CN1945432A - Radiation sensitive resin composition, and formation of interlayer insulating film and microlens - Google Patents

Radiation sensitive resin composition, and formation of interlayer insulating film and microlens Download PDF

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CN1945432A
CN1945432A CNA2006101421361A CN200610142136A CN1945432A CN 1945432 A CN1945432 A CN 1945432A CN A2006101421361 A CNA2006101421361 A CN A2006101421361A CN 200610142136 A CN200610142136 A CN 200610142136A CN 1945432 A CN1945432 A CN 1945432A
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methyl
oxetanes
ester
sensitive resin
resin composition
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米田英司
滨田谦一
志保浩司
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JSR Corp
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • 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
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds

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  • General Physics & Mathematics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Provided is a radiation-sensitive resin composition and a method for forming an interlayer insulation film and microlenses using the composition. The radiation-sensitive resin composition comprises: unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride, copolymer of oxygen heterocycles butane compound and ether linkage-containing compound such as tetrahydrofuran, and a 1,2-quinonediazido compound.

Description

Radiation sensitive resin composition, interlayer dielectric and lenticular formation
Technical field
The interlayer dielectric and lenticule and this interlayer dielectric and the lenticular method that forms that the present invention relates to be used in particular for to form interlayer dielectric and lenticular radiation sensitive resin composition, form by this radiation sensitive resin composition.
Background technology
In the electronic units such as thin film transistor (TFT) (below be designated as " TFT ") type liquid crystal display cells, magnetic head element, integrated circuit component, solid-state imager,, interlayer dielectric is set usually in order to insulate between the wiring that makes the stratiform configuration.As the material that forms interlayer dielectric, because it is few and have the material of enough flatness to be preferred for obtaining the process number of necessary pattern form, therefore is extensive use of radiation sensitive resin composition (opening 2001-354822 communique and Te Kai 2001-343743 communique with reference to the spy).
In the above-mentioned electronic unit, for example through on interlayer dielectric, forming ELD and then forming the operation of liquid crystal orientation film thereon and make TFT type liquid crystal display cells, interlayer dielectric is exposed under the hot conditions in the formation operation of ELD, or the pattern that is exposed to electrode form in the stripper of employed resist, so must enough patience be arranged to above-mentioned condition.
In recent years, for TFT type liquid crystal display cells, constantly development such as big pictureization, high brightnessization, height become more meticulous, high-speed responsiveization, slimming, owing to require the goods productive rate on the operation, therefore the radiation sensitive resin composition that requires to be used to form interlayer dielectric is high sensitive, and has also increased now and require high-performance at aspects such as low-k, high light transmissions for forming interlayer dielectric.
On the other hand, facsimile recorder, electronic copier, solid-state imager etc. are brilliant to carry the optical system material of the imaging optical system such as color filter or the joints of optical fibre, uses to have the lenticule of the lens diameter about diameter 3～100 μ m or the microlens array that it is regularly arranged.
Form that lenticular method is known to be had: after forming pattern-like film, make it melt flows, thus the method for directly utilizing as lens by heat treated corresponding to lens; Shelter the lens pattern of melt flows, lens shape is transferred to the method for substrate etc. by dry ecthing.During even such lens pattern forms, radiation sensitive resin composition also is widely used (opening flat 6-18702 communique and the flat 6-136239 communique of Te Kai with reference to the spy).
The radiation sensitive resin composition that is used to form lens pattern is a high sensitive, has desirable radius-of-curvature by its lenticule that forms, and requires high-fire resistance, high light transmission.
Be formed with as above-mentioned lenticular lens elements, then it is supplied in following operation: in order to remove as the various dielectric films on the pad of wiring formation part, coating planarization and etching resist, develop by desirable photomask irradiation radioactive ray, the etching of removing pad portion with resist after, remove planarization film and various dielectric film, the operation that pad is exposed by etching.Therefore, form in operation and the etching work procedure with filming of resist,, need solvent resistance, thermotolerance etc. for lenticule in planarization film, etching.
On the other hand, interlayer dielectric that obtains like this or lenticule, in the developing procedure that forms at that time, if development time is more than Best Times, then developer solution infiltration between pattern and substrate, and peel off easily, for fear of this phenomenon, essential strict control development time is arranged, having problems aspect the productive rate of goods and the throughput rate.
And then, following scheme has been proposed: improve in order to make interlayer dielectric and lenticular thermotolerance, skin hardness, add the antimony fluoride class acid agent (opening the 2001-330953 communique with reference to the spy) as the thermonasty acid agent in becoming the radiation sensitive resin composition of raw material, such radiation sensitive resin composition is pointed out because the problem of the toxicity that the antimony based compound causes.
Like this, be used to form interlayer dielectric and lenticular radiation sensitive resin composition requirement high sensitive, even in addition in developing procedure development time more than the stipulated time, also require not take place peeling off of pattern, and require high-fire resistance for formed interlayer dielectric, high solvent resistance, low-k, high light transmission etc., on the other hand, when forming lenticule, except as the lenticular good melt shape (desirable radius-of-curvature), also require high-fire resistance, high solvent resistance, high light transmission etc., but can fully satisfy such various requirement, and yet no problem radiation sensitive resin composition did not have in the past aspect security.
Summary of the invention
The present invention finishes in view of above situation, first purpose of the present invention provides radiation sensitive resin composition, its security is no problem, susceptibility, resolution, all excellent as the storage stability of solution etc., still can form good pattern form even in developing procedure, surpass optimum development time, have excellent developing nargin (margin).
Second purpose of the present invention provides the method that forms interlayer dielectric, and this method is used above-mentioned radiation sensitive resin composition, forms the interlayer dielectric that has both excellent solvent resistance, thermotolerance, light transmission, adaptation etc.
The 3rd purpose of the present invention provides and forms lenticular method, this method is used above-mentioned radiation sensitive resin composition, forms the lenticule that has both excellent solvent resistance, thermotolerance, light transmission, adaptation etc. and have good melt shape.
Other purposes of the present invention and advantage are clear and definite by following explanation.
According to the present invention, one of above-mentioned purpose of the present invention and advantage realize by radiation sensitive resin composition, it is characterized in that containing (a1), (a2) and multipolymer (a3) [A], and 1,2-two nitrine naphtoquinone compounds [B];
Described (a1) is selected from a kind of compound at least in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides;
(a2) be selected from least a compound in the compound shown in compound shown in the following formula (1) and the following formula (2);
Figure A20061014213600061
(in the formula (1), R represents the alkyl of hydrogen atom or carbon number 1～4, R 1The alkyl of expression hydrogen atom or carbon number 1～4, R 2, R 3, R 4And R 5Represent the alkyl of hydrogen atom, fluorine atom, carbon number 1～4, the aryl of carbon number 6～20 or the perfluoroalkyl of carbon number 1～4 independently of one another, n is 1～6 integer.)
Figure A20061014213600062
(in the formula (2), R, R 1, R 2, R 3, R 4And R 5And n is identical with the definition in the above-mentioned formula (1).)
(a3) have the multipolymer of the unsaturated compound that is selected from least a structure in the structure shown in tetrahydrofuran skeleton, furans skeleton, oxinane skeleton, pyrans skeleton and the following formula (3) in the molecule,
Figure A20061014213600071
(in the formula (3), R 6Be hydrogen atom or methyl, m is 2～10 integer.)
1, two of 2-two nitrine naphtoquinone compounds [B] above-mentioned purposes of the present invention and advantage is that the formation method by interlayer dielectric realizes, it is characterized in that comprising following operation according to following order:
(1) operation of the above-mentioned radiation sensitive resin composition tunicle of formation on substrate,
(2) to the operation of at least a portion of this tunicle irradiation radioactive ray,
(3) operation that postradiation tunicle is developed, and
(4) operation that heats of the tunicle after will developing.
Three of above-mentioned purpose of the present invention and advantage realizes by lenticular formation method, it is characterized in that comprising following operation according to following order:
(1) operation of the above-mentioned radiation sensitive resin composition tunicle of formation on substrate,
(2) to the operation of at least a portion of this tunicle irradiation radioactive ray,
(3) operation that postradiation tunicle is developed, and
(4) operation that heats of the tunicle after will developing.
Description of drawings
Fig. 1 represents the synoptic diagram of lenticule cross sectional shape.
Embodiment
Below the present invention is described in detail.
Multipolymer [A]
Contained multipolymer [A] is following (a1) in the radiation sensitive resin composition of the present invention, (a2) and multipolymer (a3), described (a1) is selected from a kind of compound at least (hereinafter referred to as " unsaturated compound (a1) ") in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides, (a2) be selected from least a compound (hereinafter referred to as " unsaturated compound (a2) ") in the compound shown in compound shown in the following formula (1) and the above-mentioned formula (2), (a3) have the tetrahydrofuran of being selected from skeleton in the molecule, the furans skeleton, the oxinane skeleton, the unsaturated compound of at least a structure in the structure shown in pyrans skeleton and the above-mentioned formula (3) (hereinafter referred to as " unsaturated compound (a3) ").
As unsaturated compound (a1), can enumerate list (methyl) acrylate that has the polymkeric substance of carboxyl and hydroxyl as the acid anhydrides of monocarboxylic acid compound, dicarboxylic acid compound, dicarboxylic acid, the list of polybasic carboxylic acid [(methyl) acryloxyalkyl] ester, two ends etc.
Above-mentioned monocarboxylic acid can be enumerated as acrylic acid, methacrylic acid, crotonic acid, 2-acryloxy ethyl succinic acid, 2-methacryloxyethyl succinic acid, 2-acryloxy ethyl hexahydrophthalic acid, 2-methacryloxyethyl hexahydrophthalic acid etc.;
Above-mentioned dicarboxylic acid can be enumerated as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc.;
The acid anhydrides of above-mentioned dicarboxylic acid can be enumerated acid anhydrides as above-mentioned dicarboxylic acid compound etc.;
The list of above-mentioned polybasic carboxylic acid [(methyl) acryloxyalkyl] ester can be enumerated as mono succinate (2-acryloxy ethyl) ester, mono succinate (2-methacryloxyethyl) ester, phthalic acid list (2-acryloxy ethyl) ester, phthalic acid list (2-methacryloxyethyl) ester etc.;
Above-mentioned two ends have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl, can enumerate as ω-carboxyl polycaprolactone single-acrylate, ω-carboxyl polycaprolactone monomethacrylates etc.
Among these unsaturated compounds (a1), from copolyreaction, for the dissolubility of aqueous alkali with obtain considering preferred acrylic acid, methacrylic acid, maleic anhydride etc. easily.
Above-mentioned unsaturated compound (a1) can use separately, and also two or more kinds may be used.
In the polymkeric substance [A], from preferred 5～60 weight % of content of the repetitive of (a1) unsaturated compound, further preferred 10～50 weight % are preferably 15～40 weight % especially.By content is located at this scope, can controls the composition that obtains for the dissolubility of alkaline developer in more suitable scope.
Unsaturated compound (a2) is for being selected from least a compound of the compound shown in compound shown in the following formula (1) and the following formula (2).
Figure A20061014213600091
(in the formula (1), R represents the alkyl of hydrogen atom or carbon number 1～4, R 1The alkyl of expression hydrogen atom or carbon number 1～4, R 2, R 3, R 4And R 5Represent the alkyl of hydrogen atom, fluorine atom, carbon number 1～4, the aryl of carbon number 6～20 or the perfluoroalkyl of carbon number 1～4 independently of one another, n is 1～6 integer.)
Figure A20061014213600092
(in the formula (2), R, R 1, R 2, R 3, R 4And R 5And n is identical with the definition in the above-mentioned formula (1).)
In above-mentioned formula (1) and (2), as R, R 1, R 2, R 3, R 4With the alkyl of the carbon number 1～4 of R, can enumerate as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group etc.
