TWI510857B - Sensitive radiation linear resin composition, and interlayer insulating film and microlens and the like - Google Patents

Description

Sensitive radiation linear resin composition, interlayer insulating film and microlens, and manufacturing method thereof

The present invention relates to a radiation sensitive linear resin composition, an interlayer insulating film, and a microlens, and a method of manufacturing the same.

In an electronic component such as a thin film transistor (hereinafter referred to as "TFT") type liquid crystal display element, a magnetic head element, an integrated circuit element, or a solid-state imaging element, an interlayer insulating film is generally provided in order to insulate between wirings arranged in a layer. The material for forming the interlayer insulating film is preferably one having a small number of steps for producing a desired pattern shape, and having sufficient flatness, so that a sensitive radiation linear resin composition can be widely used (refer to Japanese Patent Laid-Open No. 2001-354822). Bulletin and Japanese Patent Laid-Open Publication No. 2001-343743.

In the above electronic component, for example, a TFT-type liquid crystal display device is manufactured by forming a transparent electrode film on the interlayer insulating film and forming a liquid crystal alignment film thereon, and therefore, the interlayer insulating film is in the step of forming a transparent electrode film. It is in a high temperature condition or in a stripping solution for the photoresist used to form the pattern of the electrodes, and therefore must have sufficient durability for these cases.

In recent years, the trend of the TFT-type liquid crystal display device is to increase the screen size, increase the brightness, high definition, high-speed response, and thinning. The composition for forming the interlayer insulating film must have high sensitivity and form an interlayer insulating film. The low dielectric constant, high transmittance, etc. must be superior to the high performance of the past.

In addition, fax machines, electronic photocopiers, solid-state imaging components, etc. are on the wafer. The optical system of the imaging optical system of the on chip color filter or the optical fiber of the optical fiber connector uses microlenses having a lens diameter of 3 to 100 μm, or microlens arrays of these microlenses arranged regularly.

When a microlens or a microlens array is formed, a photoresist pattern corresponding to a lens is formed, and then melted and flowed by heat treatment, and a method of using the lens as a lens or a lens pattern of a molten flow is formed into a mask. A method of transferring a lens shape onto a substrate by dry etching is known. When the lens pattern is formed, a sensitive radiation linear resin composition is widely used (refer to Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei.

However, the element forming the microlens or the microlens array as described above is supplied, and thereafter, the planarizing film and the etching resist film are applied to remove various insulating films on the bonding pad of the wiring forming portion, and the desired light is used. The cover is exposed and developed to remove the etching resist of the bonding pad portion, and then the planarizing film and various insulating films are removed by etching to expose the bonding pad portion. Therefore, the microlens or microlens array requires solvent resistance and heat resistance in the steps of forming the planarizing film and etching the photoresist coating film and the etching step.

The sensitive radiation linear resin composition for forming such a microlens must have high sensitivity, and the microlens formed of the composition has a desired bending radius and must have high heat resistance, high transmittance, and the like.

When the interlayer insulating film or the microlens prepared as described above develops in these development steps, when the development time slightly exceeds the optimum time, the developer penetrates between the pattern and the substrate, and peeling is likely to occur, and therefore, development must be strictly controlled. Time, there is a problem with product yield.

When the interlayer insulating film or the microlens is formed from the sensitive radiation linear resin composition, the composition is required to have high sensitivity, and in the developing step of the forming step, the development time does not occur even if the development time exceeds the set time. Peeling, showing good adhesion, and the interlayer insulating film formed by the composition is required to have high heat resistance, high solvent resistance, low dielectric constant, high transmittance, and when the microlens is formed, the microlens is required to have good melting. Shape (required bending rate radius), high heat resistance, high solvent resistance, high transmittance. However, a sensitive radiation linear resin composition that satisfies such requirements has not been known in the past.

[disclosure of invention]

The present invention has been accomplished in light of the above problems. Therefore, an object of the present invention is to provide a radiation sensitive linear resin composition having a high-sensitivity radiation sensitivity and easily forming a pattern-like film excellent in heat resistance.

