TW200903157A - Radiation-sensitive resin composition, interlayer insulation film and microlens, and method for manufacturing the same - Google Patents

Abstract

To provide a radiation-sensitive resin composition having high sensitivity to radiation, having a development margin allowing formation of a preferable pattern even through development exceeding the optimum developing time in a developing process, and capable of easily forming a patterned thin film having excellent adhesiveness with a substrate. The radiation-sensitive resin composition contains: [A] a copolymer of (a1) a specified unsaturated compound having a carboxyl group, (a2) a specified unsaturated compound having an alicyclic epoxy skeleton and (a3) an unsaturated compound except for the above (a1) and (a2); and [B] a 1,2-quinonediazide compound.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation sensitive resin composition, an interlayer insulating film, and a microlens, and a method of manufacturing the same. [Prior Art] In an electronic component such as a thin film transistor (hereinafter abbreviated as "TFT") type liquid crystal display element or a magnetic head element 'integrated circuit element' solid imaging element, etc. The wiring between the wirings is arranged to have an interlayer insulating film. In terms of the material for forming the interlayer insulating film, it is preferable to obtain the necessary pattern shape 'the number of steps is small and has sufficient flatness'. Therefore, the sensitive radiation linear resin composition is widely used (refer to 曰本特开2001- In the above-mentioned electronic component, for example, a TF T liquid crystal display device is formed by forming a transparent electrode film on the interlayer insulating film described above, and further forming a liquid crystal thereon. In the step of forming the alignment film, the interlayer insulating film is exposed to light under high temperature conditions in the step of forming the transparent electrode film, that is, in the photoresist stripping liquid used for forming the electrode pattern, so it is necessary to have sufficient Patience. In recent years, the TFT-type liquid crystal display device has a large screen, a high brightness, a high definition, a high-speed response, and a thinner thickness, and is highly sensitive in terms of the composition for forming an interlayer insulating film to be used. The interlayer insulating film formed is sought for in the low dielectric constant, the local transmittance, and the like, and is higher than the high performance of the conventional increase-5-200903157. On the other hand, in the imaging optical system of the onchip color filter or the optical material of the optical fiber connector of a facsimile machine, a photocopying machine, a solid imaging device, etc., a lens diameter of about 3 to ΙΟΟμπι is used. The microlenses 'or regularly align the microlens arrays of the microlenses. When forming a microlens or a microlens array, it is known that after forming a photoresist pattern corresponding to a lens, it is melted by heat treatment, and it is used as a lens as it is, or a molten lens pattern is used as light. The cover is a dry etching method, a method of transferring a lens shape to the bottom layer, or the like. In the case of forming the lens pattern, a sensitive radiation linear resin composition is widely used (refer to Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. However, as the element formed by the above-described microlens or microlens array, thereafter, in order to remove various insulating films on the bonding pad of the wiring forming portion, there are a coating flattening film and a photoresist film for etching, Exposure is performed using a desired mask, development is performed to remove the etching resist of the joint portion, and then the planarization film or various insulating films are removed by etching to expose the step of bonding the pad portions. Therefore, in the microlens or microlens array, in the steps of forming the planarizing film and etching the photoresist coating film and the etching step, it is necessary to have solvent resistance or heat resistance. The sensitive radiation linear resin composition used for forming such a microlens is highly sensitive, and the microlens thus formed has a desired radius of curvature, and has high heat resistance and high transmittance. Moreover, in this way, the obtained interlayer insulating film or microlens, in the development step of forming the same, the development time is only a little more than the optimum time -6-200903157 is too much, at this time, between the pattern and the substrate The developer is impregnated and becomes easily peeled off, so it is necessary to strictly control the development time, which affects the productivity of the product. In this case, when the interlayer insulating film or the microlens is formed from the sensitive radiation linear resin composition, the composition must be high in sensitivity, and in the developing step of the forming step, even if the development time is longer than the set time. It is also possible to exhibit good adhesion without pattern peeling, and the interlayer insulating film thus formed must have high heat resistance, high solvent resistance, low dielectric constant, high transmittance, high adhesion, and the like. On the other hand, when forming a microlens, the microlens must have a good melt shape (desired radius of curvature), high heat resistance, high solvent resistance, high transmittance, but linearity of the sensitive radiation that satisfies this requirement. The resin composition has been unknown to the prior art. Disclosure of the Invention The present invention has been made on the basis of the above reasons. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a high-sensitivity radiation sensitivity, a development limit having a good pattern shape even if an optimum development time is exceeded in a development step, and a linear radiation sensitivity of a pattern-like film excellent in adhesion. Composition. Another object of the present invention is to provide an interlayer insulating film which can form high heat resistance, high solvent resistance, high transmittance, and low dielectric property when used for forming an interlayer insulating film, and when used for forming a microlens, A sensitive radiation linear resin composition of a microlens having a high transmittance and a good melt shape can be formed. Further, another object of the present invention is to provide a method of forming an interlayer insulating film and a microlens by using the above-mentioned radiation radiation line 200903157 resin composition. Further, another object of the present invention is to provide an interlayer insulating film and a microlens formed by the method of the present invention. Other objects and advantages of the present invention will become apparent from the following description. The above objects and advantages of the present invention can be obtained by the following formula (1) ^C〇〇H /4 according to the present invention. , ch2 I X' (1) 烷 an alkylene group having 2 or more carbon atoms (wherein 'R represents hydrogen or methyl 'X represents a methylene group or the following formula (1 -1) to (1 -6)

(1-1) (1-2)

XVX: (1-3) -8- 200903157

(herein, X1 each independently exhibits a methylene group or an alkylene group having 2 or more carbon atoms, and a bond bond on the right-hand side of the formulae (1-1) to (1-6) is bonded to a carboxyl group). Any of the divalent groups shown in any one of the above, having an unsaturated compound having a carboxyl group,

-9 200903157 an alicyclic epoxy group-containing unsaturated compound and (a3) at least one selected from the group consisting of alkyl methacrylates, methacrylic acid cyclic esters, methacrylic acid cyclic alkyl esters, having a hydroxyl group Methacrylate 'cycloalkyl acrylate, aryl methacrylate, aryl acrylate 'unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleic imide compound 'unsaturated aromatic a compound, a conjugated diene; having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a permeose skeleton, a glycidyl skeleton, having the following formula (3)

(In the formula (3), R3 is a hydrogen atom or a methyl group, and η is a repeating number) an unsaturated compound of a skeleton; the following formula (4)

(In the formula (4), R4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a plurality of R5 are each -10 200903157 from an independently hydrogen atom, and a hydroxyl group or an alkyl group having a carbon number of 1 to 4 is a single The bond, -COO- or -CONH-, m is an integer from 0 to 3, but at least one of R5 is a hydroxyl group). An unsaturated compound having a phenolic hydroxyl group as shown, and an unsaturated group selected from the group consisting of acrylonitrile, methacrylonitrile, ethylene chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate. The copolymer of the compound and the radiation-sensitive resin composition of the [B] 1,2-quinonediazide compound are achieved. The object and the advantages of the present invention can be attained by the method of forming an interlayer insulating film or a microlens characterized by the following steps in the order described below. (1) a step of forming a coating film of the above-mentioned radiation-sensitive resin composition on a substrate, (2) a step of irradiating at least a portion of the coating film with radiation, (3) a developing step, and (4) a heating step . Further, the object and the advantage of the present invention can be attained by the interlayer insulating film or the microlens formed by the above method. BEST MODE FOR CARRYING OUT THE INVENTION The radiation sensitive resin composition of the present invention is described in detail below. Copolymer [A] -11 - 200903157 Copolymer [A], preferably by radical polymerization of compound (al), compound (a2) and compound (a3) by the presence of a 'polymerization initiator in a solvent' And manufacturing. The copolymer [A] used in the present invention is preferably a constituent unit derived from the compound (a1) based on the total of the repeating units derived from the compound (al) 'compound (a2) and the compound (a3). It contains 5 to 40% by weight, particularly preferably 5 to 25% by weight. When the repeating unit uses less than 5% by weight of the copolymer, it is difficult to dissolve in the aqueous alkali solution in the developing step, and on the other hand, if it exceeds 4% by weight, the solubility of the copolymer in the aqueous alkali solution is too large. Propensity. The compound (al) is a carboxyl group-containing unsaturated compound represented by the above formula (1). In the above formula (1), in the above formula (1-1) to (1 to 6), the alkylene group having 2 or more carbon atoms of X1 is preferably an alkylene group having 2 to 6 carbon atoms. Illustrative 1, vinyl, 1,2-vinyl, 1,2-propenyl, 1,3 -propenyl, M-dimethyl-1,2-vinyl, 2,2-dimethyl- i,2-vinyl, 1-methyl-1,3-propenyl, 2-methyl-1,3-propenyl, 1,3-butenyl, 1,4-butenyl, 1,5 - pentenyl and the like. In the above formula (1_6), the cyclohexene ring is preferably bonded at a double bond position between the carbon-carbon of the 3-position and the 4-position with respect to -X^OCO-' in the formula (1-6). . In the compound (a 1 ), 2-ethyl carboxyethyl (meth) acrylate ' 2- (meth) propylene is used in view of copolymerization reactivity, solubility in an aqueous alkali solution, and easy availability. Mercaptooxyethyl succinic acid, 2-(methyl)propenyl isopropyl isopropyl succinic acid, 2-(methyl) propylene decyl oxyethyl phthalic acid, 2-(methyl) propylene hydrazino Propyl decanoic acid, 2-(methyl)propenyl decyloxyethyl hexa-12- 200903157 hydroquinone, 2-(methyl)propenyl isopropyl isopropyl hexahydro phthalic acid, 2-(methyl) Preferably, acryloyloxyethyl-3,4,5,6-tetrahydrofurfuric acid or 2-(methyl)propenyloxypropyl-3,4,5,6-tetrahydrofurfuric acid is preferred. These compounds (a 1) may be used singly or in combination. The copolymer [A] used in the present invention preferably contains a constituent unit derived from the compound (a2) based on the total of the repeating units derived from the compound (a1), the compound (a2), and the compound (a3). 1 〇 to 80% by weight, particularly preferably 3 to 80% by weight. When the repeating unit is less than 10% by weight, the heat resistance of the obtained interlayer insulating film or microlens tends to lower the surface hardness and the peeling liquid resistance. On the other hand, when the amount of the repeating unit exceeds 80% by weight The storage stability of the radiation sensitive resin composition is lowered. The compound (a2) is an unsaturated compound having an alicyclic epoxy group selected from the above formulas (2-1) to (2-3). The compound (a2) has the above alicyclic epoxy group, preferably methacrylate, acrylate, styrene compound or vinyl ether compound, and particularly preferably methacrylate. In the case of the compound (a2), it is preferably the following formula -13- 200903157