As R 2, R 3, R 4And R 5The aryl of carbon number 6～20, can enumerate as phenyl, tolyl etc.As R 2, R 3, R 4And R 5The perfluoroalkyl of carbon number 1～4, can enumerate as trifluoromethyl, pentafluoroethyl group, seven fluorine n-pro-pyls, seven fluorine isopropyls, nine fluorine normal-butyls, nine fluorine isobutyls, nine fluorine sec-butyls, the nine fluorine tert-butyl groups etc.
As the compound shown in the above-mentioned formula (1), can enumerate oxetanes as 3-(acryloyl-oxy ylmethyl), 3-(acryloyl-oxy ylmethyl)-2-methyl oxetanes, 3-(acryloyl-oxy ylmethyl)-3-ethyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-trifluoromethyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-pentafluoroethyl group oxetanes, 3-(acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2,2-difluoro oxetanes, 3-(acryloyl-oxy ylmethyl)-2,2,4-trifluoro oxetanes, 3-(acryloyl-oxy ylmethyl)-2,2,4,4-tetrafluoro oxetanes, 3-(2-acryloxy ethyl) oxetanes, 3-(2-acryloxy ethyl)-2-ethyl oxetanes, 3-(2-acryloxy ethyl)-3-ethyl oxetanes, 3-(2-acryloxy ethyl)-2-trifluoromethyl oxetanes, 3-(2-acryloxy ethyl)-2-pentafluoroethyl group oxetanes, 3-(2-acryloxy ethyl)-2-phenyl oxetanes, 3-(2-acryloxy ethyl)-2,2-difluoro oxetanes, 3-(2-acryloxy ethyl)-2,2,4-trifluoro oxetanes, 3-(2-acryloxy ethyl)-2,2,4, acrylate such as 4-tetrafluoro oxetanes;
3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-2-methyl oxetanes, 3-(methacryloxy methyl)-3-ethyl oxetanes, 3-(methacryloxy methyl)-2-trifluoromethyl oxetanes, 3-(methacryloxy methyl)-2-pentafluoroethyl group oxetanes, 3-(methacryloxy methyl)-2-phenyl oxetanes, 3-(methacryloxy methyl)-2,2-difluoro oxetanes, 3-(methacryloxy methyl)-2,2,4-trifluoro oxetanes, 3-(methacryloxy methyl)-2,2,4,4-tetrafluoro oxetanes, 3-(2-methacryloxyethyl) oxetanes, 3-(2-methacryloxyethyl)-2-ethyl oxetanes, 3-(2-methacryloxyethyl)-3-ethyl oxetanes, 3-(2-methacryloxyethyl)-2-trifluoromethyl oxetanes, 3-(2-methacryloxyethyl)-2-pentafluoroethyl group oxetanes, 3-(2-methacryloxyethyl)-2-phenyl oxetanes, 3-(2-methacryloxyethyl)-2,2-difluoro oxetanes, 3-(2-methacryloxyethyl)-2,2,4-trifluoro oxetanes, 3-(2-methacryloxyethyl)-2,2,4, acrylate such as 4-tetrafluoro oxetanes.
As the compound shown in the above-mentioned formula (2), can enumerate oxetanes as 2-(acryloyl-oxy ylmethyl), 2-(acryloyl-oxy ylmethyl)-2-methyl oxetanes, 2-(acryloyl-oxy ylmethyl)-3-methyl oxetanes, 2-(acryloyl-oxy ylmethyl)-4-methyl oxetanes, 2-(acryloyl-oxy ylmethyl)-2-trifluoromethyl oxetanes, 2-(acryloyl-oxy ylmethyl)-3-trifluoromethyl oxetanes, 2-(acryloyl-oxy ylmethyl)-4-trifluoromethyl oxetanes, 2-(acryloyl-oxy ylmethyl)-2-pentafluoroethyl group oxetanes, 2-(acryloyl-oxy ylmethyl)-3-pentafluoroethyl group oxetanes, 2-(acryloyl-oxy ylmethyl)-4-pentafluoroethyl group oxetanes, 2-(acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 2-(acryloyl-oxy ylmethyl)-3-phenyl oxetanes, 2-(acryloyl-oxy ylmethyl)-4-phenyl oxetanes, 2-(acryloyl-oxy ylmethyl)-2,3-difluoro oxetanes, 2-(acryloyl-oxy ylmethyl)-2,4-difluoro oxetanes, 2-(acryloyl-oxy ylmethyl)-3,3-difluoro oxetanes, 2-(acryloyl-oxy ylmethyl)-3,4-difluoro oxetanes, 2-(acryloyl-oxy ylmethyl)-4,4-difluoro oxetanes, 2-(acryloyl-oxy ylmethyl)-3,3,4-trifluoro oxetanes, 2-(acryloyl-oxy ylmethyl)-3,4,4-trifluoro oxetanes, 2-(acryloyl-oxy ylmethyl)-3,3,4,4-tetrafluoro oxetanes;
2-(2-acryloxy ethyl) oxetanes, methacrylic acid 2-[2-(2-methyl oxetanyl)] ethyl ester, methacrylic acid 2-[2-(3-methyl oxetanyl)] ethyl ester, 2-(acryloxy ethyl)-2-methyl oxetanes, 2-(2-acryloxy ethyl)-4-methyl oxetanes, 2-(2-acryloxy ethyl)-2-trifluoromethyl oxetanes, 2-(2-acryloxy ethyl)-3-trifluoromethyl oxetanes, 2-(2-acryloxy ethyl)-4-trifluoromethyl oxetanes, 2-(2-acryloxy ethyl)-2-pentafluoroethyl group oxetanes, 2-(2-acryloxy ethyl)-3-pentafluoroethyl group oxetanes, 2-(2-acryloxy ethyl)-4-pentafluoroethyl group oxetanes, 2-(2-acryloxy ethyl)-2-phenyl oxetanes, 2-(2-acryloxy ethyl)-3-phenyl oxetanes, 2-(2-acryloxy ethyl)-4-phenyl oxetanes, 2-(2-acryloxy ethyl)-2,3-difluoro oxetanes, 2-(2-acryloxy ethyl)-2,4-difluoro oxetanes, 2-(2-acryloxy ethyl)-3,3-difluoro oxetanes, 2-(2-acryloxy ethyl)-3,4-difluoro oxetanes, 2-(2-acryloxy ethyl)-4,4-difluoro oxetanes, 2-(2-acryloxy ethyl)-3,3,4-trifluoro oxetanes, 2-(2-acryloxy ethyl)-3,4,4-trifluoro oxetanes, 2-(2-acryloxy ethyl)-3,3,4, acrylate such as 4-tetrafluoro oxetanes;
2-(methacryloxy methyl) oxetanes, 2-(methacryloxy methyl)-2-methyl oxetanes, 2-(methacryloxy methyl)-3-methyl oxetanes, 2-(methacryloxy methyl)-4-methyl oxetanes, 2-(methacryloxy methyl)-2-trifluoromethyl oxetanes, 2-(methacryloxy methyl)-3-trifluoromethyl oxetanes, 2-(methacryloxy methyl)-4-trifluoromethyl oxetanes, 2-(methacryloxy methyl)-2-pentafluoroethyl group oxetanes, 2-(methacryloxy methyl)-3-pentafluoroethyl group oxetanes, 2-(methacryloxy methyl)-4-pentafluoroethyl group oxetanes, 2-(methacryloxy methyl)-2-phenyl oxetanes, 2-(methacryloxy methyl)-3-phenyl oxetanes, 2-(methacryloxy methyl)-4-phenyl oxetanes, 2-(methacryloxy methyl)-2,3-difluoro oxetanes, 2-(methacryloxy methyl)-2,4-difluoro oxetanes, 2-(methacryloxy methyl)-3,3-difluoro oxetanes, 2-(methacryloxy methyl)-3,4-difluoro oxetanes, 2-(methacryloxy methyl)-4,4-difluoro oxetanes, 2-(methacryloxy methyl)-3,3,4-trifluoro oxetanes, 2-(methacryloxy methyl)-3,4,4-trifluoro oxetanes, 2-(methacryloxy methyl)-3,3,4,4-tetrafluoro oxetanes;
2-(2-methacryloxyethyl) oxetanes, methacrylic acid 2-[2-(2-methyl oxetanyl)] ethyl ester, methacrylic acid 2-[2-(3-methyl oxetanyl)] ethyl ester, 2-(2-methacryloxyethyl)-2-methyl oxetanes, 2-(2-methacryloxyethyl)-4-methyl oxetanes, 2-(2-methacryloxyethyl)-2-trifluoromethyl oxetanes, 2-(2-methacryloxyethyl)-3-trifluoromethyl oxetanes, 2-(2-methacryloxyethyl)-4-trifluoromethyl oxetanes, 2-(2-methacryloxyethyl)-2-pentafluoroethyl group oxetanes, 2-(2-methacryloxyethyl)-3-pentafluoroethyl group oxetanes, 2-(2-methacryloxyethyl)-4-pentafluoroethyl group oxetanes, 2-(2-methacryloxyethyl)-2-phenyl oxetanes, 2-(2-methacryloxyethyl)-3-phenyl oxetanes, 2-(2-methacryloxyethyl)-4-phenyl oxetanes, 2-(2-methacryloxyethyl)-2,3-difluoro oxetanes, 2-(2-methacryloxyethyl)-2,4-difluoro oxetanes, 2-(2-methacryloxyethyl)-3,3-difluoro oxetanes, 2-(2-methacryloxyethyl)-3,4-difluoro oxetanes, 2-(2-methacryloxyethyl)-4,4-difluoro oxetanes, 2-(2-methacryloxyethyl)-3,3,4-trifluoro oxetanes, 2-(2-methacryloxyethyl)-3,4,4-trifluoro oxetanes, 2-(2-methacryloxyethyl)-3,3,4, methacrylates such as 4-tetrafluoro oxetanes etc.
Among these unsaturated compounds (a2), wide from the development nargin such as radiation sensitive resin composition that obtain, and chemical sproof viewpoint such as interlayer dielectric that raising obtains and lenticule is considered, preferred 3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-3-ethyl oxetanes, 3-(methacryloxy methyl)-2-trifluoromethyl oxetanes, 3-(methacryloxy methyl)-2-phenyl oxetanes, 2-(methacryloxy methyl) oxetanes, 2-(methacryloxy methyl)-4-trifluoromethyl oxetanes etc.
Above-mentioned unsaturated compound (a2) can use separately, and also two or more kinds may be used.
In the polymkeric substance [A], preferred 5～60 weight % of content of the structural unit of being derived by unsaturated compound (a2) are preferably 10～50 weight % especially.By content being located at this scope, can make the storage stability of composition excellent more with interlayer dielectric that obtains or lenticular stable on heating balance.
Unsaturated compound (a3) is to have the unsaturated compound that is selected from least a structure in the structure shown in tetrahydrofuran skeleton, furans skeleton, oxinane skeleton, pyrans skeleton and the following formula (3) in the molecule.
Figure A20061014213600131
(in the formula (3), R 6Be hydrogen atom or methyl, m is 2～10 integer).
The object lesson of unsaturated compound (a3) has: as the unsaturated compound with tetrahydrofuran skeleton, can enumerate as (methyl) acrylic acid tetrahydro furfuryl ester, 2-methacryloxypropioniacid acid tetrahydro furfuryl ester, (methyl) acrylic acid tetrahydrofuran-3-base ester etc.;
As unsaturated compound, can enumerate 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, acrylic acid 2-furans-2-base-1-methyl ethyl ester, 6-(2-furyl)-6-methyl isophthalic acid-teracrylic acid-ketone etc. with furans skeleton;
As unsaturated compound with oxinane structure, can enumerate as methacrylic acid (oxinane-2-yl) methyl esters, 2 6-dimethyl-8-(oxinane-2-base oxygen base)-Xin-1-alkene-3-ketone, 2-methacrylic acid oxinane-2-base ester, 1-(oxinane-2-oxygen base)-butyl-3-alkene-2-ketone etc.;
As unsaturated compound, can enumerate as 4-(1,4-two oxa-s-5-oxo-6-heptenyl)-6-methyl-2-pyrone, 4-(1,5-two oxa-s-6-oxo-7-octenyl)-6-methyl-2-pyrone etc. with pyran structure;
As unsaturated compound, can enumerate the compound shown in the difference of following formula (4)～(6) with the structure shown in the above-mentioned formula (3).