Another object of the present invention is to provide an interlayer insulating film which can form a high heat resistance, a high solvent resistance, a high transmittance, and a low dielectric property when forming an interlayer insulating film, and can additionally have an interlayer insulating film for forming a microlens. A radiation sensitive linear resin composition of a microlens having a high transmittance and a good melt shape.

Another object of the present invention is to provide a method of forming an interlayer insulating film and a microlens using the above-described radiation sensitive linear resin composition.

Another object of the present invention is to provide an interlayer insulating film having various properties such as high heat resistance, high solvent resistance, low dielectric constant, and high permeability, and a molten shape which exhibits good heat resistance and high solvent resistance. High transmittance Microlenses of various characteristics.

Other objects and advantages of the present invention will be apparent from the description.

According to the present invention, the object and the advantages of the present invention are attained by the following sensitive radiation linear resin composition comprising: [A] a polymer (hereinafter referred to as "polymer [A]") and [B] a 1,2-quinonediazide compound, wherein the polymer [A] has a group selected from at least one selected from the group consisting of a carboxyl group and a carboxylic acid anhydride group, and is selected from the group consisting of epoxy ethyl and oxygen. a group of at least one of the groups of cyclobutyl groups and an n-valent group represented by the following formula (1), (In the formula (1), R ^I is a methylene group or an alkylene group having an alkyl group of 2 to 10 or an alkylmethylene group, a Y-line single bond, -CO-, -O-CO- ^* (but attached) There is a "*" link and R ^I bond) or -NHCO- ^* (but with a "*" link and R ^I ), n is an integer from 2 to 10, and X can have one or a plurality of ether bonds having a carbon number of from 2 to 70, or n is 3, and X is a trivalent group represented by the following formula (2), and "+" represents a bond, (In the formula (2), each of the R ^II groups is independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and "*" each represents a linking bond).

The object and the advantages of the present invention are attained by the following method for forming an interlayer insulating film or a microlens, which comprises the following steps in the following order: (1) forming a radiation sensitive linear resin composition on the substrate a step of coating a film, (2) a step of irradiating at least a portion of the coating film with radiation, (3) a developing step, and (4) a heating step.

The object and advantage of the present invention are achieved by the third interlayer insulating film or microlens formed by the above method.

Best form for implementing the invention

The sensitive radiation linear resin composition of the present invention is detailed below.

Polymer [A]

The polymer [A] is a group containing at least one selected from the group consisting of a carboxyl group and a carboxylic anhydride group; a group selected from at least one of an epoxy group and an oxocyclobutyl group; and the above formula (1) a polymer representing the n-valent group;

The alkylene group having 2 to 10 carbon atoms of R ^{I in} the above formula (1) is preferably an alkylene group having 2 to 6 carbon atoms, preferably a linear alkyl group having 2 to 6 carbon atoms or the following Equation (3) represents the basis, (In the formula (3), R ^III is a methyl group or a linear alkyl group having a carbon number of 2 to 4, and a " ^* " linkage is added to the S bond). The alkyl group-extended methyl group having 2 to 10 carbon atoms of R ^I is preferably a group represented by the following formula (4).

Y of the above formula (1) is preferably -O-CO- ^* (but a " ^* " linkage is added to the R ^I bond).

n of the above formula (1) is preferably an integer of 2 to 8, more preferably an integer of 2 to 6, or 8, more preferably 2, 3, 4, 6, or 8.

In the above formula (1), when n is 2, X is, for example, a linear or branched alkyl group having 2 to 10 carbon atoms, and the following formula (5) (In the formula (5), each of R ^IV is independently a hydrogen atom or a methyl group, and ml is an integer of 1 to 20, and " ^* " means a divalent group represented by a linking bond; and when X is 3, X is For example, the following formula (6) (In the formula (6), " ^* " indicates a trivalent group or the like represented by a linking bond); and when n is 4, 6, or 8, X is, for example, the following formula (7). (In the formula (7), m2 is an integer of 0 to 2, and " ^* " means a 4, 6 or 8 valence group represented by a linkage bond).

The content of at least one of the polymers [A] selected from the group consisting of a carboxyl group and a carboxylic anhydride group is preferably from 0.1 to 10 mmol/g, more preferably from 0.5 to 5 mmol/g. The content of at least one of the polymers [A] selected from the group consisting of epoxyethyl and oxocyclobutyl groups is preferably from 0.1 to 10 mmol/g, more preferably from 1 to 5 mmol/g. The content ratio of the n-valent represented by the above formula (1) is preferably 0.005 to 1 mmol/g, more preferably 0.01 to 0.5 mmol/g.

The styrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the polymer [A] is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ³ to 5 × 10 ⁴ . When the Mw is less than 2 × 10 ³ , the development tolerance may be insufficient, the residual film ratio of the obtained film may be lowered, or the resulting interlayer insulating film or microlens may have poor pattern shape and heat resistance. When the Mw exceeds 1 × 10 ⁵ , the sensitivity may be lowered or the shape of the pattern may be poor. Further, the molecular weight distribution (hereinafter referred to as "Mw/Mn") of the polymer [A] defined by the value obtained by dividing the Mw by Mn (the number average molecular weight in terms of polystyrene) is preferably 5.0 or less, more preferably 4.0 or less. . When Mw/Mn exceeds 5.0, the resulting interlayer insulating film or microlens has a poor pattern shape. The radiation sensitive linear resin composition containing the above polymer [A] does not cause development residue upon development, and can easily form a predetermined pattern shape.

When the polymer [A] is the above-mentioned polymer, it may be obtained by any method, and for example, an unsaturated compound formed by the following (a1) and (a2) may be contained in the presence of a compound represented by the following formula (8). a polymer obtained by radical copolymerization, wherein (a1) is at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter referred to as "compound (a1)"), and (a2) is selected from the group consisting of a ring. An unsaturated compound of at least one group of oxyethyl and oxocyclobutyl groups (hereinafter referred to as "compound (a2)"), (In the formula (8), each of X, Y, R ^I and n is synonymous with X, Y, R ^I and n of the above formula (1)).

The compound (a1) is at least one selected from the group consisting of a radically polymerizable unsaturated carboxylic acid and an unsaturated carboxylic anhydride, for example, a monocarboxylic acid or a dicarboxylic acid. a mono(meth)propenyloxyalkyl ester of an acid, a dicarboxylic anhydride, a polycarboxylic acid, a mono(meth)acrylate having a polymer having a carboxyl group and a hydroxyl group at both terminals, and a polycyclic compound having a carboxyl group; And its anhydride and so on.

Specific examples of such a monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, etc.; and dicarboxylic acids such as maleic acid, trans-butenedioic acid, citraconic acid, mesaconic acid, itaconic acid, etc. The dicarboxylic acid anhydride is, for example, an anhydride of the compound exemplified above as the dicarboxylic acid; and the mono[(meth)acryloxyalkylalkyl] ester of the polycarboxylic acid is, for example, mono[2-(methyl)propene succinate. a methoxyethyl ester, a mono [2-(methyl) propylene methoxyethyl] phthalate, etc.; a mono(meth) acrylate having a polymer having a carboxyl group and a hydroxyl group at both terminals, for example, ω a carboxypolycaprolactone mono(meth)acrylate or the like; a polycyclic compound having a carboxyl group and an anhydride thereof, for example, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[ 2.2.1] Hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.21]hept-2-ene, 5- Carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1] Hept-2-ene anhydride and the like.

Among these, from the viewpoints of copolymerization reactivity, solubility in an aqueous alkali solution, and ease of availability, it is preferred to use an anhydride of a monocarboxylic acid or a dicarboxylic acid, particularly acrylic acid, methacrylic acid, or maleic anhydride. These compounds (a1) can be used singly or in combination.

The compound (a2) has an epoxy group selected from a radical polymerizable property. An unsaturated compound having at least one group of a group of oxycyclobutyl groups.

The epoxy group-containing unsaturated compound may, for example, be glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate or glycidol α-n-butyl acrylate. Ester, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxy methacrylate Hexyl methyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl-2,3-epoxypropyl ether, m-vinylbenzyl-2,3-epoxypropyl ether , p-vinylbenzyl-2,3-epoxypropyl ether, etc., wherein glycidyl methacrylate, methacrylic acid-3,4-epoxycyclohexylmethyl ester, methacrylic acid-6,7-ring Oxyheptyl ester, o-vinylbenzyl-2,3-epoxypropyl ether, m-vinylbenzyl-2,3-epoxypropyl ether, p-vinylbenzyl-2,3-epoxypropyl Ether and other copolymerization reactivity and improvement To give the heat-resistant layer between the insulating film and the microlens, the surface hardness of the preferred aspects.