R1

-14- 200903157

R1

CH2=C

R2

O

R1

R2

O -15- 200903157 R1

R1

R1

-16- 200903157 (In the formula, R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 is a divalent hydrocarbon group having 1 or more carbon atoms). The divalent hydrocarbon group having 1 or more carbon atoms of R2 is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms, more preferably a divalent hydrocarbon group having 2 to 6 carbon atoms, particularly preferably 1,1-vinyl, 1, 2-vinyl, anthracene, 2-propenyl, iota, 3-propenyl, 1,1-dimethyl-1,2-vinyl, 2,2-dimethyl-1,2-vinyl' 1 -Methyl-1,3-propenyl '2-methyl-l,3-propenyl, 1,3-butenyl, ;!, 4-butenyl or 1,5-pentenyl. In the compound (a2), particularly preferred is 3,4-epoxycyclohexylmethyl (meth) acrylate '3,4-epoxytricyclo[5_2·102' decane-8-yl (methyl Acrylate and 2,3-epoxycyclopentylmethyl (meth) acrylate. The copolymer [Α] used in the present invention is preferably a constituent unit derived from the compound (a3) based on the total of the repeating units derived from the compound (a1), the compound (a2)' and the compound (a3). It contains 5 to 80% by weight, and particularly preferably contains 10 to 60% by weight. When the repeating unit is less than 5% by weight, the storage stability of the radiation sensitive linear resin composition is impaired. On the other hand, when the amount of the repeating unit exceeds 80% by weight, the resulting interlayer insulating film or microlens is obtained. The heat resistance 'surface hardness or peeling liquid resistance will be insufficient. In the specific example of the compound (a3), the methyl methacrylate-based vinegar may, for example, be methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, secondary butyl methacrylate, or the like. Grade butyl methacrylate '2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, thirteen-based methacrylate, n-stearyl methacrylate, etc. -17- 200903157 The methacrylic acid cyclic alkyl ester may, for example, be methacrylic acid vinegar 'isopropyl acrylate or the like; and the methacrylic acid cyclic alkyl ester may, for example, be cyclohexyl methacrylic acid Ester, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.〇2'6]decane-8-yl methacrylate, tricyclo[5.2.1.02,6]decane-8- Ethoxyethyl methacrylate, isocarbyl methacrylate, etc.; methacrylate having a hydroxyl group, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3- Hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacryl Ester, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glucoside, 4-hydroxyphenyl methacrylate, etc.; in the case of a cyclic alkyl acrylate, a ring can be exemplified Hexyl acrylate, 2-methylcyclohexyl acrylate 'tricyclo[5.2.1·02'6]decane-8-yl acrylate, tricyclo[5.2.1.0''6]nonane-8-yloxy B Acrylate, iso-tyry acrylate, etc.; aryl methacrylate, phenyl methacrylate, benzyl methacrylate, etc.; aryl acrylate can be exemplified by phenyl acrylate , benzyl propyl acrylate, etc.; unsaturated dicarboxylic acid diester 'may be exemplified by diethyl maleate, diethyl fumarate 'iconic acid diethyl ester, etc.; The compound may, for example, be bicyclo [2.2.1] hept-2-dilute, 5-methylbicyclo [2.2.1] hept-2-lean 5-ethylbicyclo[2.2.1]g.2-dilute, 5-methoxybicyclo[2.2.1]hept-2-ene' 5-ethoxybicyclo[22.丨]heptane--18- 200903157 2-ene' 5,6·dimethoxybicyclo[2.2. 1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-tris-butoxycarbonyl Ring [2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicycloalkene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(tris-butoxy) Carbonyl)bicyclo[2.2.1]hept-2-ene' 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.21]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1 Hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6 -bis(2·-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, etc.; in the case of the maleimide compound, benzene can be exemplified Benzene butadiene imine, n-cyclohexyl maleimide, n-benzyl maleimide, n-(4-hydroxyphenyl) maleimide, positive (4 -hydroxybenzyl) maleimide, n-ammonium imino-3 - maleimide benzoate, n-ammonium imino-4-butylimide Butyrate n-amyl imino-6-m-butyleneimine hexanoate, n-ammonium imino-3-butylimide Propionate, n-(4-oxaridyl) maleimide, etc.; unsaturated aromatic compound, exemplified by styrene, α-methylstyrene, m-methylstyrene, p-methyl Styrene, vinyl toluene, p-methoxystyrene, etc.; conjugated diene, 1,3-butadiene, isoprene ' 2,3-dimethyl-1,3-butadiene Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydroindenyl (meth) acrylate, 2-methylpropenyl oxy-propionic acid tetrahydrofurfuryl ester, and 3-(methyl) propylene. Mercaptooxytetrahydrofuran-2-one, etc.; -19- 200903157 The unsaturated compound containing a furan skeleton may, for example, be 2-methyl-5-furan-3-yl-1-pentan-3-arylopyryl (Methyl) acrylate, 1-furan-2-butyl-3-indan-2-one, 1·furanyl-3-3methoxy-3-ene-2-one '6-furan- 2-yl-2-methyl-1-hexanone '6-furan-2-yl-hex-1-storage-3-ketone'-acrylic acid 2-pyran-2-yl-ethyl-ethyl vinegar '6-furan-2-yl-6-methyl-1-hepten-3-one, etc.; an unsaturated compound containing a tetrahydropyran skeleton, 'exemplified (tetrachloroguanidine) -2 -yl)methylmethyl acrylate vinegar '2,6-monomethyl- 8-(tetrahydrofuran-2-yloxy)-oct-1-en-3-one' 2-methyl Acridine tetrahydropyran-2-yl ester, 1-(tetrahydrofuran-2-oxo)-butyl ketone, etc.; unsaturated compound containing a melane skeleton' can be exemplified as 4-0, 4 -dioxa-5-based (〇x〇)-6-heptyl)-6-methyl-2 -pyrone, 4-(1,5-dioxa- 6-fluorenyl-7-octyl)-6-methyl-2-pyridinone (pyrr〇ne); etc.; unsaturated compound containing a glycidyl skeleton, 'exemplified by glycidyl acrylate 'Glycidyl methacrylate' Glycidyl ethacrylate, n-propyl acrylate acid propylene vinegar 'α-n-butyl acrylate acid propylene vinegar, 0 - B gangrene glycidyl Ether, m-ethyl succinyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc.: in terms of the unsaturated compound containing the skeleton represented by the above formula (3), the number of repeating units η is 2 to 10 Polyethylene glycol mono(meth)acrylate', repeating unit number η is 2 to 10, polypropylene glycol mono(meth)acrylate, etc.; The unsaturated compound containing a phenolic hydroxyl group represented by the formula (4) may, for example, be a formula (5)-(9)-20-200903157

R4 R5 NH-(CH2)m

R5 R5

R5 (5)

(7)