Figure A20061014213600141
(in formula (4)～(6), R 7Independent separately, be hydrogen atom or methyl; A is independent separately in formula (4) and (5), is 2～10 integer; A is 3～10 integer in the formula (6).)
Wherein, consider the preferred compound shown in (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid tetrahydrofuran-3-base ester, 1-(oxinane-2-oxygen) butyl-3-alkene-2-ketone, (methyl) acrylic acid furfuryl group ester, the above-mentioned formula (4) etc. that uses from the viewpoint that development nargin is wide.These compounds can use separately, also can make up more than 2 kinds and use.
In the polymkeric substance [A], from preferred 3～50 weight % of content of the repetitive of unsaturated compound (a3), further preferred 5～40 weight %.By content being located at this scope, the development of composition is improved more.
Polymkeric substance [A], except from above-mentioned unsaturated compound (a1), (a2) and the repetitive (a3), also can at random contain from (a4) and above-mentioned unsaturated compound (a1), (a2) and (a3) repetitive of different other ethylene series unsaturated compounds (hereinafter referred to as " unsaturated compound (a4) ").Unsaturated compound (a4), as long as can with above-mentioned unsaturated compound (a1), (a2), (a3) copolymerization, just be not particularly limited, can enumerate as alkyl acrylate, methacrylic acid cycloalkyl ester, acrylic acid cycloalkyl ester, methacrylic acid cycloalkyl ester, acrylic acid aryl ester, aryl methacrylate, unsaturated dicarboxylic diester, acrylic acid hydroxyalkyl acrylate, methacrylic acid hydroxyl Arrcostab, two ring unsaturated compounds, unsaturated dicarbapentaborane imide derivative, styrene and derivant and other unsaturated compounds.
As the aforesaid propylene acid alkyl ester, can enumerate as methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate etc.;
As above-mentioned alkyl methacrylate, can enumerate as methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, the secondary butyl ester of methacrylic acid, metering system tert-butyl acrylate etc.;
As the acrylic acid cycloalkyl ester, can enumerate cyclohexyl acrylate, acrylic acid 2-methyl cyclohexane ester, acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester (hereinafter referred to as " acrylic acid dicyclopentenyl ester "), acrylic acid 2-two cyclopentene oxygen base ethyl esters, isobornyl acrylate etc.;
As the methacrylic acid cycloalkyl ester, can enumerate as cyclohexyl methacrylate, methacrylic acid 2-methyl cyclohexane ester, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester (hereinafter referred to as " methacrylic acid dicyclopentenyl ester "), methacrylic acid 2-two cyclopentene oxygen base ethyl esters, isobornyl methacrylate etc.;
As aforesaid propylene acid aryl ester, can enumerate as phenyl acrylate, benzyl acrylate etc.;
As above-mentioned aryl methacrylate, can enumerate as phenyl methacrylate, benzyl methacrylate etc.;
As above-mentioned unsaturated dicarboxylic diester, can enumerate as diethyl maleate, DEF, diethyl itaconate etc.;
As aforesaid propylene acid hydroxyalkyl acrylate, can enumerate as methacrylic acid hydroxyl methyl esters, acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester, 2-hydroxyethyl methacrylate, methacrylic acid-3-hydroxy methacrylate, methacrylic acid-4-hydroxyl butyl ester, diglycol monotertiary methacrylate, methacrylic acid-2,3-dihydroxy propyl ester, 2-methacryloxyethyl glucoside etc.;
As above-mentioned methacrylic acid hydroxyl Arrcostab, can enumerate as 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester etc.;
As above-mentioned two ring unsaturated compounds, can enumerate as 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-hydroxyl two ring [2.2.1] hept-2-ene"s, 5-carboxyl two ring [2.2.1] hept-2-ene"s, 5-hydroxymethyl two ring [2.2.1] hept-2-ene"s, 5-(2-hydroxyethyl) 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-dihydroxy two ring [2.2.1] hept-2-ene"s, 5,6-two (hydroxyethyl) two ring [2.2.1] hept-2-ene"s, 5,6-dimethoxy two ring [2.2.1] hept-2-ene"s, 5,6-diethoxy two ring [2.2.1] hept-2-ene"s, 5-hydroxy-5-methyl base two ring [2.2.1] hept-2-ene"s, 5-hydroxyl-5-ethyl two ring [2.2.1] hept-2-ene"s, 5-hydroxymethyl-5-methyl bicyclic [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl two ring [2.2.1] hept-2-ene"s, 5-cyclohexyl oxygen base carbonyl two ring [2.2.1] hept-2-ene"s, 5-phenyloxycarbonyl two ring [2.2.1] hept-2-ene"s, 5,6-two (tert-butoxycarbonyl) two ring [2.2.1] hept-2-ene"s, 5,6-two (cyclohexyl oxygen base carbonyl) two ring [2.2.1] hept-2-ene"s etc.;
As above-mentioned unsaturated dicarbapentaborane imide derivative, can enumerate as N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimido-3-maleimide benzoate, N-succinimido-4-maleimide butyrate, N-succinimido-6-maleimide caproate, N-succinimido-3-maleimide propionate, N-(9-acridinyl) maleimide etc.;
As above-mentioned styrene and derivant thereof, can enumerate as styrene, α-Jia Jibenyixi, a methyl styrene, p-methylstyrene, a vinyltoluene, to vinyltoluene, to methoxy styrene etc.;
As above-mentioned other unsaturated compounds, can enumerate as vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1, the 3-butadiene, isoprene, 2,3-dimethyl-1, the 3-butadiene, glycidyl acrylate, glycidyl methacrylate, the α-Yi Jibingxisuan ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, acrylic acid 3,4-epoxy butyl ester, methacrylic acid 3,4-epoxy butyl ester, α-Yi Jibingxisuan 3,4-epoxy butyl ester, acrylic acid-6,7-epoxy heptyl ester, methacrylic acid α-3,4-epoxy butyl ester, ethylacrylic acid-6,7-epoxy heptyl ester, adjacent vinyl benzyl glycidol ether, between the vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether etc.
Among these unsaturated compounds (a4), consider in the dissolubility of aqueous alkali from copolyreaction and the multipolymer [A] that obtains, preferable methyl acrylic acid tertiary butyl ester, acrylic acid 2-methyl cyclohexane ester, methacrylic acid dicyclopentenyl ester, two ring [2.2.1] hept-2-ene"s, N-phenylmaleimide, N-cyclohexyl maleimide, styrene, to methoxy styrene, 1,3-butadiene, glycidyl methacrylate, adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to the vinyl benzyl glycidol ether etc.
Above-mentioned unsaturated compound (a4) can use separately, and also two or more kinds may be used.
Below the preferred 80 weight % of the content of the structural unit of deriving by unsaturated compound (a4) in the multipolymer [A], more preferably 10～80 weight %, preferred especially 20～70 weight %.By content being located at this scope, can control the storage stability of the composition that obtains and the dissolubility in alkaline developer in more suitable scope.
As preferred multipolymer of the present invention [A], more specifically can enumerate:
Be selected from least a kind of unsaturated compound (a1) in acrylic acid, methacrylic acid and the maleic anhydride;
Be selected from least a kind of unsaturated compound (a2) in 3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-3-ethyl oxetanes, 3-(methacryloxy methyl)-2-trifluoromethyl oxetanes, 3-(methacryloxy methyl)-2-phenyl oxetanes, 2-(methacryloxy methyl) oxetanes and 2-(methacryloxy the methyl)-4-trifluoromethyl oxetanes;
Be selected from least a kind of unsaturated compound (a3) in the compound shown in (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid tetrahydrofuran-3-base ester, 1-(oxinane-2-oxygen) butyl-3-alkene-2-ketone, (methyl) acrylic acid furfuryl group ester and the above-mentioned formula (4); With
Be selected from methacrylic acid tertiary butyl ester, acrylic acid 2-methyl cyclohexane ester, methacrylic acid dicyclopentenyl ester, two ring [2.2.1] hept-2-ene"s, N-phenylmaleimide, N-cyclohexyl maleimide, styrene, to methoxy styrene, 1,3-butadiene, glycidyl methacrylate, adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to the multipolymer of at least a kind of unsaturated compound (a4) in the vinyl benzyl glycidol ether.
The polystyrene conversion weight-average molecular weight of multipolymer [A] (hereinafter referred to as " Mw ") is preferably 1 * 10 3～5 * 10 5, more preferably 3 * 10 3～3 * 10 5, further preferred 5 * 10 3～1 * 10 5
Molecular weight distribution by ratio (Mw/Mn) definition of the Mw of multipolymer [A] and polystyrene conversion number-average molecular weight (hereinafter referred to as " Mn ") is preferred below 5.0, and more preferably 1.0～3.0.
Contain radiation sensitive resin composition, when developing, can not produce residual, the film minimizing of developing, can form the pattern of regulation shape easy as can with such Mw and multipolymer of Mw/Mn [A].
Multipolymer [A] has at least a kind and oxetanes ring structure among carboxyl and the acid anhydride, has the dissolubility of appropriateness in aqueous alkali, though simultaneously not with special hardening agent and usefulness, also can solidify easily by heating.The radiation sensitive resin composition that contains multipolymer [A] can not produce residual, the film minimizing of developing when developing, can easily form the tunicle of predetermined pattern.
Multipolymer [A] can use separately, and also two or more kinds may be used.
As mentioned above, for example, with unsaturated compound (a1), unsaturated compound (a2) and unsaturated compound (a3), and the unsaturated compound (a4) that according to circumstances adds synthesizes above-mentioned multipolymer [A] by polymerization in the presence of radical polymerization initiator in appropriate solvent.
As solvent used in the above-mentioned polymerization, can enumerate as alcohol, ether, glycol ether, ethylene glycol alkyl ether acetic acid esters, diglycol ether, propylene glycol, propylene glycol alkyl ether acetic acid ester, propylene glycol alkyl ether propionic ester, aromatic hydrocarbons, ketone, ester etc.