An unsaturated compound having an oxocyclobutyl group, for example, 3-(acryloxymethyl)oxycyclobutane, 3-(acryloxymethyl)-3-methyloxycyclobutane, 3-( Propylene methoxymethyl)-3-ethyloxycyclobutane, 3-(acryloxymethyl)-2-trifluoromethylcyclobutane, 3-(acryloxymethyl)- 2-pentafluoroethyloxycyclobutane, 3-(propenyloxymethyl)-2-phenyloxycyclobutane, 3-(acryloxymethyl)-2,2-difluorooxane Butane, 3-(acryloxymethyl)-2,2,4-trifluorooxocyclobutane, 3-(acryloxymethyl)-2,2,4,4-tetrafluorooxane Butane, 3-(2-propenyloxyethyl)oxycyclobutane, 3-(2-propenyloxyethyl)-2-ethyloxycyclobutane, 3-(2-propenyloxyethyl)-3-ethyloxycyclobutane, 3-(2-propenyloxyethyl)-2-trifluoromethyloxycyclobutane, 3-(2 -propenyloxyethyl)-2-pentafluoroethyloxycyclobutane, 3-(2-propenyloxyethyl)-2-phenyloxycyclobutane, 3-(2-propene oxime Benzyl)-2,2-difluorooxocyclobutane, 3-(2-propenyloxyethyl)-2,2,4-trifluorooxocyclobutane, 3-(2-propene oxime Benzyl)-2,2,4,4-tetrafluorooxocyclobutane, 2-(acryloxymethyl)oxycyclobutane, 2-(acryloxymethyl)-2-methyl Oxycyclobutane, 2-(propylene methoxymethyl)-3-ethyloxycyclobutane, 2-(acryloxymethyl)-2-trifluoromethylcyclobutane, 2-( Propylene methoxymethyl)-2-pentafluoroethyloxycyclobutane, 2-(acryloxymethyl)-2-phenyloxycyclobutane, 2-(acryloxymethyl)- 2,2-difluorooxocyclobutane, 2-(acryloxymethyl)-2,2,4-trifluorooxocyclobutane, 2-(acryloxymethyl)-2,2, 4,4-tetrafluorooxocyclobutane, 2-(2-propenyloxyethyl)oxycyclobutane, 2-(2- Eneoxyethyl)-2-ethyloxycyclobutane, 2-(2-propenyloxyethyl)-3-ethyloxycyclobutane, 2-(2-propenyloxyethyl) 2-trifluoromethyloxycyclobutane, 2-(2-propenyloxyethyl)-2-pentafluoroethyloxycyclobutane, 2-(2-propenyloxyethyl)- 2-phenyloxocyclobutane, 2-(2-propenyloxyethyl)-2,2-difluorooxocyclobutane, 2-(2-propenyloxyethyl)-2,2, Acrylates such as 4-trifluorooxocyclobutane, 2-(2-propenyloxyethyl)-2,2,4,4-tetrafluorooxocyclobutane; 3-(methacryloxyloxy) Methyl)oxycyclobutane, 3-(methacryloxymethyl)-3-methyloxetane, 3-(methacryloxymethyl)-3-ethyloxetane Alkane, 3-(methacryloxymethyl)-2-trifluoromethylcyclobutane, 3-(methacryloxymethyl)-2-pentafluoroethyloxy