R4

R5 - 21 - (9) 200903157 (In the formulas (5) to (9), R4 and R5 are the same as those in the above formula (4), and m' is an integer of 1 to 3). Compounds shown and the like. In the above, an alkyl methacrylate, a cyclic alkyl methacrylate, a maleimide compound, an unsaturated aromatic compound; a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a meridane skeleton, a glycidyl skeleton, an unsaturated compound of the skeleton represented by the above formula (3); an unsaturated compound containing a phenolic hydroxyl group represented by the above formula (4), preferably having a copolymerization reactivity and an aqueous alkali solution From the viewpoint of solubility, especially styrene, tertiary butyl methacrylate, tricyclic [5. 2. 1·02'6] 癸院-8-ylmethyl acrylate, p-methoxyphene, 2-methylcyclohexyl acrylate, n-phenyl maleimide, n-cyclohexyl Maleicimide 'tetrahydroindenyl (meth) acrylate, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate having a repeating unit number η = 2 to 10 ' 3-(Methyl)acryloyloxytetrahydrofuran-2-one, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, hydrazine hydroxy styrene, hydrazine-hydroxyl Styrene or hydrazine: -methyl-hydrazine-hydroxystyrene is preferred. These compounds (a3)' may be used singly or in combination. The copolymer [A] used in the present invention, preferably a specific example, may be exemplified by 2-methylpropenyloxyethyl decanoic acid/3,4-epoxycyclohexylmethyl (meth)acrylic acid. Ester / styrene / tricyclic [5. 2. 1. 〇2,6]decane _8_yl (meth) acrylate ' 2-(methyl) propylene sulfoxy hexahydro phthalic acid / 3,4_epoxycyclohexylmethyl (A Acrylate/4-(methyl)propenyl morpholinyl/3_(methyl)propenyloxytetrahydrofuran-2-one/styrene, 2-(methyl)acrylamido-22- 200903157 Oxygen Propyl hexahydrophthalic acid / 3,4-epoxycyclohexylmethyl (meth) acrylate / n-cyclohexyl maleimide / styrene, (meth) propylene thioethyl amber Acid / 3,4-epoxytricyclo[5. 2. 1. 02'6] decane-8-yl (meth) acrylate / tricyclo [5. 2. 1.  〇 2,6]decane-8-yl (meth) acrylate / 4-hydroxyphenyl (meth) acrylate. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the copolymer [A] used in the present invention is preferably from 2χ103 to ΙχΙΟ5, more preferably from 5x10 to 5x10. When the Mw is less than 2×10 3 , the development limit is insufficient, the residual film ratio of the obtained film is lowered, and the pattern shape of the interlayer insulating film or the microlens, the heat resistance and the like are deteriorated. On the other hand, when it exceeds l×10 5 , The sensitivity is lowered and the shape of the pattern is deteriorated. Further, the molecular weight distribution (hereinafter referred to as "Mw/Mn") is preferably 5. 0 or less, more preferably 3. 0 is below. If Mw/Mn exceeds 5. When 0, the resulting interlayer insulating film or microlens has a poor pattern shape. The radiation-sensitive resin composition containing the above-mentioned copolymer [A] can be formed without any development residue during development, and it is easy to form a solvent having a pattern shape and a solvent used for the production of the copolymer [A]. Alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, Ketones, esters, etc. In the specific examples, the alcohol may, for example, be methanol, ethanol benzyl alcohol, 2-phenylethyl alcohol or 3-phenyl-1-propanol; and the ether may, for example, be tetrahydrofuran or the like; The alcohol ether may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl-23 - 200903157 ether or the like; and ethylene glycol alkyl ether acetate may, for example, be methyl cellosolve acetate. , ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc.; diethylene glycol, may be exemplified by diethylene glycol monomethyl ether , diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; propylene glycol monoalkyl ether, propylene glycol can be exemplified Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; propylene glycol alkyl ether propionate, propylene glycol methyl acid propionate, propylene glycol ethyl ether propionic acid Ester, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc.; propylene glycol alkyl ether acetate, propylene glycol methyl acid acetate 'propylene glycol B' Ethyl acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc.; aromatic hydrocarbons, for example, toluene, xylene, etc.; and ketone, methyl ethyl ketone, cyclohexane Ketone, 4-trans-based 4-methyl-2-pentane, etc.; esters can be exemplified by methyl acetate 'ethyl acetate, propylene acetate, butyric acid vinegar '2-propionic acid ethyl vinegar' 2 - methyl 2-methylpropionic acid methyl acetonate, ethyl 2-pyridyl-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, Propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate 2-hydroxy-3-methylbutane Methyl ester, methyl methoxyacetate 'acetic acid ethyl acetate' propyl methoxyacetate, methoxyacetic acid butyl-24- 200903157 ester 'ethoxy ethoxyacetate, ethyl ethoxyacetate, Propyl ethoxyacetate butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxy propyl acetate, butyl propyl acetate, methyl butoxyacetate, Oxygen B Ethyl ester, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methyl Butyl oxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 2-butyl Methyl oxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methyl Ethyl oxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-B Propyl oxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propyl Butyl oxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, etc. Among them, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate is preferred, especially diethylene glycol dimethyl ether, diethylene glycol Methyl ether, C Alcohol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate, 3 - methoxy-propionic acid methyl preferred. As the polymerization initiator to be used in the production of the copolymer [A], a conventional radical polymerization initiator can be generally used. It may, for example, be 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy Azo compounds such as benzyl-2,4-dimethylvaleronitrile; phenylhydrazine peroxide, laurel peroxide, tertiary butyl peroxytrimethyl acetate '1,1'-double - ( -25- 200903157 tertiary butyl peroxy) an organic peroxide such as cyclohexane; and hydrogen peroxide. When a peroxide of a radical polymerization initiator is used, a peroxide and a reducing agent can also be used together as a redox type initiator. In the production of the copolymer [A], a molecular weight modifier can be used to adjust the molecular weight. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide: n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tridecyl mercaptan, thioglycolic acid, and the like. Thiol compound; xanthogen sulfide, diisopropyl xanthyl ester, 2-disulfide, etc., xanthate, 2-compound; onion oleyl, Α-methylstyrene dimer, and the like. [Β] Component The [Β] component used in the present invention is a 1,2-quinonediazide compound which generates a carboxylic acid by irradiation with radiation, and a phenolic compound or an alcoholic compound (hereinafter referred to as " A condensate of a parent core ") with a 1,2-naphthoquinonediazidesulfonic acid halide. The above-mentioned mother nucleus may, for example, be trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone 'pentahydroxydiphenyl ketone' hexahydroxydiphenyl ketone or (polyhydroxyphenyl)alkane, and other mother nucleus. In the specific examples, the trihydroxydiphenyl ketone may, for example, be 2,3,4-trihydroxydiphenyl ketone or 2,4,6-trihydroxydiphenyl ketone; or the like; As the ketone, 2,2,4,4,-tetrahydroxydiphenyl ketone, 2,3,4,3'-tetrahydroxydiphenyl ketone, 2,3,4,4,-tetrahydroxyl group can be exemplified. Diphenyl ketone, 2,3,4,2·-tetrahydroxy-4'-methyldiphenyl ketone, 2,3,4,4,-tetrahydroxy-3,.  -26- 200903157 methoxydiphenyl ketone, etc.; pentahydroxydiphenyl ketone, exemplified by 2,3,4,2',6'-pentahydroxydiphenyl ketone; hexahydroxydiphenyl ketone The aspect may, for example, be 2,4,6,3',4',5^hexahydroxydiphenyl ketone, 3,4,5,3',4',5'-hexahydroxydiphenyl ketone or the like; The polyhydroxyphenyl)alkane may, for example, be bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1 J-tri ( p-Hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tri 2,5-Dimethyl-4-hydroxyphenyl)-3-propenylpropyl, 4,4'-[1-[4-[1-[4-]-phenylphenyl]-1-methyl Phenyl]ethylidene]bisphenol, bis(2, %dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane '3,3,3',3'-tetramethyl-1 , 1'-helical biguanide-5,6,7,5,6,7,-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan, etc.; For other parent cores, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7- via the basic color '2-[double {(5) -isopropyl-4-carbyl- 2-methyl)phenyl}methyl], 1-[1-(3-{1-(4-hydroxyphenyl)-1-methylethyl}_ 4,6-dihydroxyphenyl)_ι_ Methyl ethyl]-3-(1-(3-{1-(4-hydroxyphenyl)-1-methylethyl}-4,6-dihydroxyphenyl)-1-methylethyl) Benzene, fluorene 6-bis{1-(4-hydroxyphenyl)-1-methylethyl}-1,3-dihydroxybenzene, and the like. Further, a 1,2-naphthoquinonediazidesulfonylamine which changes the ester bond of the above-exemplified parent core to a guanamine bond can also be suitably used, and 2,3,4-trihydroxy group can be exemplified. Phenylketone-1,2-naphthoquinonediazide-4-sulfonic acid decylamine and the like. Among these cores, 2,3,4,4,-tetrahydroxydiphenyl ketone, 4,4,-[1-[4-[1-[4-hydroxyphenyl]_1-methylethyl Phenyl]ethylidene]bisphenol is preferred, -27- 200903157 In the case of 1,2-naphthoquinonediazidesulfonic acid halide, it is preferred to use 1,2-naphthoquinonediazidesulfonic acid chloride. Specific examples thereof include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride, among which are used. I, 2-naphthoquinonediazide-5-sulfonic acid chloride is preferred. In the condensation reaction, it is preferred to use 1,2-naphthalene equivalent to 30 to 8 5 mol%, more preferably 5 to 7 mol%, based on the number of OH groups in the phenolic compound or the alcohol compound. Bismuth azide sulfonic acid halide. The condensation reaction can be carried out by a known method. These [B] components may be used singly or in combination of two or more. The use ratio of the component [B] is preferably 5 to 100 parts by weight, more preferably 1 to 50 parts by weight, per 100 parts by weight of the copolymer [A]. When the ratio is less than 5 parts by weight, the difference in solubility between the irradiated portion and the unirradiated portion of the aqueous alkali solution serving as the developer is small, and the patterning is difficult, and the heat resistance of the interlayer insulating film or the microlens is obtained. And the solvent resistance is insufficient. On the other hand, when the ratio exceeds 100 parts by weight, the solubility in the aqueous alkali solution in the irradiated portion is insufficient, and development is difficult. Other components The radiation sensitive resin composition of the present invention contains an essential component of the above copolymer [A] and [B] components, but may contain, as needed, [c] a thermosensitive acid generating compound '[D] has at least 1 Polymerizable compound having an ethylenically unsaturated double bond '[E] an epoxy resin other than the copolymer [A], [F] a surfactant or a [G] adhesion aid. -28- 200903157 The above [C] sensible acid generating compound can be used to increase the heat resistance hardness. Specific examples thereof include a key salt of an onium salt, a benzothiazole key salt, and a scale salt. Specific examples of the above sulfonium salt include an alkyl phosphonium salt, a benzyl group, a dibenzyl phosphonium salt, a substituted benzyl phosphonium salt, and the like. In the specific examples, the alkyl phosphonium salt may, for example, be 4-ethenylphenyldimethylhexafluoroantimonate, 4-ethenyloxyphenyldimethylsulfonium hexafluoroarsenate, base-4-( Benzyloxycarbonyloxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(phenoxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(phenylhydrazono)phenylarsenic arsenate The acid salt, dimethyl-3-chloro-4-ethyloxyphenyl hexafluoroantimonate _ benzyl sulfonium salt, benzyl-4-hydroxyphenyl methyl decanoate, Benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, 4-ethylphenylbenzylmethylphosphonium hexafluoroantimonate, benzyl-4-methoxyphenylphosphonium hexafluoroantimonate, Benzyl-2-methyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, benzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroarsenate, 4-methylbenzyl-4-hydroxyl Phenylmethyl sulfonium hexafluorophosphate; and the like; in the case of the dibenzyl sulfonium salt, dibenzyl-4-hydroxyphenyl decanoate, dibenzyl-4-hydroxyphenyl sulfonium hexafluorophosphate, 4-Ethylphenyldibenzylphosphonium hexafluoroantimonate, dibenzyl-4-methoxyphenyl decanoate, dibenzyl-3-chloro-4-hydroxyphenylphosphonium hexafluoroarsenate Salt, two: 3-methyl-4-hydroxy -5- three butylphenyl gilt hexafluoroantimonate, benzyl.  