As above-mentioned alcohol, can enumerate as methyl alcohol, ethanol, benzylalcohol, 2-phenylethanol, 3-phenyl-1-propyl alcohol etc.; As ether, can enumerate as tetrahydrofuran etc.;
As glycol ether, can enumerate as glycol monoethyl ether, ethylene glycol monoethyl ether etc.;
As ethylene glycol alkyl ether acetic acid esters, can enumerate as Ethylene Glycol Methyl ether acetic acid ester, ethylene glycol monoethyl ether acetate, ethylene glycol n-propyl ether acetic acid esters, ethylene glycol n-butyl ether acetic acid ester etc.;
As diglycol ether, can enumerate as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, diglycol ethyl-methyl ether etc.;
As propylene glycol, can enumerate as propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether etc.;
As propylene glycol alkyl ether acetic acid ester, can enumerate as methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol n-propyl ether acetic acid esters, propylene glycol n-butyl ether acetic acid esters etc.;
As propylene glycol alkyl ether propionic ester, can enumerate as methyl proxitol propionic ester, propylene glycol ethylether propionic ester, propylene glycol n-propyl ether propionic ester, propylene glycol n-butyl ether propionic ester etc.;
As aromatic hydrocarbons, can enumerate as toluene, dimethylbenzene etc.; As ketone, can enumerate as MEK, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone etc.;
As ester, can enumerate as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid n-propyl, the positive butyl ester of glycolic acid, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid n-propyl, the positive butyl ester of 3-hydracrylic acid, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 2-hydroxy-3-methyl ethyl butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid n-propyl, the positive butyl ester of methoxyacetic acid, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid n-propyl, the positive butyl ester of ethoxyacetic acid, the positive propoxy methyl acetate, positive propoxy ethyl acetate, the positive propoxy n-propyl acetate, the positive propoxy n-butyl acetate, the n-butoxy methyl acetate, n-butoxy ethyl acetate, the n-butoxy n-propyl acetate, the n-butoxy n-butyl acetate, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxypropionic acid n-propyl, the positive butyl ester of 2-methoxypropionic acid, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-propionic acid n-propyl, the positive butyl ester of 2-ethoxy-propionic acid, 2-positive propoxy methyl propionate, 2-positive propoxy ethyl propionate, 2-positive propoxy propionic acid n-propyl, 2-positive propoxy n-butyl propionate, 2-n-butoxy methyl propionate, 2-n-butoxy ethyl propionate, 2-n-butoxy propionic acid n-propyl, 2-n-butoxy n-butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxypropionic acid n-propyl, the positive butyl ester of 3-methoxypropionic acid, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid n-propyl, the positive butyl ester of 3-ethoxy-propionic acid, 3-positive propoxy methyl propionate, 3-positive propoxy ethyl propionate, 3-positive propoxy propionic acid n-propyl, 3-positive propoxy n-butyl propionate, 3-n-butoxy methyl propionate, 3-n-butoxy ethyl propionate, 3-n-butoxy propionic acid n-propyl, 3-n-butoxy n-butyl propionate etc.
Among these solvents, preferred ethylene glycol alkyl ether acetic acid esters, diglycol ether, propylene glycol, propylene glycol alkyl ether acetic acid ester etc., preferred especially diethylene glycol dimethyl ether, diglycol ethyl-methyl ether, propylene glycol monomethyl ether, methyl proxitol acetate.
Above-mentioned solvent may be used singly or in combination of two or more kinds.
As radical polymerization initiator used in the above-mentioned polymerization, can enumerate as 2,2 '-azoisobutyronitrile, 2,2 '-azo is two-(2, the 4-methyl pentane nitrile), 2, and 2 '-azo is two-azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, the peroxidating valeric acid tert-butyl ester, 1,1 '-organic peroxides such as two (tert-butyl peroxide) cyclohexane; Hydrogen peroxide etc.When using superoxide, also can use superoxide to be used as the oxidation-reduction type initiating agent with reductive agent as radical polymerization initiator.
These radical polymerization initiators may be used singly or in combination of two or more kinds.
During above-mentioned polymerization,, can also use molecular weight regulator in order to regulate the molecular weight of multipolymer [A].
As the object lesson of molecular weight regulator, can enumerate halogenated hydrocarbons such as chloroform, carbon tetrabromide; Mercaptan such as positive hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, mercaptoacetic acid; Xanthates such as sulfuration dimethyl yellow ortho esters, dithiodiisopropyl xanthate; Terpinolene, α-Jia Jibenyixi dimer etc.
These molecular weight regulators may be used singly or in combination of two or more kinds.
1,2-two nitrine naphtoquinone compounds [B]
Radiation sensitive resin composition of the present invention contained 1,2-two nitrine naphtoquinone compounds [B] produce acid by the irradiation of radioactive ray, for example 1,2-two azido benzoquinone sulphonic acid esters, 1,2-diazido naphthoquinone sulphonic acid ester, 1,2-two azido benzoquinone sulfonamide, 1,2-diazido naphthoquinone sulfonamide etc.
As above-mentioned 1,2-diazido naphthoquinone sulphonic acid ester, can enumerate as 1 of trihydroxybenzophenone, 1 of 2-diazido naphthoquinone sulphonic acid ester, tetrahydroxybenzophenone, 1 of 2-diazido naphthoquinone sulphonic acid ester, pentahydroxybenzophenone, 1 of 2-diazido naphthoquinone sulphonic acid ester, hexahydroxy benzophenone, 2-diazido naphthoquinone sulphonic acid ester, other (polyhydroxy phenyl) alkane 1,2-diazido naphthoquinone sulphonic acid ester etc.Its object lesson has: 1 of trihydroxybenzophenone, and 2-diazido naphthoquinone sulphonic acid ester for example has 2,3,4-trihydroxybenzophenone-1,2-diazido naphthoquinone-4-sulphonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-diazido naphthoquinone-5-sulphonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-diazido naphthoquinone-6-sulphonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-diazido naphthoquinone-7-sulphonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-diazido naphthoquinone-8-sulphonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-diazido naphthoquinone-4-sulphonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-diazido naphthoquinone-5-sulphonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-diazido naphthoquinone-6-sulphonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-diazido naphthoquinone-7-sulphonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-diazido naphthoquinone-8-sulphonic acid ester etc.;
1 of tetrahydroxybenzophenone, 2-diazido naphthoquinone sulphonic acid ester for example has 2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-4-sulphonic acid ester, 2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-5-sulphonic acid ester, 2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-6-sulphonic acid ester, 2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-7-sulphonic acid ester, 2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-8-sulphonic acid ester, 2,3,4,3 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-4-sulphonic acid ester, 2,3,4,3 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-5-sulphonic acid ester, 2,3,4,3 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-6-sulphonic acid ester, 2,3,4,3 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-7-sulphonic acid ester, 2,3,4,3 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-8-sulphonic acid ester, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-4-sulphonic acid ester, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-5-sulphonic acid ester, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-6-sulphonic acid ester, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-7-sulphonic acid ester, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-diazido naphthoquinone-8-sulphonic acid ester;
2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl ketone-1,2-diazido naphthoquinone-4-sulphonic acid ester, 2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl ketone-1,2-diazido naphthoquinone-5-sulphonic acid ester, 2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl ketone-1,2-diazido naphthoquinone-6-sulphonic acid ester, 2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl ketone-1,2-diazido naphthoquinone-7-sulphonic acid ester, 2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl ketone-1,2-diazido naphthoquinone-8-sulphonic acid ester, 2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone-1,2-diazido naphthoquinone-4-sulphonic acid ester, 2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone-1,2-diazido naphthoquinone-5-sulphonic acid ester, 2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone-1,2-diazido naphthoquinone-6-sulphonic acid ester, 2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone-1,2-diazido naphthoquinone-7-sulphonic acid ester, 2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone-1,2-diazido naphthoquinone-8-sulphonic acid ester etc.
1 of above-mentioned pentahydroxybenzophenone, 2-diazido naphthoquinone sulphonic acid ester can be enumerated as 2,3,4,2 ', 6 '-pentahydroxybenzophenone-1,2-diazido naphthoquinone-4-sulphonic acid ester, 2,3,4,2 ', 6 '-pentahydroxybenzophenone-1,2-diazido naphthoquinone-5-sulphonic acid ester, 2,3,4,2 ', 6 '-pentahydroxybenzophenone-1,2-diazido naphthoquinone-6-sulphonic acid ester, 2,3,4,2 ', 6 '-pentahydroxybenzophenone-1,2-diazido naphthoquinone-7-sulphonic acid ester, 2,3,4,2 ', 6 '-pentahydroxybenzophenone-1,2-diazido naphthoquinone-8-sulphonic acid ester etc.;
1 of above-mentioned hexahydroxy benzophenone, 2-diazido naphthoquinone sulphonic acid ester can be enumerated as 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-diazido naphthoquinone-4-sulphonic acid ester, 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-diazido naphthoquinone-5-sulphonic acid ester, 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-diazido naphthoquinone-6-sulphonic acid ester, 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-diazido naphthoquinone-7-sulphonic acid ester, 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-diazido naphthoquinone-8-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-diazido naphthoquinone-4-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-diazido naphthoquinone-5-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-diazido naphthoquinone-6-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-diazido naphthoquinone-7-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-diazido naphthoquinone-8-sulphonic acid ester etc.;
Above-mentioned other (polyhydroxy phenyl) alkane 1,2-diazido naphthoquinone sulphonic acid ester, can enumerate as two (2, the 4-dihydroxy phenyl) methane-1,2-diazido naphthoquinone-4-sulphonic acid ester, two (2, the 4-dihydroxy phenyl) methane-1,2-diazido naphthoquinone-5-sulphonic acid ester, two (2, the 4-dihydroxy phenyl) methane-1,2-diazido naphthoquinone-6-sulphonic acid ester, two (2, the 4-dihydroxy phenyl) methane-1,2-diazido naphthoquinone-7-sulphonic acid ester, two (2, the 4-dihydroxy phenyl) methane-1,2-diazido naphthoquinone-8-sulphonic acid ester, two (4-hydroxy phenyl) methane-1,2-diazido naphthoquinone-4-sulphonic acid ester, two (4-hydroxy phenyl) methane-1,2-diazido naphthoquinone-5-sulphonic acid ester, two (4-hydroxy phenyl) methane-1,2-diazido naphthoquinone-6-sulphonic acid ester, two (4-hydroxy phenyl) methane-1,2-diazido naphthoquinone-7-sulphonic acid ester, two (4-hydroxy phenyl) methane-1,2-diazido naphthoquinone-8-sulphonic acid ester, three (4-hydroxy phenyl) methane-1,2-diazido naphthoquinone-4-sulphonic acid ester, three (4-hydroxy phenyl) methane-1,2-diazido naphthoquinone-5-sulphonic acid ester, three (4-hydroxy phenyl) methane-1,2-diazido naphthoquinone-6-sulphonic acid ester, three (4-hydroxy phenyl) methane-1,2-diazido naphthoquinone-7-sulphonic acid ester, three (4-hydroxy phenyl) methane-1,2-diazido naphthoquinone-8-sulphonic acid ester;
1,1,1-three (4-hydroxy phenyl) ethane-1,2-diazido naphthoquinone-4-sulphonic acid ester, 1,1,1-three (4-hydroxy phenyl) ethane-1,2-diazido naphthoquinone-5-sulphonic acid ester, 1,1,1-three (4-hydroxy phenyl) ethane-1,2-diazido naphthoquinone-6-sulphonic acid ester, 1,1,1-three (4-hydroxy phenyl) ethane-1,2-diazido naphthoquinone-7-sulphonic acid ester, 1,1,1-three (4-hydroxy phenyl) ethane-1,2-diazido naphthoquinone-8-sulphonic acid ester, two (2,3,4-trihydroxy phenyl) methane-1,2-diazido naphthoquinone-4-sulphonic acid ester, two (2,3,4-trihydroxy phenyl) methane-1,2-diazido naphthoquinone-5-sulphonic acid ester, two (2,3,4-trihydroxy phenyl) methane-1,2-diazido naphthoquinone-6-sulphonic acid ester, two (2,3,4-trihydroxy phenyl) methane-1,2-diazido naphthoquinone-7-sulphonic acid ester, two (2,3,4-trihydroxy phenyl) methane-1,2-diazido naphthoquinone-8-sulphonic acid ester, 2,2-two (2,3,4-trihydroxy phenyl) propane-1,2-diazido naphthoquinone-4-sulphonic acid ester, 2,2-two (2,3,4-trihydroxy phenyl) propane-1,2-diazido naphthoquinone-5-sulphonic acid ester, 2,2-two (2,3,4-trihydroxy phenyl) propane-1,2-diazido naphthoquinone-6-sulphonic acid ester, 2,2-two (2,3,4-trihydroxy phenyl) propane-1,2-diazido naphthoquinone-7-sulphonic acid ester, 2,2-two (2,3,4-trihydroxy phenyl) propane-1,2-diazido naphthoquinone-8-sulphonic acid ester;
1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane-1,2-diazido naphthoquinone-4-sulphonic acid ester, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane-1,2-diazido naphthoquinone-5-sulphonic acid ester, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane-1,2-diazido naphthoquinone-6-sulphonic acid ester, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane-1,2-diazido naphthoquinone-7-sulphonic acid ester, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane-1,2-diazido naphthoquinone-8-sulphonic acid ester, 4,4 '-1-{4-[1-(4-hydroxy phenyl)-1-Methylethyl] and phenyl } ethylidene } bis-phenol-1,2-diazido naphthoquinone-4-sulphonic acid ester, 4,4 '-1-{4-[1-(4-hydroxy phenyl)-1-Methylethyl] and phenyl } ethylidene } bis-phenol-1,2-diazido naphthoquinone-5-sulphonic acid ester, 4,4 '-1-{4-[1-(4-hydroxy phenyl)-1-Methylethyl] and phenyl } ethylidene } bis-phenol-1,2-diazido naphthoquinone-6-sulphonic acid ester, 4,4 '-1-{4-[1-(4-hydroxy phenyl)-1-Methylethyl] and phenyl } ethylidene } bis-phenol-1,2-diazido naphthoquinone-7-sulphonic acid ester, 4,4 '-1-{4-[1-(4-hydroxy phenyl)-1-Methylethyl] and phenyl } ethylidene } bis-phenol-1,2-diazido naphthoquinone-8-sulphonic acid ester;
Two (2,5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane-1,2-diazido naphthoquinone-4-sulphonic acid ester, two (2,5-dimethyl-4-hydroxy phenyl)-and 2-hydroxy phenyl methane-1,2-diazido naphthoquinone-5-sulphonic acid ester, two (2,5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane-1,2-diazido naphthoquinone-6-sulphonic acid ester, two (2,5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane-1,2-diazido naphthoquinone-7-sulphonic acid ester, two (2,5-dimethyl-4-hydroxy phenyl)-and 2-hydroxy phenyl methane-1,2-diazido naphthoquinone-8-sulphonic acid ester, 3,3,3 ' 3 '-tetramethyl-1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol-1,2-diazido naphthoquinone-4-sulphonic acid ester, 3,3,3 ' 3 '-tetramethyl-1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol-1,2-diazido naphthoquinone-5-sulphonic acid ester, 3,3,3 ' 3 '-tetramethyl-1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol-1,2-diazido naphthoquinone-6-sulphonic acid ester, 3,3,3 ' 3 '-tetramethyl-1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol-1,2-diazido naphthoquinone-7-sulphonic acid ester, 3,3,3 ' 3 '-tetramethyl-1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol-1,2-diazido naphthoquinone-8-sulphonic acid ester, 2,2,4-trimethyl-7,2 ', 4 '-trihydroxy flavane-1,2-diazido naphthoquinone-4-sulphonic acid ester, 2,2,4-trimethyl-7,2 ', 4 '-trihydroxy flavane-1,2-diazido naphthoquinone-5-sulphonic acid ester, 2,2,4-trimethyl-7,2 ', 4 '-trihydroxy flavane-1,2-diazido naphthoquinone-6-sulphonic acid ester, 2,2,4-trimethyl-7,2 ', 4 '-trihydroxy flavane-1,2-diazido naphthoquinone-7-sulphonic acid ester, 2,2,4-trimethyl-7,2 ', 4 '-trihydroxy flavane-1,2-diazido naphthoquinone-8-sulphonic acid ester etc.
