous alkali, or the various organic solvents that dissolve the present composition are used as developer solution.
As developing method, can adopt suitable methods such as launching coating process (liquid is contained the り method), infusion process, concussion infusion process, douche such as flowing.Development time, according to the composition of radiation sensitive linear resin composition and difference can be for example 30～120 seconds.
In addition, previously known radiation sensitive linear resin composition, if development time surpasses the degree of 20～25 seconds than optimum value, because the pattern formed can come off, thereby must strict control development time, and for the situation of radiation sensitive linear resin composition of the present invention, though the time exceeded than optimum development time reach more than 30 seconds, also can form good pattern, aspect the goods yield rate, have advantage.
After (3) developing procedure, preferably carrying out the flushing that for example flowing water cleans processes, and preferably by adopting high-pressure sodium lamp etc. to carry out radiation exposure (post-exposure) to the whole face of filming of patterning, to residual (B) 1 in the filming of patterning, the 2-quinone di-azido compound carries out resolution process.Radiation exposure in this post-exposure operation, be preferably 2000～5000J/m 2left and right.
[(4) heating process]
Finally, in the operation of (4), by carry out heat treated (curing afterwards processing) with heating arrangements such as heating plate, baking ovens, filming of patterning is cured to processing.Heating-up temperature in the operation of these (4) is for example 120～250 ℃.According to the kind of heating machine and difference for example, when on heating plate, carrying out heat treated, can be 5～30 minutes, when in baking oven, carrying out heat treated, can be 30～90 minutes heat time heating time.Now, can also adopt substep baking process of carrying out heating process more than 2 times etc.
Like this, can on substrate surface, form the pattern-like film corresponding to the purpose interlayer dielectric.
<interlayer dielectric >
From following embodiment, the interlayer dielectric as above formed, good to the cohesive of substrate, thermotolerance, solvent resistance and the transparency etc. are good, and specific inductive capacity is low.The interlayer dielectric that therefore, can be suitable as various electronic products is used.
[embodiment]
By the following examples the present invention is carried out to more specific description, but the present invention is not limited to these embodiment.In addition, below, the weight-average molecular weight of polymkeric substance (Mw) and number-average molecular weight (Mn) are measured by the gel permeation chromatography (GPC) that adopts following condition.
" HLC 8220 systems " that determinator: East ソ mono-(strain) manufactures
Separating column: the TSK gel GMH that 4 Gen East ソ mono-(strain) manufacture hR-N is connected in series and uses
Column temperature: 40 ℃
Eluting solvent: tetrahydrofuran (producing with light Pure pharmaceutical worker industry (strain))
Flow velocity: 1.0ml/ minute
Sample concentration: 1.0 quality %
Sample injection rate IR: 100 μ m
Detecting device: differential refractometer
Standard substance: monodisperse polystyrene
In addition, the solution viscosity of radiation sensitive linear resin composition, the E type viscosity meter that Cai Yong East capital Meter device (strain) is manufactured is measured under 30 ℃.
Synthesizing of<multipolymer (A) >
Synthesis example 1
In the flask that cooling tube and stirrer are housed, add 7 weight portions 2,2 '-azo two (2,4-methyl pentane nitrile), 200 weight portion diglycol ethyl-methyl ethers.Continue to add 16 weight portion methacrylic acids, 16 weight portion methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, 20 parts by weight of acrylic acid 2-methylcyclohexyl esters, 40 weight portion glycidyl methacrylate, 10 parts by weight of styrene and 3 weight portion α-methylstyrenedimers, with after nitrogen replacement, start slowly to stir.Make the temperature of solution rise to 70 ℃, keep this temperature 4 hours, obtain the polymer solution containing multipolymer (A-1).
The weight-average molecular weight (Mw) of the polystyrene conversion of multipolymer (A-1) is 8000, and molecular weight distribution (Mw/Mn) is 2.3.In addition, and the solids content concn of the polymer solution made here (refer to that the weight of polymkeric substance contained in polymer solution accounts for the ratio of the general assembly (TW) of polymer solution, lower same.) be 34.4 % by weight.