Oxybenzyl-4-hydroxyphenylphosphonium hexafluorophosphate; etc.; substituted benzyl sulfonium salt, chlorobenzyl-4-hydroxyphenyl hexafluoroantimonate, p-nitrobenzyl- 4-hydroxyphenylmethylhydrazine hexa or ammonium salt sulfonium hydrazinyl dimethyl hexafluorohexafluoro fluorenyloxymethyl decanoic acid hexafluoro hexafluoroP-based 4-methyl fluoro chain - 29- 200903157 acid salt, p-chlorobenzyl-4-hydroxyphenylmethyl sulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethyl hexafluoroantimonate ' 3 5-Dichlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, hydrazine-chlorobenzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, and the like. Specific examples of the above benzothiazole moieties include 3-benzylbenzothiazole gun hexafluoroantimonate, 3-benzylbenzothiazole iron hexafluorophosphate '3-benzylbenzothiazole gun four Fluoroborate, 3 · (p-methoxybenzyl) benzothiazole, hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazole, hexafluoroantimonate, 3-benzyl a benzyl benzothiazole iron salt such as 5-5-chlorobenzothiazole hexafluoroantimonate. Among these, it is preferred to use a phosphonium salt and a benzothiazole moieties, particularly 4-ethyloxyphenyl dimethyl hexafluoroarsenate, benzyl-4-hydroxyphenylmethyl hydrazine. Hexafluoroantimonate, 4-ethenyloxyphenylbenzylmethylphosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, 4-ethenyloxyphenylbenzyl Based on hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate is preferred. For the above-mentioned commercial products, Sun Aid SI-L85, the same as SI-L110, the same as SI-L145, the same as SI-L150, and the same as SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.). The use ratio of the component [C] is preferably 20 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the copolymer [A]. When the amount is more than 20 parts by weight, precipitates are precipitated in the coating film forming step, which hinders the formation of a coating film. A polymerizable -30-200903157 compound (hereinafter referred to as "[D] component") having at least one of the above-mentioned [D] ethylenically unsaturated double bonds may, for example, be a preferred monofunctional (methyl) group. Acrylate, bifunctional (meth) acrylate or trifunctional or higher (meth) acrylate. The monofunctional (meth) acrylate may, for example, be 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isocarbyl (meth) acrylate, or methoxy. Butyl (meth) acrylate, 2-(methyl) propylene sulfoxy ethoxyethyl 2-hydroxypropyl phthalate, and the like. For the commercial products, Aronix M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARADTC-110S, and TC-120S (above, Nippon Kayaku Co., Ltd.) can be exemplified. ), bisuko-to 158, the same as 2311 (above, Osaka Organic Chemical Industry Co., Ltd.). The bifunctional (meth) acrylate may, for example, be ethylene glycol (meth) acrylate, 1,6-hexane diol di(meth) acrylate or 1,9-nonanediol bis (a) Acrylate, polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, diphenoxyethanol oxime acrylate, diphenoxyethanol oxime acrylate, and the like. For such commercial products, Aronix M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, and R-604 (above, Japan) Chemical company, bisuko-to 260, 312, 335HP (above, Osaka Organic Chemical Industry Co., Ltd.). The trifunctional or higher (meth) acrylate may, for example, be trimethylolpropane tri(meth) acrylate, neopentyl alcohol tri(meth) acrylate, or tris((meth) propylene oxime). Ethyl) phosphate, neopentyl alcohol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(-31 - 200903157 methyl) acrylate, etc. Commercial product 'can be exemplified Arc> nix M_309, same as M-400, same M-405, same M-450, same as M-7100 ' with M-803 0, same with M- 8 060 (above, East Asia Synthesis Company KA) KAYARAD TMPTA, same as DPHA, DPCA-20, DPCA-30 'DPCA 60, DPCA-120 (above, Nippon Kayaku Co., Ltd.)' bisuko-to 295, same as 300, same as 3 60, Same as GPT, the same as 3PA, the same as 400 (above, Osaka Organic Chemical Industry Co., Ltd.). Among these, it is preferred to use a trifunctional or higher (meth) acrylate, among which trimethylolpropane tri(meth)acrylate, neopentyltetrakis(meth)acrylate, dioxane Tetraol hexa(meth) acrylate is particularly preferred. These monofunctional, bifunctional or trifunctional or higher (meth) acrylates may be used singly or in combination. The use ratio of the component [D] is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less based on 100 parts by weight of the copolymer [A]. By including the component [D] in such a ratio, the heat resistance, surface hardness, and the like of the interlayer insulating film or the microlens obtained from the radiation-sensitive resin composition of the present invention can be improved. When the amount used exceeds 5 parts by weight, a film dry spot is formed in the step of forming a coating film for the radiation-sensitive resin composition on the substrate. The epoxy resin other than the above [E] copolymer [A] (hereinafter referred to as "[E] component") is not particularly limited insofar as it does not affect the compatibility, and bisphenol is preferably exemplified. Type A epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidylamine - 32-200903157 type epoxy resin, heterocyclic epoxy resin 'glycidyl methyl acrylate, a (co)polymerized resin. Among these, bisphenol A type epoxy resin, cresol formaldehyde varnish type epoxy resin, glycidyl ester type epoxy resin, etc. are particularly preferable. The use ratio of the component [E] is preferably 30 parts by weight or less, more preferably 1 to 20 parts by weight, per 100 parts by weight of the copolymer [A]. By including the [E] component in such a ratio, the heat resistance, surface hardness, and the like of the protective film or the insulating film obtained from the radiation sensitive resin composition of the present invention can be further improved. When the ratio exceeds 30 parts by weight, when the coating film of the radiation sensitive resin composition is formed on the substrate, the film thickness uniformity may be insufficient. Further, the copolymer [A] may also be referred to as "epoxy resin", but differs from the [E] component in that it has alkali solubility. The component [E] is alkali-insoluble. . In the radiation sensitive resin composition of the present invention, the above [F] surfactant may be further used to improve coatability. As the [F] surfactant which can be used herein, a fluorine-based surfactant, a polyoxyn surfactant or a nonionic surfactant is preferably used. Specific examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2,2-tetrafluorooctyl Hexyl hexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, eight Propylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexapropanediol bis(1,1,2,2,3,3-hexafluoropentyl)ether sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. Sodium fluoroalkyl benzene sulfonate; fluoroalkyl oxyethylene ether; fluoroalkyl ammonium iodide, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethylene; perfluoroalkyl-33-200903157 alkoxide; A fluoroalkyl ester or the like. For such commercial products, BM-1 000, BM-1100 (above, BM Chemie), megafuck F142D, F172, F173 and F183, F178, F191, and F471 (above, Dainippon Ink Chemical Industry Co., Ltd., Fluorad FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M), Safron S-112, same as S-113, with S-131, same S-141, same as S-145, with S-382, with SC-101, with SC-102, with SC-103, with SC-104, with SC-105, with SC-106 (made by Asahi Glass Co., Ltd.) f -top EF301, the same as 303, the same as 352 (manufactured by New Akita Chemical Co., Ltd.), etc., may be exemplified by the trade name DC3PA, DC7PA, FS-1 2 5 > SF-8428 > SH11PA > SH21PA 'SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ- 6032 (above 'Toray· Dow Corning. Commercial products such as Teflon Co., Ltd., TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, Momentive performance materials contract company). As the nonionic surfactant, for example, a polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or polyoxyethylene oleyl ether; polyoxyethylene octylbenzene; a polyoxyethylene aryl ether such as a polyether ethylene nonyl phenyl ether; a polyoxyethylene dilaurate; a polyoxyethylene condensate such as polyoxyethylene dilaurate; (Methyl)-propyl anabolic acid copolymer 'Polyflow Νο·57, the same as 95 (manufactured by Kyoeisha Chemical Co., Ltd.). These surfactants can be used individually or in combination of 2 or more types. -34- 200903157 The [F] surfactant is preferably used in an amount of 5 parts by weight or less based on 100 parts by weight of the copolymer [A], more preferably 〇. 〇 1 to 2 parts by weight of the range. When the amount of the surfactant to be used exceeds 5 parts by weight, when the coating film is formed on the substrate, dry film spots of the coating film are likely to occur. In the radiation sensitive resin composition of the present invention, the [G] adhesion aid can be further used to improve the adhesion to the substrate. In the case of such a [G] adhesion aid, a functional decane coupling agent is preferably used, and a decane coupling agent having a reactive substituent such as a carboxyl group, a methyl propylene group, an isocyanate group or an epoxy group may, for example, be mentioned. Specifically, trimethoxydecyl benzoic acid, r -methyl propylene methoxy propyl trimethoxy decane, ethylene triethoxy decane, ethylene trimethoxy decane, and r - isocyanate propyl tri Ethoxy decane, r-glycidylpropyltrimethoxydecane, bis-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. The [G] adhesion aid is preferably used in an amount of 20 parts by weight or less, more preferably in parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the adhesion aid exceeds 20 parts by weight, development remains in the developing step. Radiation-sensitive linear resin composition The radiation-sensitive resin composition of the present invention can be prepared by uniformly mixing the above-mentioned #polymer [A] and [B] components and other components which can be arbitrarily added. The radiation sensitive resin composition of the present invention is preferably dissolved in an appropriate solvent and used in a solution state. A radiation-sensitive resin composition in which the copolymer [A] and [B] components and any other components added are mixed at a predetermined ratio in a state in which the solution can be prepared in the range of -35-200903157 can be exemplified. In order to prepare a solvent to be used for the radiation sensitive resin composition of the present invention, it is possible to use an average of the components of the copolymers [A] and [B] and any other components which are optionally blended, and which do not react with the respective components. As such a solvent, the same ones exemplified for the solvent used for the production of the above copolymer [A] can be exemplified. Among such solvents, alcohol, glycol ether, ethylene glycol alkyl ether acetate, and ester are used from the viewpoints of solubility of each component, reactivity with each component, and formation of a coating film. And diethylene glycol is preferred. Among these, benzyl alcohol '2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate 'diethylene glycol monoethyl ether acetate Ester, diethylene glycol diethyl ether 'diethylene glycol ethyl methyl ether' diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methoxypropionic acid Methyl ester, ethyl ethoxypropionate is particularly preferred. Further, the solvent can be simultaneously used in combination with a high boiling point solvent to improve the uniformity in the film thickness. The high-boiling solvent which can be used may, for example, be n-methylformamide, N,N-dimethylformamide, N-methyl N-methylanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl selenium 'benzyl ethyl ether, dihexyl ether, acetone acetone, isophor _, caproic acid octanoic acid, 1-octyl Alcohol '1-nonanol, benzyl acetate, ethyl benzoate, monoethyl ester early 'succinic acid diacetate, butyl vinegar, ethyl carbonate propylene ester propylene carbonate, phenyl cellosolve B Acid esters, etc. Among these, N-methylpyrrolidone, r-butyrolactone, and N,N-dimethylacetamide are preferred. When the solvent of the radiation-sensitive resin composition of the present invention is used in a high-boiling solvent-36-200903157, the amount thereof is 50% by weight or less with respect to the total solvent amount, preferably 40% by weight or less, more preferably 30% by weight or less. When the amount of the high-boiling solvent used exceeds the amount used, the film thickness uniformity and the residual film ratio of the coating film may be lowered. When the radiation sensitive resin composition of the present invention is prepared into a solution state, the solid content concentration (the composition other than the solvent in the composition solution (copolymer [A] and [B] components and the total amount of other components added arbitrarily) The ratio occupied by the film may be arbitrarily set depending on the purpose of use or the desired thickness of the film, etc., but is preferably 5 to 50% by weight, more preferably 1 to 4% by weight, and most preferably 15% by weight. 