As above-mentioned 1,2-two azido benzoquinone sulphonic acid esters can be enumerated above-mentioned each 1,1 in the 2-diazido naphthoquinone sulphonic acid ester, and the 2-naphthoquinones replaces with 1, the compound of 2-benzoquinones.
As above-mentioned 1,2-diazido naphthoquinone sulfonamide can be enumerated above-mentioned each 1, and the sulphonic acid ester in the 2-diazido naphthoquinone sulphonic acid ester replaces with the compound of sulfonamide.
As above-mentioned 1,2-two azido benzoquinone sulfonamide can be enumerated above-mentioned each 1,1 in the 2-diazido naphthoquinone sulphonic acid ester, and the 2-naphthoquinones replaces with 1,2-benzoquinones and then sulphonic acid ester is replaced with the compound of sulfonamide.
These 1, among the 2-two nitrine naphtoquinone compounds, preferred 2,2-two (2,3,4-trihydroxy phenyl) propane-1,2-diazido naphthoquinone-5-sulphonic acid ester, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane-1,2-diazido naphthoquinone-4-sulphonic acid ester or two (2,5-dimethyl-4-hydroxy phenyl)-and 2-hydroxy phenyl methane-1,2-diazido naphthoquinone-4-sulphonic acid ester.
Above-mentioned 1,2-two nitrine naphtoquinone compounds can use separately, also can mix more than 2 kinds and use.
In the radiation sensitive resin composition of the present invention 1, the usage ratio of 2-two nitrine naphtoquinone compounds is with respect to multipolymer [A] 100 weight portions, preferred 5～100 weight portions, more preferably 10～50 weight portions.By content being located at this scope, make the balance of pattern formation property, development and the interlayer dielectric that obtains and lenticular thermotolerance, solvent resistance better.
Other composition
Radiation sensitive resin composition of the present invention contains above-mentioned multipolymer [A] and the essential composition of [B] composition conduct, in addition can also contain [C] thermal sensitivity as required and become acid compound, [D] to have polymerizable compound, [E] epoxy resin, [F] surfactant or [G] bonding agent of an ethylenic unsaturated double-bond at least.
Above-mentioned [C] thermal sensitivity becomes acid compound can be used to improve formed interlayer dielectric, lenticular thermotolerance and hardness.Its object lesson has, for example  salt such as sulfonium salt, benzothiazole  salt, ammonium salt,  salt.
Become acid compound as [C] thermal sensitivity, wherein preferably use sulfonium salt and benzothiazole  salt.
Can enumerate alkyl sulfonium salt, benzyl sulfonium salt, dibenzyl sulfonium salt, substituted benzyl sulfonium salt etc. as the object lesson of above-mentioned sulfonium salt, its object lesson, alkyl sulfonium salt can be enumerated as the 4-acetyl phenyl dimethyl sulfonium hexafluoro antimonate that belongs to the alkyl sulfonium salt, 4-acetyl oxygen phenyl dimethyl sulfonium hexafluoro arsenate, dimethyl-4-(benzyloxycarbonyloxy base) phenyl sulfonium hexafluoro antimonate, dimethyl-4-(benzoyloxy) phenyl sulfonium hexafluoro antimonate, dimethyl-4-(benzoyloxy) phenyl sulfonium hexafluoro arsenate, dimethyl-3-chloro-4-acetoxyl group phenyl sulfonium hexafluoro antimonate etc.;
As the benzyl sulfonium salt, can enumerate as benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, benzyl-4-methoxybenzene ylmethyl sulfonium hexafluoro antimonate, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro arsenate, 4-methoxy-benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate etc.;
As the dibenzyl sulfonium salt, can enumerate as dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl dibenzyl sulfonium hexafluoro antimonate, dibenzyl-4-methoxyphenyl sulfonium hexafluoro antimonate, dibenzyl-3-chloro-4-hydroxy phenyl sulfonium hexafluoro arsenate, dibenzyl-3-methyl-4-hydroxyl-5-tert-butyl-phenyl sulfonium hexafluoro antimonate, benzyl-4-methoxy-benzyl-4-hydroxy phenyl sulfonium hexafluorophosphate etc.;
As the substituted benzyl sulfonium salt, can enumerate as p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, to nitrobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, to nitrobenzyl-3-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 3 5-dichloro benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, o-chlorobenzyl-3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate etc.
These [C] thermal sensitivitys become among the acid compound, preferably use 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl sulfonium hexafluoro antimonate, 3-benzyl benzothiazole  hexafluoro antimonate.
As their commercially available prod, can enumerate サ Application エ イ De SI-L85, サ Application エ イ De SI-L110, サ Application エ イ De SI-L145, サ Application エ イ De SI-L150, サ Application エ イ De SI-L160 (three new chemical industry (strain) system) etc.
With respect to multipolymer [A] 100 weight portions, [C] thermal sensitivity becomes the usage ratio of acid compound composition to be preferably below 20 weight portions, more preferably 0.01～20 weight portion, further preferred 0.1～5 weight portion.By content being located at this scope, the tunicle formation property without detriment to composition can make formed interlayer dielectric, lenticular thermotolerance, hardness further improve.
At least have the polymerizable compound (below be sometimes referred to as " [D] composition ") of an ethylenic unsaturated double-bond as above-mentioned [D], can preferably enumerate as simple function (methyl) acrylate, 2 officials can (methyl) acrylate or 3 officials can above (methyl) acrylate.
As above-mentioned simple function (methyl) acrylate, can enumerate as (methyl) acrylic acid 2-hydroxyethyl ester, (methyl) carbitol acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid 3-methoxyl butyl ester, phthalic acid 2-(methyl) acryloxy ethyl-2-hydroxy-propyl ester etc.As their commercially available prod, can enumerate as ARONIX M-101, ARONIX M-111, ARONIX M-114 (above is that make in East Asia synthetic (strain)), KAYARAD TC-110S, KAYARAD TC-120S (above is Japanese chemical drug (strain) system), BISCOAT 158, BISCOAT 2311 (above is Osaka organic chemistry industry (strain) system) etc.
As above-mentioned 2 officials energy (methyl) acrylate, can enumerate as (methyl) acrylic acid glycol ester, 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 diacrylate, two phenoxetol fluorenes diacrylates etc.Can enumerate ARONIX M-210, ARONIX M-240, ARONIX M-6200 (above is that make in East Asia synthetic (strain)) as their commercially available prod, KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (above is Japanese chemical drug (strain) system), BISCOAT 260, BISCOAT 312, BISCOAT 335HP (above is Osaka organic chemistry industry (strain) system) etc.
As above (methyl) acrylate of above-mentioned 3 officials energy, can enumerate as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, three ((methyl) acryloxy ethyl) phosphate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.As their commercially available prod, can enumerate ARONIX M-309, ARONIX M-400, ARONIX M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060 (above is that make in East Asia synthetic (strain)), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, (above is Japanese chemical drug (strain) system), BISCOAT 295, BISCOAT 300, BISCOAT 360, BISCOAT GPT, BISCOAT 3PA, BISCOAT 400 (above is Osaka organic chemistry industry (strain) system) etc.
In these compounds, preferably use above (methyl) acrylate of 3 officials energy, wherein preferred especially trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate.
These simple functions, 2 officials energy, 3 officials can use separately by above (methyl) acrylate, or make up more than 2 kinds and use.With respect to multipolymer [A] 100 weight portions, the usage ratio of [D] composition is preferably below 50 weight portions, more preferably below 30 weight portions.
By contain [D] composition with such ratio,, and can further improve interlayer dielectric or lenticular thermotolerance and skin hardness etc. to the not influence of tunicle formation property of composition.
As above-mentioned [E] epoxy resin, so long as do not influence intermiscibility, then be not particularly limited, can preferably enumerate bisphenol A type epoxy resin, phenol novolac epoxy resin, cresols novolac epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic ring epoxy resins, make (being total to) polymerization of (methyl) glycidyl acrylate and resin etc.Wherein preferred bisphenol A type epoxy resin, cresols novolac epoxy resin, glycidyl ester type epoxy resin etc.
With respect to multipolymer [A] 100 weight portions, the usage ratio of [E] epoxy resin is preferably below 30 weight portions.By contain [E] composition with such ratio, tunicle formation property, the particularly homogeneity of thickness without detriment to composition can further improve the interlayer dielectric or lenticular thermotolerance and the skin hardness etc. that obtain.
As the comonomer of multipolymer [A] and when using the monomer that contains epoxy radicals, multipolymer [A] also can be called " epoxy resin ", but multipolymer [A] is in that to have aspect the alkali-soluble insoluble with alkali [E] epoxy resin different.
As above-mentioned [F] surfactant, preferably using fluorine is surfactant, silicone type surface active agent and non-ionics.