Synthesis example 2
In the flask that cooling tube and stirrer are housed, add 8 weight portions 2,2 '-azo two (2,4-methyl pentane nitrile) and 220 weight portion diglycol ethyl-methyl ethers.Continue to add 11 weight portion methacrylic acids, 12 weight portion methacrylic acid tetrahydro furfuryl esters, 40 weight portion glycidyl methacrylate, 15 weight portion N-N-cyclohexylmaleimides, 10 weight portion lauryl methacrylates, 10 weight portion Alpha-Methyl-4-Vinyl phenols and 3 weight portion α-methylstyrenedimers, with after nitrogen replacement, start slowly to stir.Make the temperature of solution rise to 70 ℃, keep this temperature 5 hours, obtain the polymer solution containing multipolymer (A-2).
The weight-average molecular weight (Mw) of the polystyrene conversion of multipolymer (A-2) is 8000, and molecular weight distribution (Mw/Mn) is 2.3.The solids content concn of the polymer solution made here in addition, is 31.9 % by weight.
Synthesizing of<multipolymer (C) >
Synthesis example 3
To stirring apparatus is housed, in the glass flask of condenser and thermometer, add compound 28.4 mass parts as above-mentioned formula (c1-1) expression of (c1) compound, NK-エ ス テ Le M-90G (trade name as (c2) compound, Xin Zhong village chemistry (strain) is produced) 20.7 mass parts, compound 18.1 mass parts that mean as the following formula (c3-1-1-1) of (c3) compound, methyl methacrylate 5.9 mass parts and 2-ethylhexyl acrylate 23.5 mass parts as (c4) compound, as butylene glycol two ends of (c5) compound by compound 3.4 mass parts of methacrylated, isopropyl alcohol 414 mass parts as solvent, in nitrogen stream, under refluxing, add as 2 of polymerization initiator, after 2 '-azoisobutyronitrile, 0.7 mass parts and lauryl mercaptan 4 mass parts as chain-transferring agent, reflux and within 8 hours, carry out copolymerization under 75 ℃, obtain the solution that contains multipolymer (C-1).Then, remove desolventizing with evaporator under the heating condition of 70 ℃, isolate multipolymer (C-1).
The number-average molecular weight Mn of gained multipolymer (C-1) is 2800, and weight-average molecular weight Mw is 5300, and molecular weight distribution (Mw/Mn) is 1.9.
Figure GSA00000009826700371
In above formula, Me is methyl.
Synthesis example 4
In above-mentioned synthesis example 3, except making addition as the lauryl mercaptan of chain-transferring agent, be 1 mass parts, with synthesis example 3, similarly operate, obtain multipolymer (C-2).
The number-average molecular weight Mn of gained multipolymer (C-2) is 4700, and weight-average molecular weight Mw is 11000, and molecular weight distribution (Mw/Mn) is 2.3.
Synthesis example 5
In above-mentioned synthesis example 3, be not used as the lauryl mercaptan of chain-transferring agent, and make copolymerization temperature and time be respectively 73 ℃ and 10 hours, in addition, with synthesis example 3, similarly operate, obtain multipolymer (C-3).
The number-average molecular weight Mn of gained multipolymer (C-3) is 5600, and weight-average molecular weight Mw is 21000, and molecular weight distribution (Mw/Mn) is 3.8.
Synthesis example 6
To stirring apparatus is housed, in the glass flask of condenser and thermometer, add compound 39.4 mass parts as above-mentioned formula (c1-1) expression of (c1) compound, NK-エ ス テ Le M-90G (Xin Zhong village chemistry (strain) is produced) 31.6 mass parts as (c2) compound, compound 29.0 mass parts that mean as the above-mentioned formula (c3-1-1-1) of (c3) compound, isopropyl alcohol 414 mass parts as solvent, in nitrogen stream, under refluxing, add azoisobutyronitrile 0.7 mass parts as polymerization initiator, after lauryl mercaptan 4 mass parts as chain-transferring agent, reflux and within 8 hours, carry out copolymerization under 75 ℃, obtain the solution that contains multipolymer (C-4).Then, with evaporator, under the heating condition of 70 ℃, slough solvent, isolate multipolymer (C-4).