35 wt%. In this way, the prepared composition solution can be made with a pore diameter of 0. The microporous filter at the bottom of 2 μιη is filtered and used. Interlayer insulating film, formation of microlens Next, a method of forming the interlayer insulating film and the microlens of the present invention using the radiation sensitive resin composition of the present invention will be described. The method for forming an interlayer insulating film or a microlens of the present invention comprises the following steps in the following order: (1) a step of forming a coating film of the radiation sensitive resin composition of the present invention on a substrate, (2) applying the coating At least a portion of the film is irradiated with radiation, (3) a developing step, and (4) a heating step. (1) Step of forming a coating film of the radiation sensitive linear resin composition of the present invention on a substrate - 37 - 200903157 In the step (1) above, 'coating the composition solution of the present invention on the surface of the substrate' is preferably The solvent is removed by heat treatment (prebaking) to form a coating film of the radiation sensitive resin composition. The type of the substrate that can be used may, for example, be a glass substrate, a ruthenium substrate, or a substrate formed of various metals on the surfaces. The coating method of the composition solution is not particularly limited, and may be, for example, a spray method 'light coating method' spin coating method, a slit die coating method, a rod coating method, an inkjet method, or the like. A suitable method, in particular, a spin coating method is preferred. The pre-baking conditions vary depending on the species' use ratio of each component. It can be exemplified by 60 to 110. (3 pre-baking for 30 seconds to about 15 minutes. In terms of the film thickness of the formed coating film, when the interlayer insulating film is formed, the 値 after prebaking is preferably 3 to 6 μm, and when the microlens is formed, 〇5~3μηη is preferable. (2) Step of irradiating at least a part of the coating film with radiation. In the step (2), the irradiated film is irradiated on the formed coating film via a mask having a setting pattern. After that, the irradiated portion of the radiation is removed by development with a developing solution, and the pattern is formed. In this case, ultraviolet rays, far ultraviolet rays, X-ray charged particle rays, and the like are used for the radiation to be used. (wavelength: 43 6 nm), i-line (wavelength: 3, 65 nm), etc. In terms of far-ultraviolet rays, a KrF excimer laser or the like may be exemplified as a synchrotron radiation, etc. In terms of a charged particle beam, an electron may be exemplified. Beams, etc. Among these, ultraviolet rays are preferred, and -38-200903157 containing g-line and/or i-line is particularly preferable. The amount of exposure is 5 〇~1,5 when forming an interlayer insulating film. 〇〇J/m2 is better, when forming a microlens, '5 〇~2, 〇 〇〇J/m2 is preferred. (3) Developing solution for developing solution, sodium hydroxide, potassium hydroxide 'sodium carbonate, sodium citrate, sodium methyl citrate, ammonia, ethylamine can be used. , n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine 'methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide Ammonium 'tetraethylammonium hydroxide, pyrrole, piperidine, hydrazine, 8 _diazabicyclo ring [5. 4. An aqueous solution of a base (alkaline basic compound) such as -7-undecene' 1,5-diazabicyclo[43〇]_5•decane. Further, an aqueous solution of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be appropriately added to the aqueous alkali solution or a various organic solvent in which the composition of the present invention is dissolved may be used as a developing solution. Further, as the developing method, a suitable method such as a liquid-filling method, a dipping method, a shaking dipping method, and a rinsing method can be used. In this case, the development time varies depending on the composition of the composition, and may be, for example, 30 to 120 seconds. Further, in the conventional radiation-sensitive resin composition, if the development time exceeds the optimum temperature of about 2 〇 to 25 seconds, the pattern formed is easily peeled off, so that the development time must be strictly controlled, but the radiation-sensitive resin composition of the present invention is composed. Even if it exceeds the optimum development time for more than 30 seconds, it can form a good pattern and has the advantage of product productivity. (4) Heating step - 39 - 200903157 After the development step of (3) as described above, the patterned film is preferably subjected to, for example, a rinse treatment of "flowing water" and further preferably by a high pressure mercury lamp. After the radiation is completely irradiated (post-exposure), the decomposition treatment of the residual 1,2-quinonediazide compound in the film is performed, and then the film is heat-treated by a heating device such as a hot plate or an oven (post-baking treatment). 'The hardening treatment of the film is carried out. In the above post-exposure step, the exposure amount is preferably about 2,000 to 5,000 J/m2. Further, in the hardening treatment, the baking temperature is, for example, 1 20 to 25 (TC. The heating time varies depending on the type of the heating device, but for example, when heat treatment is performed on a hot plate, it may be 5 to 30 minutes in the oven) In the case of heat treatment, it may be 30 to 90 minutes. In this case, a step bake method in which two or more heating steps are performed may be used. In this way, an intended interlayer insulating film or a microlens pattern is used. The interlayer film can be formed on the surface of the substrate. The interlayer insulating film of the present invention, which is formed as described above, has good adhesion to the substrate, is excellent in solvent resistance and heat resistance, and has high transmittance and low dielectric constant. It can be applied to an interlayer insulating film of an electronic component. The microlens of the present invention formed as described above has good adhesion to a substrate, is excellent in solvent resistance and heat resistance, and has high transmittance and a good melt shape. A microlens suitable for use in a solid imaging element. The shape of the microlens of the present invention, as shown in Fig. 1(a), is a semi-convex 40-200903157 lens shape. As described above, the present invention The sensitive radiation linear resin composition has a high-sensitivity radiation sensitivity, and in the development step, it has a development limit which can form a good pattern shape even if it exceeds an optimum development time, and it is easy to form a pattern-shaped film excellent in adhesion. The interlayer insulating film and the microlens of the present invention formed of the present invention can satisfy the properties required for the interlayer insulating film and the microlens (the increasingly stringent performance required in recent years). [Embodiment] Hereinafter, a synthesis example will be exemplified. The present invention is specifically described in the following examples, but the present invention is not limited to the following examples. Synthesis Example of Copolymer [A] Synthesis Example 1 In a flask equipped with a cooling tube 'mixer, 2 2 parts by weight of 2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether, followed by 2-methylpropenyloxyethyl decanoic acid 25 parts by weight of '3,4-epoxycyclohexylmethyl methacrylate 45 parts by weight of 'phenethyl ether 1 part by weight, tricyclic [5. 2. 1. 20 parts by weight of 〇2,δ]decane-8-ylmethylpropanoic acid vinegar and 3 parts by weight of α-methylstyrene dimer, after being substituted with nitrogen, began to be slowly disturbed. The temperature of the solution was raised to 70 ° C, and the polymer solution containing the copolymer [A -1 ] was obtained by maintaining the temperature for 4 hours. -41 - 200903157 The converted polystyrene of the copolymer [A-1] has a weight average molecular weight (M w) of 10,000 and a molecular weight distribution (Mw/Mn) of 25. Further, the solid solution concentration of the polymer solution obtained here is 3 4. 5 wt%. Synthesis Example 2 In a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 g of diethylene glycol ethyl methyl ether were placed. Share. Next, 2 parts by weight of 2-methylpropenyloxyethyl hexahydrophthalic acid was added, and 3 parts by weight of '3,4-epoxycyclohexylmethylmethyl acrylate vinegar 50 parts by weight, 4-propenyl bromomorpholine 10 Parts by weight, 15 parts by weight of 3-methylpropenyloxytetrahydrofuran-2-one, 12 parts by weight of styrene, and 3 parts by weight of α-methylstyrene dimer, were substituted with nitrogen, and then slowly stirred. The temperature of the solution was raised to 70 ° C, and by maintaining the temperature for 5 hours, the converted polystyrene weight average molecular weight (Mw) of the polymer solution ruthenium copolymer [A-2] containing the copolymer [A-2] was obtained. The molecular weight distribution (Mw/Mn) was 3.8. Further, the solid solution concentration of the polymer solution obtained here is 3 2. 1% by weight. Synthesis Example 3 In a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis(2,4-diisobutylvaleronitrile) and diethylene glycol ethyl methyl ether 220 were placed. Parts by weight. Next, 20 parts by weight of 2-methylpropenyloxypropyl hexahydrophthalic acid and 45 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate, fluorene-cyclohexyl-n-butylene 10 parts by weight of the imine and 25 parts by weight of styrene, after replacing -42-200903157 with nitrogen, began to stir slowly. The temperature of the solution was raised to 8 (TC, and the polymer solution containing the copolymer [A-3] was obtained by maintaining the temperature for 5 hours. The converted polystyrene weight average molecular weight (Mw) of the copolymer [A-3] For 11,000, the molecular weight distribution (Mw/Mn) is 2. 8. Further, the solid solution concentration of the polymer solution obtained here was 32. 6 wt%. Synthesis Example 4 In a flask equipped with a cooling tube and a stirrer, 8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 g of diethylene glycol ethyl methyl ether were placed. Share. Next, 15 parts by weight of methacryloyloxyethyl succinic acid, 3,4-epoxytricyclo[5·2·1·02'6]decane-8-yl methacrylate 50 weight Share, three rings [5. 2. 1. 02'6] 25 parts by weight of decane-8-yl methacrylate and 1 part by weight of 4-hydroxyphenyl methacrylate, and after being substituted with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and by maintaining the temperature for 5 hours, a polymer solution containing the copolymer [A-4 ] was obtained. The weight average molecular weight (Mw) of the converted polystyrene of the copolymer [A-4] was 8,900', and the molecular weight distribution (Mw/Mn) was 2. 4. Further, the solid solution concentration of the polymer solution obtained here was 3 1 . 5 wt%. Comparative Synthesis Example 1 In a flask equipped with a cooling tube 'mixer, 8 parts by weight of 2,2,-azobis(2,4·dimethylvaleronitrile) and diethylene glycol ethyl methyl ether 22 were placed. 〇 by weight. Next, 18 parts by weight of methacrylic acid, 45 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate, and 10 parts by weight of styrene, tricyclo-43-200903157 [5. 2. 1. 02'6] 27 parts by weight of 癸垸-8-ylmethyl ketone vinegar and 3 parts by weight of a-methyl styrene dimer, and after being substituted with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and by maintaining the temperature for 4 hours, a polymer solution containing the copolymer [a-Ι] was obtained. The copolymer [a-Ι] has a weight average molecular weight (Mw) of 8,800 and a molecular weight distribution (Mw/Mn) of 2. 4. Further, the solid solution concentration of the polymer solution obtained here is 3 1. 9% by weight. Comparative Synthesis Example 2 In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and diethylene glycol ethyl methyl ether 2 were placed. 00 parts by weight. Next, 25 parts by weight of 2-glycidyloxyethyl phthalic acid and 45 parts by weight of glycidyl methacrylate were added, and 10 parts by weight of styrene, tricyclo [5. 2. 1. 02,6] 20 parts by weight of decane-8-yl methacrylate and 3 parts by weight of α-methyl styrene dimer, and after being substituted with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C 'by maintaining the temperature for 4 hours' to obtain a polymer solution containing the copolymer [a-2]. The converted polystyrene weight average molecular weight (Mw) of the copolymer [a-2] was 14, 〇〇〇, and the molecular weight distribution (Mw/Mn) was 2. 5. Further, the solid solution concentration of the polymer solution obtained herein was 34. Preparation Example 3 of a Radiation-Resistant Linear Resin Composition Example 1 A solution containing the copolymer [A - 44-200903157 1] synthesized in the above Synthesis Example 1 as a copolymer was equivalent to a copolymer [Al] 100 parts by weight (solid component)' and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl] as a component [B] Ethyl]bisphenol (1. 0 molar) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2. 30 parts by weight of the condensate (Bl) of 0 moles was mixed so that the solid content concentration became 30% by weight, and after being dissolved in diethylene glycol ethyl methyl ether, it was filtered by a micropore filter having a diameter of 2 μm A solution-like radiation sensitive resin composition (S-1) was prepared. Examples 2 to 4, Comparative Examples 1 and 2 In Example 1, except for the [Α] component and the [Β] component, the types and amounts described in Table 1 were used, and in Examples 2 and 3, the [Ε] component was further added. A radiation-sensitive resin composition (s - 2) of the same solution as in Example 1 except that 5 parts by weight of yS-(3,4-epoxycyclohexyl)ethyltrimethoxy sand was used. (S-4) and (s-1) to (s-2). Further, in Example 3, the [B] component used was a type of 1,2-quinonediazide compound described in Table 1. Example 5 In Example 1, except that the solvent was a mixed solvent of diethylene glycol ethylmethyl 7 propylene glycol monomethyl ether acetate (weight ratio: 6/4)', and further added SH-28PA ( Product name, Toray.  Dow Corning. Poly Oxygen Company) 0. The solution-like radiation sensitive resin composition (S-5) was prepared in the same manner as in Example 1 except that the solid content concentration of the composition solution was 20% by weight. -45- 200903157 Table 1