As fluorine is that the object lesson of surfactant has: except 1,1,2, and 2-tetrafluoro octyl group (1,1,2,2-tetrafluoro propyl group) ether, 1,1,2,2-tetrafluoro octyl group hexyl ether, eight glycol two (1,1,2,2-tetrafluoro butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro amyl group) ether, eight propylene glycol two (1,1,2,2-tetrafluoro butyl) ether, six propylene glycol two (1,1,2,2,3,3-hexafluoro amyl group) ether, the perfluor sodium dodecylsulphonate, 1,1,2,2,8,8,9,9,10,10-ten fluorine dodecanes, 1,1,2,2,3, outside the 3-hexafluoro decane etc., can also enumerate the fluoro-alkyl benzene sulfonic acid sodium salt, fluoro-alkyl oxyethylene group ether, the fluoro-alkyl ammonium iodide, fluoroalkyl polyoxyethylene ether, the perfluoroalkyl poly oxyethanol, the perfluoroalkyl alkoxide, fluorine is an Arrcostab etc.
Commercially available product as them can be enumerated BM-1000, BM-1100 (above is the BMChemie corporate system), MEGAFAC F142D, MEGAFAC F172, MEGAFACF173, MEGAFAC F183, MEGAFAC F178, MEGAFAC F191, MEGAFAC F471 (above is big Japanese ink chemical industry (strain) system), FLUORAD FC-170C, FC-171, FC-430, (above be Sumitomo 3M (strain) system to FC-431, SARFRON S-112, SARFRON S-113, SARFRON S-131, SARFRONS-141, SARFRON S-145, SARFRON S-382, SARFRON SC-101, SARFRON SC-102, SARFRON SC-103, SARFRON SC-104, SARFRON SC-105, SARFRON SC-106 (Asahi Glass (strain) system), FTOPEF301, FTOP 303, FTOP 352 (new autumn fields changes into (strain) system).
As above-mentioned silicone type surface active agent, can enumerate the following product of on market, selling, for example: trade name DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above is TORAY DOW CORING SILICONE (strain) system), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above is GE TOSHIBA SILICONE (strain) system).
As above-mentioned non-ionics, can use as polyoxyethylene alkyl ethers such as polyoxyethylene laurel ether, polyoxyethylene stearyl acyl ether, polyoxyethylene oleyl ethers; Polyoxyethylene aryl ether such as NONIN HS 240, polyoxyethylene nonylplenyl ether; Polyoxyethylene dialkyls such as polyoxyethylene dilaurate, polyoxyethylene distearate etc.; (methyl) acrylic acid series copolymer POLYFLOW No.57,95 (common prosperity society chemistry (strain) system) etc.
These surfactants can use separately, or make up more than 2 kinds and use.
With respect to multipolymer [A] 100 weight portions, the consumption of these [F] surfactant copolymers [A] is preferably below 5 weight portions, more preferably below 2 weight portions.
As this [G] bonding agent, can preferably use the functional silanes coupling agent, particularly have carboxyl, methacryl, isocyanate group, the substituent silane coupling agent of epoxy radicals isoreactivity.Specifically can enumerate trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanates propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.With respect to multipolymer [A] 100 weight portions, such [G] bonding agent multipolymer [A] can more preferably use with the amount below 10 weight portions preferably with below 20 weight portions.
Radiation sensitive resin composition
Radiation sensitive resin composition of the present invention can pass through above-mentioned multipolymer [A] and [B] 1, and 2-two nitrine naphtoquinone compounds and above-mentioned other composition that can add arbitrarily evenly mix and prepare.Radiation sensitive resin composition of the present invention is preferably dissolved in the appropriate solvent and uses with solution state.For example can pass through multipolymer [A] and [B] 1,2-two nitrine naphtoquinone compounds and other composition that adds arbitrarily mix in appropriate solvent to scale, prepare the radiation sensitive resin composition of solution state.
As the used solvent of preparation radiation sensitive resin composition of the present invention, can use to make multipolymer [A] and [B] 1 2-two nitrine naphtoquinone compounds and each composition uniform dissolution of any other composition that cooperates and the solvent that does not react with each composition.
As such solvent, can enumerate identical solvent with the aforementioned solvent institute example that when being used to the polymerization of making multipolymer [A], can use.
In the middle of such solvent, from the dissolubility of each composition, consider, can preferably use alcohol, glycol ether, ethylene glycol alkyl ether acetic acid esters, ester and diglycol with the reactivity of each composition, the viewpoints such as easness that form tunicle.Wherein, can especially preferably use benzylalcohol, 2-phenylethyl alcohol, 3-phenyl-1-propyl alcohol, ethylene glycol monobutyl ether acetic acid esters, diglycol only ethylether acetic acid esters, diethylene glycol diethyl ether, diglycol ethyl-methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, methoxypropionic acid methyl esters, ethoxyl ethyl propionate.
In order to improve the inner evenness of thickness, can further and use high boiling solvent.As can and the high boiling solvent of usefulness, N-NMF, N are for example arranged, dinethylformamide, N-methyl formyl aniline, N-methylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, 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 N-Methyl pyrrolidone, gamma-butyrolacton, N,N-dimethylacetamide.
As the solvent of radiation sensitive resin composition of the present invention, and when using high boiling solvent, its consumption is below the 50 weight % with respect to the solvent total amount, below the preferred 40 weight %, further below the preferred 30 weight %.By consumption being located at this scope,, can further improve the film thickness uniformity (inner evenness) of tunicle without detriment to the susceptibility and the residual film ratio of composition.
When radiation sensitive resin composition of the present invention is made solution state, composition beyond desolventizing in the solution (just multipolymer [A] and [B] 1, the total amount of 2-two nitrine naphtoquinone compounds compositions and any other composition that adds) shared ratio, can set arbitrarily according to application target and desirable film thickness value etc., be preferably 5～80 weight %, and further preferred shape admittedly divides concentration different according to the formation method of tunicle.Solid shape when adopting rubbing method to form tunicle divides concentration preferred 15～35 weight %, and the solid shape when adopting the dry film method to form tunicle divides concentration preferred 50～70 weight %.
Zhi Bei composition solution like this, via hole diameter is after the millipore filter about 0.2～0.5 μ m filters, and is available.
Radiation sensitive resin composition of the present invention can be particularly preferred for interlayer dielectric and lenticular formation.
Interlayer dielectric and lenticular formation method
The formation method of interlayer dielectric of the present invention and lenticular formation method comprise following operation according to following order:
(1) operation of formation radiation sensitive resin composition tunicle on substrate,
(2) to the operation of at least a portion of this tunicle irradiation radioactive ray,
(3) operation of developing of the tunicle after will exposing,
(4) operation that heats of the tunicle after will developing.
Below, these each operations are described.
(1) operation of formation radiation sensitive resin composition tunicle on substrate
This operation is by radiation sensitive resin composition of the present invention coating or be transferred to substrate surface, and forms the tunicle of radiation sensitive resin composition.When radiation sensitive resin composition of the present invention contains solvent, carry out prebake conditions with the coating of the composition of solution shape or after being transferred to substrate and remove and desolvate, can form tunicle thus.
As operable substrate, can enumerate substrate that is formed with various metal films as glass substrate, silicon wafer, on their surface etc.
As coating process, be not particularly limited, can adopt as spraying process, rolling method, method of spin coating (spin-coating method), slit mouth mould rubbing method, rod and be coated with proper method such as method, ink-jet application method, preferred especially spin-coating method, slit mouth mould rubbing method.
As printing transferring method, can enumerate the dry film method.
Adopt the situation of dry film method to be when the tunicle of radiation sensitive resin composition is formed at substrate: this dry film is at basilar memebrane, preferably lamination contains (hereinafter referred to as " the radiation-sensitive dry film ") that the radiation-sensitive layer of radiation sensitive resin composition of the present invention forms on the pliability basilar memebrane.
Above-mentioned radiation-sensitive dry film carries out drying after can being coated with the radiation sensitive resin composition of the present invention of preferably making liquid composition on basilar memebrane, thus lamination radiation-sensitive layer and forming.
As the basilar memebrane of radiation-sensitive dry film, for example can use synthetic resin films such as polyethylene terephthalate (PET) film, tygon, polypropylene, polycarbonate, polyvinyl chloride.The thickness of basilar memebrane is that the scope of 15～125 μ m is suitable.
Coating process during as lamination radiation-sensitive layer on basilar memebrane is not particularly limited, and for example can adopt to scrape lacquer rubbing method, rod and be coated with suitable method such as method, rolling method, curtain coating method.
As above-mentioned prebake conditions condition, also different and different according to the kind of each composition, usage ratio etc.For example can condition be made as 60～110 ℃ following about 30 seconds～15 minutes.
Formed by film thickness, when forming interlayer dielectric, for example be preferably about 3～6 μ m, when forming lenticule, for example be preferably about 0.5～3 μ m.This thickness is construed as the value of removing after desolvating when radiation sensitive resin composition of the present invention contains solvent.
(2) to the operation of at least a portion of this tunicle irradiation radioactive ray (hereinafter referred to as " exposure ")
In this operation, at least a portion of formed tunicle is exposed.When only exposing this tunicle a part of, expose by photomask usually with predetermined pattern.
As the employed radioactive ray of exposure, can enumerate as charged particle rays such as X ray, electron beams such as far ultraviolet, synchrotron radioactive ray such as ultraviolet ray, KrF excimer laser such as g line (wavelength 436nm), i lines (wavelength 365nm) etc.The radioactive ray that contain g line and/or i line are especially preferably enumerated in wherein preferred ultraviolet ray.
As exposure, for example preferred 50～3 when forming interlayer dielectric, 000J/m 2About, for example preferred 50～5 when forming lenticule, 000J/m 2About.
(3) operation of developing of the tunicle after will exposing
In this operation, with after the exposure by film development, remove exposed portion, form the pattern of regulation thus.
As developer solution used in development, can use as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-pro-pyl amine, diethylamide, diethylaminoethanol, di-n-propyl amine, triethylamine, the methyl diethylamide, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, the pyrroles, piperidines, 1,8-diazabicylo [5,4,0]-the 7-undecylene, 1,5-diazabicylo [4,3,0]-aqueous solution of alkali (alkali compounds) such as 5-nonane, according to circumstances, can use the various organic solvents that can dissolve the radiation sensitive resin composition tunicle.
Can also in the aqueous solution of above-mentioned alkali, add water-miscible organic solvent or surfactants such as methyl alcohol, ethanol in right amount.
As developing method, can utilize liquid to contain (liquid is contained り) method, infusion process, shake proper methods such as infusion process, spray process.
Development time, different and different with the kind of each composition or usage ratio etc., for example be made as about 30～120 seconds.
For known in the past radiation sensitive resin composition, if development time surpassed Best Times about 20～25 seconds, then the pattern of Xing Chenging is peeled off, and therefore essential strict control development time is arranged.For radiation sensitive resin composition of the present invention, even surpass Best Times more than 30 seconds, also can form good pattern, be very favourable aspect the productive rate of goods and the throughput rate.
(4) operation that heats of the tunicle after will developing
In this operation, the tunicle that is formed with predetermined pattern is preferably carried out carrying out washing treatment as cleaning with circulating water, also preferred by shine radioactive ray (post-exposure) comprehensively by generations such as high-pressure mercury-vapor lamps, during this is filmed remaining 1,2-two nitrine naphtoquinone compounds carry out resolution process, by heating arrangements such as hot plate, baking ovens this is filmed then and carry out heat treated (back baking), make its curing.When forming lenticule, thereby make the pattern melt flows of formation form the regulation shape by the back baking.
The exposure of post-exposure is preferably 2,000～5,000J/m 2About.