Cyclobutane, 3-(methacryloxymethyl)-2-phenyloxycyclobutane, 3-(methacryloxymethyl)-2,2-difluorooxocyclobutane, 3-(methacryloxymethyl)-2,2,4-trifluorooxocyclobutane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluoroox Cyclobutane, 3-(2-methylpropenyloxyethyl)oxycyclobutane, 3-(2-methylpropenyloxyethyl)-2-ethyloxocyclobutane, 3-( 2-methylpropenyloxyethyl)-3-ethyloxycyclobutane, 3-(2-methylpropenyloxyethyl)-2-trifluoromethyloxycyclobutane, 3-( 2-methylpropenyloxyethyl)-2-pentafluoroethyloxycyclobutane, 3-(2-methylpropenyloxyethyl)-2-phenyloxycyclobutane, 3-( 2-methylpropenyloxyethyl)-2,2-difluorooxocyclobutane, 3-(2-methylpropenyloxyethyl)-2,2,4-trifluorooxocyclobutane , 3-(2-methylpropenyloxyethyl)-2,2,4,4-tetrafluorooxocyclobutane, 2-(methacryloxymethyl)oxycyclobutane, 2- (methacryloxymethyl)-2-methyloxetane, 2-(methacryloxy) 3-ethyloxycyclobutane, 2-(methacryloxymethyl)-2-trifluoromethylcyclobutane, 2-(methacryloxymethyl)-2 - pentafluoroethyloxycyclobutane, 2-(methacryloxymethyl)-2-phenyloxycyclobutane, 3-(methacryloxymethyl)-2,2-di Fluorooxetane, 2-(methacryloxymethyl)-2,2,4-trifluorooxocyclobutane, 2-(methacryloxymethyl)-2,2,4 , 4-tetrafluorooxocyclobutane, 2-(2-methylpropenyloxyethyl)oxycyclobutane, 2-(2-methylpropenyloxyethyl)-2-ethyloxy ring Butane, 2-(2-methylpropenyloxyethyl)-3-ethyloxycyclobutane, 2-(2-methylpropenyloxyethyl)-2-trifluoromethyloxane Butane, 2-(2-methylpropenyloxyethyl)-2-pentafluoroethyloxycyclobutane, 2-(2-methylpropenyloxyethyl)-2-phenyloxy ring Ding Alkane, 2-(2-methylpropenyloxyethyl)-2,2-difluorooxocyclobutane, 2-(2-methylpropenyloxyethyl)-2,2,4-tri a methacrylate such as fluorooxocyclobutane or 2-(2-methylpropenyloxyethyl)-2,2,4,4-tetrafluorooxocyclobutane. Among these, from the viewpoint of copolymerization reactivity, 3-(acryloxymethyl)oxycyclobutane, 3-(acryloxymethyl)-3-methyloxycyclobutane, and 3 are preferably used. -(propylene methoxymethyl)-3-ethyloxycyclobutane, 3-(methacryloxymethyl)oxycyclobutane, 3-(methacryloxymethyl)-3 - methyloxycyclobutane, 3-(methacryloxymethyl)-3-ethyloxycyclobutane, and the like.