The molecular weight of gained multipolymer (C-4), number-average molecular weight is 3000, weight-average molecular weight is 6000.In addition, molecular weight distribution (Mw/Mn) is 2.0.
Synthesis example 7
To stirring apparatus is housed, in the glass flask of condenser and thermometer, add compound 28.4 mass parts as above-mentioned formula (c1-1) expression of (c1) compound, NK-エ ス テ Le M-90G (Xin Zhong village chemistry (strain) is produced) 20.7 mass parts as (c2) compound, compound 21.5 mass parts that mean as the above-mentioned formula (c3-1-1-1) of (c3) compound, methyl methacrylate 5.9 mass parts and 2-ethylhexyl acrylate 23.5 mass parts as (c4) compound, and as isopropyl alcohol 414 mass parts of solvent, in nitrogen stream, under refluxing, add as 2 of polymerization initiator, 2 '-azoisobutyronitrile, 0.7 mass parts, after lauryl mercaptan 4 mass parts as chain-transferring agent, reflux and within 8 hours, carry out copolymerization under 75 ℃, obtain the solution that contains multipolymer (C-5).Then, with evaporator, under the heating condition of 70 ℃, slough solvent, isolate multipolymer (C-5).
The number-average molecular weight Mn of gained multipolymer (C-5) is 2600, and weight-average molecular weight Mw is 5000, and in addition, molecular weight distribution (Mw/Mn) is 1.9.
Embodiment 1
[modulation of radiation sensitive linear resin composition]
To be equivalent to the amount of 100 mass parts (solid content) multipolymers (A-1), as the solution containing multipolymer (A-1) synthetic in the above-mentioned synthesis example 1 of (A) multipolymer, 30 mass parts are as 4 of (B) compound, 4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1, the condensation product (B-1) of 2-naphthoquinones two nitrine-5-sulfonic acid chloride (2.0 moles), and the multipolymer (C-1) made in the above-mentioned synthesis example 3 of 0.5 mass parts as (C) multipolymer is mixed, after adding again the diglycol methyl ethyl ether as solvent, the membrane filter that is 0.2 μ m with aperture is filtered, modulate radiation sensitive linear resin composition (S-1).
[as the performance evaluation of interlayer dielectric]
(1) ocular estimate of filming
In the formation of 550 * 650mm chromium film on glass, adopt slit die applicator (East capital ying chemical industry (strain) manufacture, model " TR632105-CL ") radiation sensitive linear resin composition (S-1) of the above modulation of coating, the pressure that setting reaches is 100Pa, remove desolventizing under vacuum after, 90 ℃ of lower prebake 2 minutes, forming thickness was filming of 1.0 μ m again.
Under sodium vapor lamp, this is filmed and carries out the visual observations outward appearance.Now, the whole smoke-like spot produced of filming is referred to as to " smog spot ", the spot that approaches pin (proximate pin) come from the preliminary drying oven is referred to as " pin spot ", investigates its appearance situation.When these spots all can not be seen basically, be evaluated as " well ", in the time can seeing slightly any in these spots, be evaluated as " defective slightly ", in the time can clearly seeing, be evaluated as " defective ".Evaluation result is listed in table 1.
(2) evaluation of susceptibility
By the formation at 550 * 650mm chromium film on glass, coating hexamethyldisilazane (HMDS), then heating 1 minute under 60 ℃, carry out the HMDS processing to it.
Formation after this HMDS processes chromium film on glass, adopt the slit die applicator (radiation sensitive linear resin composition (S-1) of the above modulation of " TR632105-CL " coating, the pressure that setting reaches is 100Pa, remove desolventizing under vacuum after, 90 ℃ of lower prebake 2 minutes, forming thickness was filming of 3.0 μ m again.
The MPA-600FA exposure machine that adopts キ ヤ ノ Application (strain) to manufacture, lines by thering are 3.0 μ m and the mask of gap (10 pairs 1) pattern, using exposure as variable, gained is filmed after useful to irradiation of rays, adopt the tetramethyl ammonium hydroxide aqueous solution of concentration shown in table 1, adopt the expansion coating process (liquid is contained the り method) that flows to be developed under 25 ℃.Here development time, when adopting the developer solution that tetramethyl ammonium hydroxide concentration is 0.4 quality %, be 80 seconds, when adopting the developer solution of 2.38 quality %, is 50 seconds.Next, carry out 1 minute flowing water with ultrapure water and rinse, then make its drying, the formation after processing with HMDS form pattern on the glass substrate of chromium film.