In addition, the heating-up temperature of back baking for example is about 120～250 ℃.Heat time heating time is different and different with the kind of heating instrument, as when on hot plate, carrying out heat treated, and can be being set at heat time heating time about 5～30 minutes; When in baking oven, carrying out heat treated, can be being set at heat time heating time about 30～90 minutes.At this moment also can adopt sectional type baking that carries out heat treated more than 2 times etc.
Like this can be at the interlayer dielectric or lenticular, the pattern-like film of substrate surface formation corresponding to purpose.
Interlayer dielectric and lenticule
Interlayer dielectric of the present invention and lenticule are distinguished preferably as mentioned above, are formed by radiation sensitive resin composition of the present invention.
Interlayer dielectric of the present invention can be particularly preferred for electronic units such as TFT type liquid crystal display cells, magnetic head element, integrated circuit component, solid-state imager.
The lenticular good semi-convex lens shape that is shaped as of the present invention.Lenticule of the present invention and the lenticule battle array that it is regularly arranged can be preferably used as the brilliant imaging optical system of color filter or the optical system material of the joints of optical fibre of carrying such as facsimile recorder, electronic copier, solid-state imager especially.
As above, radiation sensitive resin composition of the present invention has excellent susceptibility and resolution, the excellent storage stability of composition solution, even and surpass optimum development time in the developing procedure, also have the excellent developing nargin that can form good pattern form, particularly can be preferably used as the lenticule of the interlayer dielectric of various electronic units and solid-state imager etc.
For the formation method and the lenticular formation method of interlayer dielectric of the present invention, even development time surpasses optimum development time, also can form good pattern, can form the interlayer dielectric and the lenticule that have both above-mentioned excellent specific property easily.
Interlayer dielectric of the present invention has both excellent solvent resistance, thermotolerance, light transmission, adaptation etc., and specific inductive capacity is low.
Lenticule of the present invention has both excellent solvent resistance, thermotolerance, light transmission, adaptation etc., and has good melt shape.
Embodiment
Embodiment and comparative example below are shown, are described more specifically the present invention, but the present invention is not limited to following embodiment.
The synthesis example of multipolymer
Synthesis example 1
In the flask that possesses condenser pipe, stirring machine, add 2, two (2, the 4-methyl pentane nitrile) 7 weight portions of 2 '-azo, methyl proxitol acetate 220 weight portions.Then add methacrylic acid 22 weight portions, methacrylic acid dicyclopentenyl ester 28 weight portions, 3-(methacryloxy methyl)-2-phenyl oxetanes 40 weight portions, methacrylic acid tetrahydro furfuryl ester 10 weight portions, α-Jia Jibenyixi dimer 1.5 weight portions, carry out nitrogen replacement on one side then, Yi Bian begin slow stirring.Make solution temperature rise to 70 ℃, keep this temperature to carry out polymerization in 4 hours, obtain the solution (solid component concentration 33.8 weight %) of multipolymer [A].
The Mw of [A] multipolymer that obtains is 14,000, and Mw/Mn is 2.1.Mw and Mn are to use GPC (gel permeation chromatography) (TOSOH (strain) makes HLC-8020) to measure the mean molecular weight of the polystyrene conversion that obtains.With this multipolymer [A] as " multipolymer (A-1) ".
Synthesis example 2
In the flask that possesses condenser pipe, stirring machine, add 2, two (2, the 4-methyl pentane nitrile) 7 weight portions of 2 '-azo, methyl proxitol acetate 220 weight portions.Then add styrene 5 weight portions, methacrylic acid 11 weight portions, 3-(methacryloxy methyl)-3-ethyl oxetanes 45 weight portions, styrene 5 weight portions, methacrylic acid tetrahydro furfuryl ester 10 weight portions and α-Jia Jibenyixi dimer 1.5 weight portions, carry out nitrogen replacement on one side then, Yi Bian begin slow stirring.Make solution temperature rise to 70 ℃, keep this temperature to carry out polymerization in 4 hours, obtain the solution (solid component concentration 32.8 weight %) of multipolymer [A].
The Mw of [A] multipolymer that obtains is 22,000, and Mw/Mn is 2.1.With this multipolymer [A] as " multipolymer (A-2) ".
Synthesis example 3
In the flask that possesses condenser pipe, stirring machine, add 2, two (2, the 4-methyl pentane nitrile) 7 weight portions of 2 '-azo, methyl proxitol acetate 150 weight portions.Compound (mean value of a is 2.2 in the formula) 15 weight portions and α-Jia Jibenyixi dimer 1.5 weight portions that then add styrene 5 weight portions, methacrylic acid 25 weight portions, N-cyclohexyl-maleimide, 3-(methacryloxy methyl)-2-trifluoromethyl oxetanes 35 weight portions, above-mentioned formula (4) expression, carry out nitrogen replacement on one side then, Yi Bian begin slow stirring.Make solution temperature rise to 70 ℃, keep this temperature to carry out polymerization in 4 hours, obtain the solution (solid component concentration 32.7 weight %) of multipolymer [A].
The Mw of [A] multipolymer that obtains is 18,500, and Mw/Mn is 2.2.With this multipolymer [A] as " multipolymer (A-3) ".
Synthesis example 4
In the flask that possesses condenser pipe, stirring machine, add 2, two (2, the 4-methyl pentane nitrile) 7 weight portions of 2 '-azo, methyl proxitol acetate 220 weight portions.Then add styrene 20 weight portions, methacrylic acid 10 weight portions, 2-(methacryloxy methyl)-4-trifluoromethyl oxetanes 50 weight portions, methacrylic acid tetrahydro furfuryl ester 20 weight portions and α-Jia Jibenyixi dimer 2.0 weight portions, carry out nitrogen replacement on one side then, Yi Bian begin slow stirring.Make solution temperature rise to 70 ℃, keep this temperature to carry out polymerization in 5 hours, obtain the solution (solid component concentration 32.0 weight %) of multipolymer [A].
The Mw of [A] multipolymer that obtains is 16,500, and Mw/Mn is 1.7.With this multipolymer [A] as " multipolymer (A-4) ".
Compare synthesis example 1
In the flask that possesses condenser pipe, stirring machine, add 2, two (2, the 4-methyl pentane nitrile) 7 weight portions of 2 '-azo, diglycol ethyl-methyl ether 220 weight portions.Then add methacrylic acid 23 weight portions, methacrylic acid dicyclopentenyl ester 47 weight portions, glycidyl methacrylate 20 weight portions and α-Jia Jibenyixi dimer 2.0 weight portions, Yi Bian carry out nitrogen replacement then, Yi Bian begin slow stirring.Make solution temperature rise to 70 ℃, keep this temperature to carry out polymerization in 5 hours, obtain the solution (solid component concentration 32.8 weight %) of multipolymer [A].
The Mw of the multipolymer that obtains is 24,000, and Mw/Mn is 2.3.With this multipolymer as " multipolymer (a-1) ".
Compare synthesis example 2
In the flask that possesses condenser pipe, stirring machine, add 2, two (2, the 4-methyl pentane nitrile) 7 weight portions of 2 '-azo, methyl proxitol acetate 220 weight portions.Then add methacrylic acid 22 weight portions, methacrylic acid dicyclopentenyl ester 28 weight portions, 3-(methacryloxy methyl)-2-phenyl oxetanes 40 weight portions, styrene 10 weight portions and α-Jia Jibenyixi dimer 1.5 weight portions, carry out nitrogen replacement on one side then, Yi Bian begin slow stirring.Make solution temperature rise to 70 ℃, keep this temperature to carry out in 4 hours, obtain the solution (solid component concentration 31.8 weight %) of multipolymer [A].
The Mw of the multipolymer that obtains is 18,000, and Mw/Mn is 2.01.With this multipolymer as " multipolymer (a-2) ".
The preparation of radiation sensitive resin composition and evaluation
Embodiment 1
The solution that contains polymkeric substance [A-1] that obtains in above-mentioned synthesis example 1 as [A] composition is equivalent to the amount of 100 weight portions to convert by polymkeric substance [A-1], as 4 of [B] composition, 4 '-1-{4-[1-(4-hydroxy phenyl)-1-Methylethyl] and phenyl } ethylidene } bis-phenol-1,2-diazido naphthoquinone-5-sulphonic acid ester 30 weight portions, triphenylsulfonium triflate 1 weight portion as [C] composition, γ-methacryloxypropyl trimethoxy silane 5 weight portions as other compositions mix, it is dissolved in the methyl proxitol acetate, and make solid component concentration reach 30 weight %, be that the millipore filter of 0.2 μ m filters with the aperture then, make composition (S-1).
The evaluation of storage stability
Get the part of the above-mentioned composition of making (S-1), be enclosed within the glass spiral pipe, in 1 week of heating in 40 ℃ baking oven, measure heating front and back viscosity change rate.The results are shown in the table 1.Here, the viscosity rate of change is that 0～+ 5% situation storage stability is good.
The evaluation of development nargin
On a plurality of silicon substrates, with spinner respectively behind the coating composition (S-1), under 90 ℃ on hot plate prebake conditions 2 minutes, form tunicle.The mask of the pattern by having line-spacing (line and space) (10 to 1) uses Canon's (strain) system PLA-501 exposure meter (extra-high-pressure mercury vapour lamp), and it is 80W/m that the tunicle that obtains is radiated at wavelength 365nm place intensity 2Ultraviolet ray after 40 seconds, as developer solution, change development times down with the tetramethyl ammonium hydroxide aqueous solution of concentration 0.4 weight % at 25 ℃, with the liquid method of containing each substrate is developed.Then carry out flowing water washing in 1 minute, drying, the pattern of formation thickness 3.0 μ m on wafer with ultrapure water.At this moment, so that live width reaches the necessary minimum development time of 3.0 μ m as optimum development time, be shown in Table 1.During from optimum development time continuation development, measure the time of peeling off 3.0 μ m line patterns, be shown in Table 1 as development nargin.This value we can say that development nargin is good more than 30 seconds the time.
I. the evaluation of interlayer dielectric
(1) evaluation of resolution
The formation of-pattern-like film-
Use spinner coating composition (S-1) afterwards on glass substrate, prebake conditions is 3 minutes on 80 ℃ hot plate, forms tunicle.
Then, the tunicle that the obtains photomask by predetermined pattern being radiated at wavelength 365nm place intensity is 100W/m 215 seconds of ultraviolet ray.Utilize 0.5 weight % tetramethylammonium hydroxide aqueous solution afterwards after carrying out development in 1 minute under 25 ℃,, remove unwanted part, form pattern by pure water washing 1 minute.
Then, be 100W/m to the patterned illumination that forms in wavelength 365nm place intensity 230 seconds of ultraviolet ray after, by heating in 220 ℃ baking oven (back baking) 60 minutes, obtain the pattern-like film of thickness 3.0 μ m.Except the prebake conditions temperature is changed into 90 ℃ or 100 ℃, carry out operation same as described above, obtain 3 kinds of different pattern-like films of prebake conditions temperature.
The evaluation of-resolution-
To the pattern-like film that obtains, estimate for " * " for " zero ", unresolvable situation with the situation that sampling pattern (5 μ m * 5 μ m holes) can be differentiated.
(2) evaluation of heat-resisting dimensional stability
In " formation of pattern-like film-" of above-mentioned " evaluation of (1) resolution ",, be determined at the thickness that carries out in 220 ℃ the baking oven before and after the back baking 60 minutes for the patterns that 80 ℃ of prebake conditions temperature form down.The results are shown in the table 2.At this, the rate of change of thickness is in ± 5% the time, we can say that heat-resisting dimensional stability is good.
(3) Tou Mingxing evaluation
Use spinner coating composition (S-1) afterwards on glass substrate, prebake conditions is 3 minutes on 80 ℃ hot plate, forms tunicle.
Then, be 100W/m to the tunicle WBR that obtains in wavelength 365nm place intensity 230 seconds of ultraviolet ray.Then, by heating in 220 ℃ baking oven (back baking) 60 minutes, obtain the film of thickness 3.0 μ m.