These compounds (a2) can be used singly or in combination.

The polymer [A] may be a copolymer containing only the unsaturated compound formed by the compound (a1) and the compound (a2), or the compound (a1) and the compound (a2), and further contain the compound (a1) (a3), A copolymer of an unsaturated compound formed by an unsaturated compound other than the compound (a2) (hereinafter sometimes referred to as "the compound (a3)").

The compound (a3) is not particularly limited as long as it is a radical polymerizable unsaturated compound other than the compound (a1) or the compound (a2). The compound (a3) is, for example, an alkyl methacrylate, an alkyl acrylate, a cyclic alkyl methacrylate, a methacrylate having a hydroxyl group, a cyclic alkyl acrylate, an aryl methacrylate, an aryl acrylate, or an unsaturated group. a dicarboxylic acid diester, a bicyclic unsaturated compound, a maleimide compound, an unsaturated aromatic compound, a conjugated diene; a phenolic hydroxyl group-containing unsaturated compound represented by the following formula (I); having tetrahydrofuran Skeleton, furan skeleton, tetrahydropyran skeleton, pyran An unsaturated compound having a skeleton or a skeleton represented by the following formula (II); and other unsaturated compounds.

(In the formula (I), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² to R ⁶ are the same or different in a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and B is a single The bond, -COO- or -CONH-, m is an integer from 0 to 3, but at least one of R ² to R ⁶ is a hydroxyl group) (in the formula (II), R ⁷ is a hydrogen atom or a methyl group)

Preferred examples of the compound (a3), wherein alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, methacrylic acid Tributyl ester, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-octadecyl methacrylate, etc.; An alkyl acrylate such as methacrylate, isopropyl acrylate or the like; a cyclic alkyl methacrylate such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2.6 ] Decane-8-yl methacrylate, tricyclo[5.2.1.0 ^2.6 ]decane-8-yloxyethyl methacrylate, isobornyl methacrylate, etc.; methacrylate having a hydroxyl group, for example There are hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxy Propyl methacrylate, 2-methyl propyleneoxyethyl Glycosides, 4-hydroxyphenyl methacrylate and the like; cyclic alkyl acrylate esters such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2.6] decane-8-yl methacrylate, Tricyclo[5.2.1.0 ^2.6 ]decane-8-yloxyethyl acrylate, isobornyl acrylate, etc.; aryl methacrylate such as phenyl methacrylate, benzyl methacrylate, etc.; Esters such as phenyl acrylate, benzyl acrylate, etc.; unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; bicyclic unsaturated compounds such as Bicyclo [22.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.21 ???hept-2-ene, 5-ethoxybicyclo[2.21]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxy Bicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene 5-phenoxycarbonyl Bicyclo[2.2.1]hept-2-ene, 5,6-di(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(cyclohexyloxycarbonyl) Bicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2- Alkene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5 -hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hept-2-ene and the like; maleimide compound such as N-phenyl maleimide, N-cyclohexylmethyleneimine, N-benzyl cis Butyleneimine, N-(4-hydroxyphenyl) maleimide, N-(4-hydroxybenzyl) maleimide, N-succinimide-3 - maleimide benzoate, N-succinimide-4-butyleneimine butyrate, N-succinimide-6-butylene Aminohexanoate, N-succinimide-3-cis Butylene diimide propionate, N-(9-acridinyl) maleimide, etc.; unsaturated aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene , p-methyl styrene, vinyl toluene, p-methoxy styrene, etc.; conjugated dienes such as 1,3-butadiene, isoprene, 2,3-dimethyl-1, And a compound represented by the following formula (I-1) to (I-5); (In the formula (I-1), n is an integer of 1 to 3, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} the same as those of the formula (I)) (In the formula (I-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} the same as defined in the above formula (I)) (In the formula (I-3), n is an integer of 1 to 3. The definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} the same as those of the above formula (I)) (In the formula (I-4), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} the same as defined in the above formula (I)) (In the formula (I-5), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} the same as defined in the above formula (I))

The unsaturated compound having a tetrahydrofuran skeleton is, for example, tetrahydrofurfuryl (meth) acrylate, 2-(methyl)propoxy methoxy-propionic acid tetrahydrofurfuryl ester, 3-(methyl)propoxy tetrahydrofuran- 2-ketone or the like; an unsaturated compound having a furan skeleton, for example, 2-methyl-5-(3-furyl)-1-penten-3-one, mercapto (meth) acrylate, 1-furan- 2-butyl-3-en-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6-(2-furyl)-2-methyl- 1-hexen-3-one, 6-furan-2-yl-hex-1-en-3-one, 2-furan-2-yl-1-methyl-ethyl (meth)acrylate, 6- (2-furyl)-6-methyl-1-hepten-3-one or the like; an unsaturated compound having a tetrahydropyran skeleton, for example, (tetrahydropyran-2-yl)methyl (methyl Acrylate, 2,6-dimethyl-8-(tetrahydropyran-2-yloxy)-oct-1-en-3-one, 4-(meth)acrylic acid tetrahydropyran-2 -yl ester, 1-(tetrahydropyran-2-oxo)-butyl-3-en-2-one, etc.; having unsaturation of pyran skeleton For example, 4-(1,4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyranone, 4-(1,5-dioxa-6- Oxo-7-octenyl)-6-methyl-2-pyranone; The unsaturated compound containing the skeleton represented by the above formula (II), for example, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) mono (meth) acrylate Esters and the like; other unsaturated compounds such as acrylonitrile, methacrylonitrile, ethylene chloride, chlorinated vinylidene, acrylamide, methacrylamide, vinyl acetate, 4-propenyloxymorpholine, 4 - Methyl propylene methoxy morpholine or the like.