Now, investigation makes the gap pattern of 3.0 μ m lines and gap (10 pairs 1) dissolve required exposure fully.Usining this value lists in table 1 as susceptibility.When this value is 2000J/m 2when following, susceptibility can be regarded as well, when being 1700J/m 2when following, susceptibility can be regarded as very excellent.
(3) evaluation of development nargin
Similarly the glass that has formed the chromium film is carried out to the HMDS processing with above-mentioned " evaluation of (2) susceptibility ".Formation after this HMDS processes chromium film on glass, adopt the slit die applicator (radiation sensitive linear resin composition (S-1) of the above modulation of " TR632105-CL " coating, the pressure that setting reaches is 100Pa, remove desolventizing under vacuum drying after, 90 ℃ of lower prebake 2 minutes, forming thickness was filming of 3.0 μ m again.
The MPA-600FA exposure machine that adopts キ ヤ ノ Application (strain) to manufacture, lines by thering are 3.0 μ m and the mask of gap (10 pairs 1) pattern, the exposure of the sensitivity value of measuring in above-mentioned to be equivalent to " (2) sensitivity assessment ", gained is filmed and exposed, then, adopt the tetramethyl ammonium hydroxide aqueous solution of concentration shown in table 1, using development time as variable, adopt the expansion coating process (liquid is contained the り method) that flows to be developed under 25 ℃.Next, carry out 1 minute flowing water with ultrapure water and rinse, then make its drying, the formation after processing with HMDS the formation pattern on glass of chromium film.
Now, so that the live width of lines is the required development time of 3.0 μ m is that optimum development time is listed in table 1.And, when further continuation from this optimum development time is developed, measure until the time of 3.0 μ m line images while coming off, this time is listed in to table 1 as development nargin.When this value is more than 30 seconds the time, development nargin can be regarded as well.
(4) evaluation of solvent resistance
In the formation of 550 * 650mm chromium film on glass, adopt slit die applicator (East capital ying chemical industry (strain) manufacture, model " TR632105-CL ") radiation sensitive linear resin composition (S-1) of the above modulation of coating, the pressure that setting reaches is 100Pa, remove desolventizing under vacuum after, 90 ℃ of lower prebake 2 minutes, formation was filmed again.The MPA-600FA exposure machine that adopts キ ヤ ノ Application (strain) to manufacture, take cumulative exposure as 9000J/m 2this is filmed and is exposed, then in cleaning oven, under 220 ℃, heat 1 hour the cured film that is 3.0 μ m at the formation thickness on glass that has formed the chromium film.
Here, measure the thickness (T1) of gained cured film.Then, the chromium film glass substrate that formed this cured film is controlled to dipping in the dimethyl sulfoxide of 70 ℃ in temperature and, after 20 minutes, again measures the thickness (t1) of cured film, calculate the Thickness Variation rate that caused by dipping | t1-T1|/T1} * 100[%].This results are shown in table 1.When this value is 5% when following, solvent resistance can be regarded as well.
(5) stable on heating evaluation
With the cured film that is similarly 3.0 μ m at the formation thickness on glass that has formed the chromium film in above-mentioned " evaluation of (4) solvent resistance ".
Measure the thickness of the cured film of gained (T2) here.Then, the chromium film glass substrate that has formed this cured film is placed in to cleaning oven, appends heating after 1 hour under 240 ℃, again measure the thickness (t2) of cured film, calculate by append the Thickness Variation rate that heating causes | t2-T2|/T2} * 100[%].This results are shown in table 1.When this value is 5% when following, thermotolerance can be regarded as well.