In Table 1, each of the abbreviations denotes the following compounds. : Condensate of hydroxyphenyldiphenyl-methylethyl]phenyl-powder (1_〇mole) and 1,2-naphthoquinonediazide-5-sulfonic acid sulfonic acid chloride (2.0 mol) Β 2· 4'4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]biguanide (1.〇莫耳) with 1 a condensate of 2_naphthoquinonediazide-5-sulfonic acid sulfonic acid chloride (2.5 mol) Β3: 2,3,4,4'·tetrahydroxydiphenyl ketone (1.0 mol) and 1, Condensate of 2_naphthoquinonediazide-5-sulfonate (2.44 mole) /3 -(3,4-epoxycyclohexyl)ethyltrimethoxydecane F: SH-28PA (trade name Performance Evaluation of Interlayer Insulating Films by Toray. Dow Corning Co., Ltd. Example 6 to 1 〇, Comparative Example 3, 4 - 46 - 200903157 Using the above-described Examples 1 to 5 and Comparative Example 1, 2 The radiation-sensitive resin composition was evaluated for various characteristics of the interlayer insulating film in the following manner. [Evaluation of Sensitivity] On Examples 6 to 9 on the substrate, and Comparative Examples 3 to 4, the compositions described in Table 2 were applied using a rotator, and then 9 (TC was pre-baked on a hot plate 2) In a minute, a coating film having a film thickness of 3.0 μm was formed. Further, in Example 10, the composition described in Table 2 was applied by a slit die coater, and the pressure was reduced from normal pressure to 0.5 T rr in 15 seconds. After removing the solvent, it was prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 3. Ομηη. On the obtained coating film, a pattern mask having a set pattern was introduced. Using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Co., Ltd., each exposure was carried out under the exposure time as a variable, and in a tetramethylammonium hydroxide aqueous solution of the concentration shown in Table 2, at 25 t, 80 seconds. The solution was developed by liquid-filling method, followed by washing with ultrapure water for 1 minute, and then drying to form a pattern on the substrate. At this time, 'check the necessary exposure amount so that the line and the pitch of 3.0 μm ( 1 〇 The pattern of 1) is completely dissolved, and the enthalpy is shown in Table 2. The enthalpy is below 600 J/m2. The sensitivity was good. [Evaluation of development limit] On the sand substrate, 'Examples 6 to 9 and Comparative Examples 3 to 4 were coated with the composition described in Table 2 using a rotator, and then 9 〇t: The film was formed by pre-baking for 2 minutes on a hot plate to form a film thickness of 3. The composition shown in Table 2 was applied in Example 10 using a slit-47-200903157 die coater for 15 seconds. The pressure was reduced from normal pressure to 0 · 5 T 〇rr, and the solvent was removed, and then pre-baked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 3·〇μιηη. The coating film was passed through a mask having a line and pitch (10 to 1) pattern of 3 · 0 μm 'using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon's equivalent to the above [[sensitivity The exposure amount of the sensitivity 测定 measured in the evaluation] was subjected to exposure, and developed in a tetramethylammonium hydroxide aqueous solution having a concentration shown in Table 2 at a temperature of 25 ° C using a developing time as a variable. The water was washed with ultrapure water for 1 minute, and then dried to form a pattern on the substrate. At this time, the line width became 3 The development time necessary for μιη is the optimum development time, as shown in Table 2. Further, the time until the development of the line pattern of 3.0 μm was measured from the optimum development time, and the development limit is shown in Table 2. When the enthalpy exceeds 30 seconds, the development limit is good. [Evaluation of Solvent Resistance] Examples 6 to 9 were used on the ruthenium substrate, and the compositions described in Table 2 were coated with the rotators on each of the comparative examples 3 to 4. Thereafter, the film was prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film. In the example 10, the coating of the composition described in Table 2 was carried out by a slit die coater for 15 seconds. The time was reduced from normal pressure to 〇5 Torr. After the solvent was removed, it was prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film. The obtained coating film was irradiated with a PLA-501F exposure machine -48-200903157 (ultra-high pressure mercury lamp) manufactured by Canon Inc., and the respective exposure amounts were 3, 〇〇〇J/m2' by the ruthenium substrate. Inside the oven, at 2 2 〇. (: heating for 1 hour) to obtain a cured film having a film thickness of 3·0 μm. The film thickness (T1) of the obtained cured film was measured. Then, the tantalum substrate formed of the cured film was subjected to a dimethyl group controlled at 70 t: temperature. After immersing in the yttrium for 20 minutes, the film thickness (ti) of the cured film was measured, and the rate of change of the film thickness by immersion {丨tl_T1 | /T1 }χ1〇〇[%] was calculated. The results are shown in Table 2. When the enthalpy is 5% or less, the solvent resistance is good. Further, since the formed film does not need to be patterned in the evaluation of the solvent resistance, the radiation irradiation step and the development step can be omitted, and only the coating film forming step is performed. Evaluation of the post-baking step and the heating step. [Evaluation of heat resistance] Each of the cured films was formed in the same manner as in the above [Evaluation of Solvent Resistance], and the film thickness (T2) of the obtained cured film was measured. The substrate having each of the cured films was additionally baked at 240 ° C for 1 hour in a clean oven, and then the film thickness (t2) of the cured film was measured, and the rate of change in film thickness due to additional baking was calculated { I t2- T2 | /Τ2}χ1〇〇[%]. The results are shown in Table 2. When the 値 is 5% or less, heat resistance [Evaluation of Transparency] In the evaluation of the solvent resistance, a glass substrate "Corning 7〇59 (manufactured by Corning)" was used instead of the ruthenium substrate, and the other method was used to form a hardening on the glass substrate. The film was measured for the light transmittance of the glass substrate having the cured film by using a spectrophotometer "1 50-20 type Double beam (manufactured by Hitachi, Ltd.)" at a wavelength of 400 to 800 nm van-49 - 200903157. The minimum light transmittance is shown in Table 2. When the 値 is 90% or more, the transparency is good. [Evaluation of Specific Dielectric Rate] On the honed SUS3〇4 substrate, Example 6~ 9. Comparative Examples 3 to 4 The composition described in Table 2 was applied by using a rotator, and then baked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.Οηη. 〇, the composition described in Table 2 was applied by a slot coater, and the pressure was reduced from normal pressure to 0.5 Torr for 15 seconds. After the solvent was removed, it was preheated at 90 ° C on a hot plate. Baking for 2 minutes to form a coating film having a film thickness of 3. Ομηι. Exposure was carried out by a PLA-501F exposure machine (super-pressure mercury lamp) manufactured by Canon Inc., so that the cumulative irradiation amount was 3,0 0 0 /m 2 , and the substrate was baked in a clean oven for 2 hours under TC (1 hour). A cured film was obtained, and a Pt/Pd electrode pattern was formed by vapor deposition on each of the cured films to prepare a sample for dielectric constant measurement. For each substrate, Yokogawa Hewlett- was used.