(150-20 type twin-beam ((strain) Hitachi system) in the control sides setting and as substrate glass substrate of the same race, is measured the light transmission of the above-mentioned film that obtains at wavelength 400nm place to use spectrophotometer.The results are shown in the table 2.At this, transmissivity is that 90% situation we can say that the transparency is good.
(4) evaluation of heat-resisting discolouration
The substrate with tunicle after measuring in above-mentioned " (3) transparency evaluation " heat 1 hour in 250 ℃ baking oven after, similarly be determined at the light transmission at wavelength 400nm place with " evaluation that (3) are transparent ".The rate of change of the transmissivity before and after the heating is shown in Table 2.At this, the rate of change of transmissivity we can say that less than 5% o'clock heat-resisting discolouration is good.
(5) evaluation of adaptation
With the last stage part operation similarly of above-mentioned " evaluation of (3) transparency ", obtain the film of thickness 3.0 μ m.The substrate that will have this film carries out the gridiron pattern disbonded test according to JIS-K5400 place 4 hours in 120 ℃, the autoclave of humidity 100% after.Remaining gridiron pattern number is as shown in table 2 among 100 of the gridiron pattern numbers of this moment.
II. lenticular evaluation
(1) evaluation of susceptibility
Use spinner coating composition (S-1) respectively on a plurality of silicon substrates, so that the thickness that removes after desolvating reaches 2.5 μ m, prebake conditions 3 minutes on 70 ℃ hot plate forms a plurality of substrates with tunicle then.
Then, make the mask of the pattern of the tunicle that the obtains line-spacing (10 to 1) by having live width 0.8 μ m, after changing exposure each substrate being exposed, utilize 2.38 weight % tetramethylammonium hydroxide aqueous solutions to develop 1 minute at 25 ℃, by pure water washing 1 minute, obtain the pattern-like film.
With the above-mentioned a plurality of substrates of microscopic examination, the lowest exposure amount that research can resolution distance live width (0.08 μ m).The results are shown in the table 3.This value is 1,000J/m 2When following, we can say that susceptibility is good.
(2) Tou Mingxing evaluation
Use spinner coating composition (S-1) afterwards on glass substrate, prebake conditions is 3 minutes on 70 ℃ hot plate, forms tunicle.
Then, be 100W/m to the tunicle WBR that obtains in wavelength 365nm place intensity 230 seconds of ultraviolet ray.Then, by heating in 160 ℃ baking oven (back baking) 60 minutes, obtain the film of thickness 2.5 μ m.
(150-20 type twin-beam ((strain) Hitachi system) in the control sides setting and as substrate glass substrate of the same race, is measured the light transmission of the above-mentioned film that obtains at wavelength 400nm place to use spectrophotometer.The results are shown in the table 3.At this, transmissivity is 90% when above, we can say that the transparency is good.
(3) evaluation of heat-resisting discolouration
With after measuring the substrate that obtains in above-mentioned " (2) transparency evaluation " and in 250 ℃ baking oven, heat 1 hour, similarly be determined at the light transmission at wavelength 400nm place with " evaluation that (2) are transparent " with tunicle.The rate of change of the transmissivity before and after the heating is as shown in table 3.At this, the rate of change of transmissivity we can say that less than 5% o'clock heat-resisting discolouration is good.
(5) evaluation of solvent resistance
With the last stage part operation similarly of above-mentioned " evaluation of (3) transparency ", obtain the film of thickness 2.5 μ m.The substrate that will have this film impregnated in 50 ℃ the isopropyl alcohol 10 minutes, measures the Thickness Variation rate before and after the dipping.The results are shown in the table 3.This value is 0～+ 5% o'clock, and solvent resistance is good.
(6) evaluation of adaptation
Replace the glass substrate except using silicon substrate to measure,, obtain the film of thickness 2.5 μ m with the last stage part operation similarly of above-mentioned " evaluation of (3) transparency ".The substrate that will have this film carries out the gridiron pattern disbonded test according to JIS-K5400 place 4 hours in 120 ℃, the autoclave of humidity 100% after.Remaining gridiron pattern number is as shown in table 3 among 100 of the gridiron pattern numbers of this moment.
(7) evaluation of microlens shape
On a plurality of silicon substrates, with spinner coating composition (S-1), so that the thickness that removes after desolvating reaches 2.5 μ m, prebake conditions 3 minutes on 70 ℃ hot plate forms the substrate with tunicle then.
Then, by having the pattern mask of 4.0 μ m point-2.0 μ m apart from pattern, (NA=0.50, λ=365nm) are at exposure 3,000J/m to use the NSR1755i7A reduced projection exposure machine that NIKON (strain) makes 2Make the tunicle exposure that obtains down, with the tetramethylammonium hydroxide aqueous solution of concentration 1.1 weight % 25 ℃, developed 1 minute with liquid Sheng method.After then washing with water, drying forms pattern on wafer.Then, the PLA-501F exposure machine made from Canon's (strain) (extra-high-pressure mercury vapour lamp) exposes, and makes the accumulative total exposure reach 3,000J/m 2Then, on the hot plate 160 ℃ of down heating after 10 minutes, again 230 ℃ down heating made the pattern melt flows in 10 minutes, form lenticule.
The size (diameter) and the cross sectional shape of the lenticular bottom that forms (face that joins with substrate) are as shown in table 3.The size of lenticule bottom surpasses 4.0 μ m and during less than 5.0 μ m, we can say good.If its size reaches more than the 5.0 μ m, between the then adjacent lens be state of contact, not preferred.In addition, good when cross sectional shape is (a) such semi-convex lens shape in mode chart shown in Figure 1, during for (b) such trapezoidal, bad.
Embodiment 2～4, comparative example 1
Except that using the solution contain the multipolymer shown in the table 1 to replace containing the solution of multipolymer (A-1) respectively, prepare composition similarly to Example 1, estimate.The results are shown in table 1～3.
Comparative example 2
The solution that will contain the multipolymer (a-2) of gained in the above-mentioned relatively synthesis example 2 is scaled the amount that multipolymer (a-2) is equivalent to 100 weight portions, as 4 of (B) composition, 4 '-1-{4-[1-(4-hydroxy phenyl)-1-Methylethyl] and phenyl } ethylidene } bis-phenol-1,2-diazido naphthoquinone-5-sulphonic acid ester 30 weight portions, γ-methacryloxypropyl trimethoxy silane 5 weight portions as other compositions mix, it is dissolved in the methyl proxitol acetate, and make solid component concentration reach 30 weight %, be that the millipore filter of 0.5 μ m filters with the aperture then, make composition.
Except using above-mentioned composition replacement composition (S-1), estimate similarly to Example 1.The results are shown in table 1～3.In comparative example 2, when forming lenticule, owing to be state of contact between the adjacent lens, and can not estimate lenticular cross sectional shape.
Table 1
Multipolymer in the composition Storage stability (viscosity rate of change) Development nargin
Optimum development time (second) Development nargin (second)
Embodiment 1 A-1 2％ 70 40
Embodiment 2 A-2 2％ 80 40
Embodiment 3 A-3 1％ 70 40
Embodiment 4 A-4 1％ 80 30
Comparative example 1 a-1 9％ 90 20
Comparative example 2 a-2 2％ 90 30
Table 2
Resolution Heat-resisting dimensional stability (Thickness Variation rate) The transparency (transmissivity) Heat-resisting discolouration (rate of change of transmissivity) Adaptation (remaining gridiron pattern number)
The prebake conditions temperature
80℃ 90℃ 100℃
Embodiment 1 ○ ○ ○ -3％ 97％ -2％ 100
Embodiment 2 ○ ○ ○ -3％ 95％ -3％ 100
Embodiment 3 ○ ○ ○ -3％ 95％ -3％ 100
Embodiment 4 ○ ○ ○ -3％ 94％ -2％ 100
Comparative example 1 ○ ○ ○ -6％ 93％ -5％ 100
Comparative example 2 ○ ○ ○ -4％ 89％ -2％ 100
Table 3
Susceptibility (J/m 2) The transparency (transmissivity) Heat-resisting discolouration (rate of change of transmissivity) Solvent resistance (Thickness Variation rate) Adaptation (remaining gridiron pattern number) Microlens shape
The diameter (μ m) of bottom Shape
Embodiment 1 700 96％ -3％ +2％ 100 4.5 (a)
Embodiment 2 800 92％ -3％ +2％ 100 4.6 (a)
Embodiment 3 850 95％ -4％ +3％ 100 4.4 (a)
Embodiment 4 750 94％ -3％ +3％ 100 4.6 (a)
Comparative example 1 1100 86％ -7％ +7％ 100 4.8 (b)
Comparative example 2 1000 86％ -7％ +7％ 100 5.1 Can not estimate

Claims (8)

1. radiation sensitive resin composition is characterized in that containing:
(a1), (a2) and multipolymer (a3) [A], and 1,2-two nitrine naphtoquinone compounds [B];
Described (a1) is selected from least a compound in unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides,
(a2) be selected from least a compound in the compound shown in compound shown in the following formula (1) and the following formula (2),
Figure A2006101421360002C1
In the formula (1), R represents the alkyl of hydrogen atom or carbon number 1～4, R 1The alkyl of expression hydrogen atom or carbon number 1～4, R 2, R 3, R 4And R 5Represent the alkyl of hydrogen atom, fluorine atom, carbon number 1～4, the aryl of carbon number 6～20 or the perfluoroalkyl of carbon number 1～4 independently of one another, n is 1～6 integer,
Figure A2006101421360002C2
In the formula (2), R, R 1, R 2, R 3, R 4And R 5And n is identical with the definition in the above-mentioned formula (1),
(a3) have the unsaturated compound that is selected from least a structure in the structure shown in tetrahydrofuran skeleton, furans skeleton, oxinane skeleton, pyrans skeleton and the following formula (3) in the molecule,
Figure A2006101421360003C1
In the formula (3), R 6Be hydrogen atom or methyl, m is 2～10 integer.
2. radiation sensitive resin composition according to claim 1, wherein, multipolymer [A] is above-mentioned (a1), (a2) and (a3) composition and multipolymer (a4), and described (a4) is and (a1), (a2) and (a3) other different ethylene series unsaturated compounds of composition.
3. radiation sensitive resin composition according to claim 1 and 2, it is used to form interlayer dielectric.
4. the formation method of interlayer dielectric is characterized in that comprising following operation according to following order:
(1) operation of the described radiation sensitive resin composition tunicle of formation claim 1 on substrate,
(2) to the operation of at least a portion of this tunicle irradiation radioactive ray,
(3) operation that postradiation tunicle is developed, and
(4) operation that heats of the tunicle after will developing.
5. interlayer dielectric, it is formed by the described radiation sensitive resin composition of claim 1.
6. claim 1 or 2 described radiation sensitive resin compositions, it is used to form lenticule.
7. lenticular formation method is characterized in that comprising following operation according to following order:
(1) operation of the described radiation sensitive resin composition tunicle of formation claim 1 on substrate,
(2) to the operation of at least a portion of this tunicle irradiation radioactive ray,
(3) operation that postradiation tunicle is developed, and
(4) operation that heats of the tunicle after will developing.
8. lenticule, it is formed by the described radiation sensitive resin composition of claim 1.
CNA2006101421361A 2005-10-03 2006-10-08 Radiation sensitive resin composition, and formation of interlayer insulating film and microlens Pending CN1945432A (en)

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CN101359174B (en) * 2007-07-30 2012-11-28 Jsr株式会社 Radiation-sensitive resin composition, layer insulation film and microlens and manufacture method thereof
CN101458452A (en) * 2007-12-14 2009-06-17 Jsr株式会社 X-ray sensitive resin composition, barrier body and protection film of liquid crystal display member and their forming methods
CN102629077A (en) * 2011-06-29 2012-08-08 北京京东方光电科技有限公司 Preparation methods of resin dielectric layer and its material, liquid crystal panel and display member

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