(6) evaluation of the transparency
In above-mentioned " evaluation of (4) solvent resistance ", except the glass substrate " NA35 (manufacture of NH テ Network ノ グ ラ ス (strain) society) " that adopts 550 * 650mm replaces having formed the glass substrate of chromium film, similarly operated, formed cured film on glass substrate.The employing spectrophotometer " 150-20 type twin-beam ((strain) Li System does manufacturing) ", using and there is no the glass of diaphragm glass substrate as the reference product, measure the transmittance of the glass substrate with this cured film in 400～800nm wavelength coverage.Minimum light transmission rate value is now listed in table 1.When this value is 90% when above, the transparency can be regarded as well.
(7) evaluation of thickness homogeneity
Similarly on glass substrate, form cured film with above-mentioned " evaluation of (6) transparency ".To this cured film, measure thickness at the measuring point places of 20, obtain according to the following formula the thickness homogeneity.
Thickness homogeneity (%)=(maximal value-minimum value of coating thickness) * 100/ ((the coating thickness mean values of 20 points) * 2)
If the coating thickness homogeneity of trying to achieve like this is below 1%, homogeneity can be regarded as well.
In addition, above-mentioned 20 measuring points, following definite.; deduction is from the scope of the inside 50mm in each edge of the long limit of substrate (550 * 650mm) and minor face; using medial region (450～550mm) as measuring zone; in this zone; on the straight line of long side direction and short side direction; every 40mm, each determines 10 points (adding up to 20 points) respectively, usings it as measuring point.
(8) evaluation of relative dielectric constant
Make on the SUS304 substrate processed of flattening surface carrying out polishing by polishing wheel for sisal hemp (numb rag wheel), adopt the radiation sensitive linear resin composition (S-1) of the above modulation of spin-coating method coating, the pressure that setting reaches is 100Pa, remove desolventizing under vacuum after, 90 ℃ of lower prebake 2 minutes, forming thickness was filming of 3.0 μ m again.The MPA-600FA exposure machine that adopts キ ヤ ノ Application (strain) to manufacture, take cumulative exposure as 9000J/m 2gained is filmed and exposed, this substrate is heated 1 hour in cleaning oven under 220 ℃, on the SUS substrate, form cured film.Adopt vapour deposition method to form the Pt/Pd electrode pattern on this cured film, produce the sample that Dielectric Coefficient is used.
To having the substrate of this electrode pattern, the HP16451B electrode and the accurate LCR instrument of HP4284A that adopt Yokogawa ヒ ユ mono-レ Star ト パ Star カ mono-De (strain) to manufacture, by the CV method, with its relative dielectric constant of frequency measurement of 10kHz.Measurement result is listed in table 1.When this value is 3.9 when following, specific inductive capacity can be regarded as well.
Embodiment 2～7, comparative example 1～3
[modulation of radiation sensitive linear resin composition]
In embodiment 1, except the kind of each composition of radiation sensitive linear resin composition and consumption are as shown in table 1 respectively, modulate similarly to Example 1 radiation sensitive linear resin composition (S-2)～(S-7) and (s-1)～(s-3).
Adopt these compositions to be estimated.
The B-1 as compound (B) used in these embodiment and comparative example is 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1, the condensation product of 2-naphthoquinones two nitrine-5-sulfonic acid chloride (2.0 moles).
In comparative example 1 and 2, adopt the following table surface-active agent to replace multipolymer (C).
C-1 (comparative example 1): the trade name that polysiloxane-based surfactant (You East レ ダ ウ コ mono-ニ Application グ シ リ コ mono-Application (strain) is produced: SH-193).
C-2 (comparative example 2): ((strain) ネ オ ス produces fluorine class surfactant, trade name: Off タ mono-ジ エ Application ト 222F)
In addition, in comparative example 3, multipolymer (C) and surfactant are all less than using.
[as the performance evaluation of interlayer dielectric]
In embodiment 1, except the radiation sensitive linear resin composition (S-2)～(S-7) that uses respectively above modulation with (s-1)～(s-3) replace radiation sensitive linear resin composition (S-1), carrying out similarly to Example 1 various evaluations.Evaluation result is listed in table 1.