Packard's (at the time) HP 1 645 1 B electrode and the HP4284A precision LCR meter measure the specific dielectric ratio at a frequency of 10 kHz. The results are shown in Table 2. When the enthalpy is 3.9 or less, the dielectric constant is good, and the film formed by the evaluation of the dielectric constant does not need to be patterned. Therefore, the radiation irradiation step and the development step are omitted, and only the coating film forming step is performed. Evaluation of the baking step and the heating step. -50- 200903157 Table 2 Sensitivity Evaluation Development Limit Solvent Resistance Heat Resistance Composition Developer Sensitivity Apparent Development Film Thickness Change Film Thickness Transparency Ratio Type (J/m2) Shadow Time Limit Rate (%) Rate (%) Electricity rate (wt%) (seconds) (seconds) (%) Example 6 rs-ii 0.4 600 80 55 3 2 93 3.1 Example 7 TS-21 0.4 550 80 55 3 2 92 3.2 Example 8 TS -31 0.4 550 80 55 3 2 92 3.2 Example 9 [S-4] 2.38 550 80 45 3 2 94 3.2 Example 10 iS-51 0.4 600 80 55 3 2 93 3.1 Comparative Example 3 rs-n 0.4 700 80 25 6 6 93 3.3 Comparative Example 4 Ts-21 0.4 550 80 40 3 2 93 3.6 Performance Evaluation of Microlens Example 1 1 to 1 4, Comparative Example 5, 6 Using the above Examples 1 to 5 and Comparative Example 1, 2 modulation The radiation sensitive resin composition was evaluated for various characteristics of the microlens as follows. Further, the evaluation of the solvent resistance, the evaluation of the heat resistance, and the evaluation of the transparency were referred to the results of the evaluation of the performance of the above interlayer insulating film. [Evaluation of Sensitivity] The composition described in Table 3 was applied to the ruthenium substrate using a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 2.0 Mm. On the obtained coating film, the exposure time was changed by exposure of the NSR 1 75 5i7A reduction projection exposure machine (ΝΑ = 0.50, λ = 3 6 5 nm) by a Nikon NSR 1 75 5i7A pattern mask. The solution was developed in a tetramethylammonium hydroxide aqueous solution at a concentration shown in Table 3 at a temperature of 25 ° C for 1 minute - 51 - 200903157. It is then rinsed with water and then dried to form a pattern on the substrate. It is necessary to measure the necessary exposure time for the line width of the 0·8 μπι line and the pitch pattern (1 to 1) to be 0 · 8 μηι. The sensitivity is shown in Table 3. When the enthalpy is 2,000 J/m 2 or less, the sensitivity is good. [Evaluation of development limit] The composition described in Table 3 was applied to the ruthenium substrate by a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 2. Ο μηη. On the obtained coating film, the projection exposure machine (ΝΑ = 0·50, λ = 3 6 5 nm) was reduced by a NSR1755i7A manufactured by Nikon Corporation through a pattern mask having a set pattern, which is equivalent to the above [[sensitivity] In the evaluation, the exposure amount of the enthalpy in which the sensitivity was measured was exposed, and the solution was developed in a tetramethylammonium hydroxide aqueous solution at a concentration shown in Table 3 at a temperature of 25 ° C for 1 minute. It is then rinsed with water and then dried to form a pattern on the wafer. The measurement is made such that the line width of the 〇 _ 8 # m line and the pitch pattern (1 to 1) becomes the necessary exposure time of μ 8 μιη. The sensitivity is shown in Table 3. Further, when the development was continued from the optimum development time, the measurement width was measured. The time until the pattern peeling of the pattern of 8 μm (development limit) was shown in Table 3. If the enthalpy exceeds 30 seconds, the development limit is good. [Formation of microlenses] The composition described in Table 3 was applied to the ruthenium substrate by a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 2.0 μm. On the obtained coating film, a projection mask having a pattern of 4.0 μηι.2·0 μιη pitch-52-200903157 was used, and a projection exposure machine (NA = 0.50,; l=365 nm) was manufactured by Nikon Corporation NSR1755i7A. The exposure amount of each of the above-mentioned "[sensitivity evaluation]" is measured by exposure amount, and in the evaluation of the sensitivity of Table 3, in the tetramethylammonium hydroxide aqueous solution having the concentration described in the developer concentration, Development was carried out for 1 minute at a temperature of 25 ° C. It is then rinsed with water and then dried to form a pattern on the wafer. Thereafter, exposure was performed with a PLA-5 01F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Inc., so that the cumulative irradiation amount was 3,000]/m2. Thereafter, the film was heated at 160 ° C for 10 minutes on a hot plate, and further heated at 23 ° C for 10 minutes to melt the pattern to form a microlens. The dimensions (diameter) and cross-sectional shape of the bottom of the formed microlens (the surface in contact with the substrate) are shown in Table 3. The size of the bottom of the microlens exceeds (Ομηη, when it is less than 5.0 μηη, it means good. In addition, when the size is 5.0 μηι or more, the 'adjacent lenses are in contact with each other' is not good. The cross-sectional shape is shown in Fig. 1 In the pattern diagram shown, the shape of the semi-convex lens as in (a) is good, and the difference in the shape of a substantially mesa in (b) indicates that the composition is sensitive. Table 3 Composition type sensitivity fm Development limit micro-transformation 1 1 shape developer concentration (wt %) Sensitivity (J/m2) Optimum development time (seconds) Development limit (seconds) Bottom size (μιη) Profile shape Example 11 [S-11 0.4 1200 60 40 4.3 (8) Example 12 TS-21 0.4 1100 60 40 4.3 (a) Example 13 fS-31 0.4 1100 60 40 4.2 (a) Example 14 iS-41 2.38 1100 60 40 4.4 (a) Comparative Example 5 rs-n 0.4 1400 60 20 5.5 (8) Comparative Example 6 [s-2 ] 0.4 1100 60 30 4.2 (a) -53- 200903157 [Simple description of the diagram] Figure 1 is a schematic diagram of the shape of the microlens section -54-