Among these, an alkyl methacrylate, a cyclic alkyl methacrylate, a cyclic alkyl acrylate, a maleimide compound, an unsaturated aromatic compound, a conjugated diene, and the like are preferably used. I) an unsaturated compound containing a phenolic hydroxyl group; an unsaturated compound having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton or a skeleton represented by the above formula (II), from copolymerization reactivity and alkali From the viewpoint of the solubility of the aqueous solution, styrene, tert-butyl methacrylate, tricyclo [5.21.0 ^2,6 ]decane-8-yl methacrylate, lauryl methacrylate, and para Oxystyrene, 2-methylcyclohexyl acrylate, N-phenyl maleimide, N-cyclohexyl maleimide, tetrahydroindenyl (meth) acrylate, ethylene Polyethylene glycol mono(meth)acrylate, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl group having a repeating number of 2 to 10 (Meth) acrylamide, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxybenzene Alkene, 1,3-butadiene, 4-propenyloxymorpholine, 4-methylpropenyloxymorpholine, 3-(methyl)propenyloxytetrahydrofuran-2-one, 1-(four Hydropyran-2-oxy)-butyl-3-en-2-one or N-(3,5-dimethyl-4-hydroxybenzyl)methacrylamide.

These compounds (a3) can be used singly or in combination.

The copolymer [A] used in the present invention is based on the combination of the repeating units derived from the compounds (a1), (a2) and (a3), and the constituent unit derived from the compound (a1) preferably contains 5~. 40% by weight, particularly preferably 5 to 25% by weight. When the copolymer having less than 5% by weight of the constituent unit is used, it is difficult to dissolve in the aqueous alkali solution in the developing step, and the copolymer having more than 40% by weight tends to have an excessively large solubility in the aqueous alkali solution.

The copolymer [A] used in the present invention is based on the combination of the repeating units derived from the compounds (a1), (a2) and (a3), and the constituent unit derived from the compound (a2) preferably contains 10~. 80% by weight, particularly preferably 30 to 80% by weight. When the constituent unit is less than 10% by weight, the heat resistance, surface hardness, and peeling resistance of the obtained interlayer insulating film or microlens tend to be lowered, and when the amount of the constituent unit exceeds 80% by weight, the radiation sensitive linear resin The preservation stability of the composition tends to decrease.

The copolymer [A] used in the present invention is based on the combination of the repeating units derived from the compounds (a1), (a2) and (a3), and the constituent unit derived from the compound (a3) preferably contains 10~. 80% by weight, particularly preferably 15 to 60% by weight.

A preferred specific example of the copolymer [A] used in the present invention is a combination of unsaturated compounds such as methacrylic acid/tricyclo[5.2.1.0 ^2,6 ]decane-8-ylmethacrylate/4- Propylene methoxy morpholine / benzyl methacrylate / styrene, methacrylic acid / glycidyl methacrylate / N-cyclohexyl maleimide / (3-ethyloxycyclobutane-3 -yl)methacrylate/α-methyl-p-hydroxystyrene, methacrylic acid/glycidyl methacrylate/N-phenyl maleimide/tetrahydrofurfuryl methacrylate/ Vinylbenzyl 2,3-epoxypropyl ether, styrene/methacrylic acid/glycidyl methacrylate/N-(4-hydroxyphenyl)methacrylamide/1,3-butadiene , styrene/methacrylic acid/glycidyl methacrylate/(3-ethyloxycyclobutane-3-yl)methacrylate/tricyclo[5.2.1.0 ^2,6 ]nonane-8-yl Methacrylate, methacrylic acid/glycidyl methacrylate/tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate/N-cyclohexylmethyleneimine/n -Lauryl methacrylate /α-Methyl-p-hydroxystyrene, methacrylic acid/glycidyl methacrylate/styrene/2-methylcyclohexyl acrylate/1-(tetrahydropyran-2-oxo)-butyl- 3-en-2-one/4-hydroxybenzyl methacrylate, methacrylic acid/tricyclo [5.2.10 ^2,6 ]decane-8-yl methacrylate/2-methylcyclohexylacrylic acid Ester/N-(3,5-dimethyl-4-hydroxybenzyl)methacrylamide and the like.