Figure GSA00000009826700441
Table 2
Figure GSA00000009826700451
Embodiment 8～10
In embodiment 1, by (A) multipolymer, (B) compound and (C) after multipolymer mixes, before adding solvent, with respect to 100 mass parts multipolymers (A), further add 2 mass parts 1 at embodiment 8 respectively, 3, 5-tri-(3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl) isocyanuric acid (trade name " ア デ カ ス タ Block AO-20 ", by (strain) ADEKA, produced), further add 2 mass parts 1 in embodiment 9, 3, 5-trimethyl-2, 4, 6-tri-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (trade name " ア デ カ ス タ Block AO-330 ", by (strain) ADEKA, produced), further add 2 mass parts two (octadecyl) pentaerythritol diphosphites (trade name " ア デ カ ス タ Block PEP-8 " at embodiment 10, by (strain) ADEKA, produced).In addition, modulate similarly to Example 1 radiation sensitive linear resin composition (S-8)～(S-10), and estimated.
As a result, in all embodiment 8～10, the outward appearance of filming is " well ", and susceptibility, development nargin, solvent resistance, thermotolerance, the transparency and relative dielectric constant all show the value identical with embodiment 1.And the thickness homogeneity is to be to be 0.43% in 0.48%, embodiment 10 in 0.45%, embodiment 9 in embodiment 8.

Claims (5)

1. a radiation sensitive linear resin composition is characterized in that containing:
(A) alkali soluble resin, this alkali soluble resin is to contain the multipolymer of monomer that (a1) is selected from least one in the group that unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides form and (a2) has the polymerizable unsaturated compound of epoxy radicals;
(B) 1, the 2-quinone di-azido compound; And
(C) contain (c1) following formula (1 0) mean compound,
(c2) following general formula (2 0) compound that means and
(c3) have the group that following general formula (3) means polymerizable unsaturated compound,
(c4) have the alkyl that carbon number is 1 ~ 8 polymerizable unsaturated compound,
(c5) have the multipolymer of polymerizable unsaturated compound of the polymerizable unsaturated compound of 2 above unsaturated links in a part, with respect to 100 mass parts alkali soluble resins (A), the usage rate of multipolymer (C) is 0.01 ~ 3 mass parts,
Figure FDA00002755562000011
Formula (1 0) in, R 1for hydrogen atom or methyl, the integer that α is 0 ~ 6, the integer that β is 1 ~ 20,
Figure FDA00002755562000012
Formula (2 0) in, R 2for hydrogen atom or methyl, R 3for the carbon number alkyl that is 1 ~ 12, γ be 2 or 3, a be number of repeat unit, its mean values is 1 ~ 30,
In formula (3), R 4, R 5, R 6, R 7and R 8the group that the alkyl that is 1 ~ 20 for carbon number independently of one another, phenyl or following general formula (4) mean, the integer that b is 0 ~ 3,
In formula (4), R 9, R 10and R 11the alkyl or phenyl that is 1 ~ 20 for carbon number independently of one another, the integer that c is 0 ~ 3.
2. radiation sensitive linear resin composition claimed in claim 1, wherein above-claimed cpd (c1) is the compound that following formula (1) means, above-claimed cpd (c2) is the compound that following general formula (2) means, and (C) multipolymer be by 25 ~ 35 quality % compounds (c1),
The multipolymer of the polymerizable unsaturated compound that 20 ~ 30 quality % compounds (c2), 15 ~ 20 quality % compounds (c3), 25 ~ 35 quality % compounds (c4) and 1 ~ 5 quality % compound (c5) form,
CH 2=CR 1COO-CH 2CH 2C 8F 17 (1)
In formula (1), R 1with above-mentioned formula (1 0) in the definition identical,
CH 2=CR 2COO-(C 2H 4O) aR 3 (2)
In formula (2), R 2and R 3respectively with above-mentioned formula (2 0) in definition identical, the mean values of number of repeat unit a is 4 ~ 12.
3. an interlayer dielectric, is characterized in that being formed by the described radiation sensitive linear resin composition of claim 1 or 2.
4. the formation method of an interlayer dielectric is characterized in that comprising in the following order following operation:
(1) the described radiation sensitive linear resin composition of claim 1 or 2 is coated in to the operation that on substrate, formation is filmed,
(2) operation of at least a portion useful to irradiation of rays of this being filmed,
(3) developing procedure, and
(4) heating process.
5. an interlayer dielectric, is characterized in that being formed by method claimed in claim 4.
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