Claims (1)

200903157 X. Patent application scope 1 A radiation sensitive resin composition containing: [A] (al) an unsaturated compound having a carboxyl group represented by the following formula (1), ^COOH X (1) "wherein R represents hydrogen or methyl 'X represents a methylene group, and an alkylene group having 2 or more carbon atoms or is represented by any one of the following formulas (1-1) to (1_6); 2 price base, -55- 200903157 (here, χ1 is an independent alkyl group or an alkylene group having a carbon number of 2 or more, and a bond bond and a carboxyl group in the right side of the formula (1-1) to (1-6)) (a2) An unsaturated compound having an alicyclic epoxy group selected from the following formulas (2-1) to (2_3), and (2-1) (2-2) (2-3) (a3) at least one selected from the group consisting of alkyl methacrylate, cyclic alkyl methacrylate, cyclic alkyl methacrylate, methacrylate having a hydroxyl group, Cyclic alkyl acrylate, aryl methacrylate, aryl-56- 200903157 acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated iranide compound, unsaturated aromatic compound, cohydrohydrofuran skeleton , a furan skeleton, a tetrahydropyran skeleton, a glycerin skeleton, an unsaturated compound of a skeleton represented by the following formula (3), a cis-butane, a tetrapyran skeleton, a glycated compound, (In the formula (3), R3 is a hydrogen atom or a methyl group, and η is a compound having a phenolic hydroxyl group represented by the following formula (4)), a saturated compound, (4) In the formula (4), R4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which is independently represented by a hydrogen atom, a hydroxyl group or a carbon number of 1 to 4, -COO- or -CONH-, m is 0. An integer of ～3, which is a hydroxyl group, and acrylonitrile, methacrylonitrile, propylene methacrylate, methacrylamide, and vinyl acetate. The plural R5 is each of the yards, and X2 is a single bond. At least one of R5, a copolymer of vinylidene chloride, a group of unsaturated-57-200903157 compounds, and a [B] 1,2-quinonediazide compound. 2. The radiation sensitive resin composition according to claim 1, wherein the [A] copolymer is based on the total of the repeated units derived from the compound (al), the compound (a2) and the compound (a3). The repeating unit derived from the compound (a1), the repeating unit derived from the compound (a2), and the repeating unit derived from the compound (a3) each contain 5 to 40% by weight, 10 〜 80% by weight and 5 to 80% by weight. 3. The radiation sensitive resin composition of claim 2, wherein the content ratio of the [B] 1,2-quinonediazide compound is 5 to 100 parts by weight based on 100 parts by weight of the [A] copolymer. Share. 4. The radiation sensitive resin composition of claim 1, wherein the content ratio of the [B] 1,2-quinonediazide compound is 5 to 100 based on 100 parts by weight of the [A] copolymer. Parts by weight. The radiation sensitive resin composition according to any one of claims 1 to 4, which is an interlayer insulating film formation user. (6) A method of forming an interlayer insulating film, which comprises the following steps in the order described below, (1) forming a coating film of a radiation-sensitive resin composition as disclosed in claim 5 on the substrate Step (2) a step (3) of irradiating at least a portion of the coating film with radiation (developing step (4). The interlayer insulating film is characterized in that it is formed by a method as described in the patent application No. -58-200903157. The radiation sensitive resin composition according to any one of claims 1 to 4, which is for forming a microlens. A method of forming a microlens, characterized in that the following steps are carried out in the order described below: (1) a step of forming a coating film of a radiation sensitive resin composition as in claim 8 of the patent application ( 2) a step of irradiating at least a portion of the coating film with radiation, a step (3) a developing step (4), and a heating step. 1 〇. A microlens characterized by being formed by the method of claim 9 of the patent application. -59-