The polymer [A] is, for example, a mixture of the above unsaturated compounds in the presence of a compound represented by the above formula (8) (hereinafter referred to as "polythiol compound"), preferably in a suitable solvent. In the presence of a starter, radical polymerization is carried out to synthesize.

The above polythiol compound is a component having a function as a chain transfer agent when the polymer [A] is synthesized.

As the polyvalent thiol compound, for example, an ester compound of a hydrothiocarboxylic acid and a polyhydric alcohol can be used.

The above-mentioned hydrothiocarboxylic acid is, for example, mercaptoacetic acid, 3-hydrothiopropionic acid, 3-hydrothiobutyric acid, 3-hydrothiovaleric acid or the like; and the polyhydric alcohol is, for example, ethylene glycol or tetraethylene glycol. Butanediol, trimethylolpropane Alkane, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,3,5-tris(2-hydroxyethyl) cyanurate, sorbitol, and the like.

Specific examples of preferred polythiol compounds for use in the present invention, such as trimethylolpropane (3-hydrothiopropionate), pentaerythritol tetrakis(3-hydrothiopropionate), tetraethylene glycol (3) -Hexylthiopropionate), dipentaerythritol (3-hydrothiopropionate), pentaerythritol tetrakis (hydrothioacetate), 1,4-bis(3-hydrothiobutoxy)butyl Alkane, pentaerythritol tetrakis(3-hydrothiobutyrate), 1,3,5-tris(3-hydrothiobutoxy)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-trione and the like.

The above polythiol compound may be used singly or in combination of two or more.

The ratio of the polythiol compound used in the synthesis of the polymer [A] is preferably from 0.5 to 30 parts by weight, more preferably from 1 to 20 parts by weight, particularly preferably from 1.5 to 10 parts by weight based on 100 parts by weight of the total unsaturated compound. Parts by weight. When the ratio of use of the polythiol compound is less than 0.05 part by weight, the molecular weight adjustment may not be sufficiently performed. On the other hand, when it exceeds 30 parts by weight, it is difficult to obtain a high polymerization conversion ratio.

As the polymerization initiator used for the production of the polymer [A], a radical polymerization initiator can be generally used. For example 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2 Azo compound such as 4-dimethylvaleronitrile; benzhydryl peroxide, lauryl peroxide, t-butyl peroxyvalerate, 1,1'-bis-(third An organic peroxide such as butyl peroxy)cyclohexane; and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, a peroxide can also be used as a redox type initiator together with a reducing agent.

The use ratio of the polymerization initiator is preferably from 0.1 to 50 parts by weight, more preferably from 0.1 to 20 parts by weight, per 100 parts by weight of the wholly unsaturated compound.

The solvent used in the production of the polymer [A], for example, an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol, a propylene glycol monoalkyl ether, a propylene glycol alkyl ether acetate, a propylene glycol alkane. Ether propionate, aromatic hydrocarbon, ketone, ester, and the like.

In these specific examples, the alcohol may be, for example, methanol, ethanol, benzyl alcohol, 2-phenylethanol or 3-phenyl-1-propanol; the ether is, for example, tetrahydrofuran; and the glycol ether is, for example, ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, etc.; ethylene glycol alkyl ether acetate such as methyl glycol ether acetate, ethyl glycol ether acetate, ethylene glycol monobutyl ether acetate, B a diol monoethyl ether acetate or the like; a diethylene glycol ether such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglyme, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; propylene glycol Monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; propylene glycol alkyl ether propionate such as propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate , propylene glycol butyl ether propionate, etc.; propylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc.; a hydrocarbon such as toluene, xylene, etc.; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc.; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropionic acid Ester, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate , propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutyl Methyl ester, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxy acetic acid Propyl ester, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, butoxyacetate Ester, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxy Butyl propyl acrylate , methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate , ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , 3-methoxypropionic acid propyl ester, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate , 3-ethoxypropionic acid butyl ester, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate An ester of methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate or butyl 3-butoxypropionate.

The preferred ones are ethylene glycol alkyl ether acetate, diethylene glycol, and propylene glycol. An alkyl ether or a propylene glycol alkyl ether acetate or the like, particularly preferably diglyme, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate or 3-methoxypropionic acid. Methyl ester.

The polymerization temperature is 0 to 150 ° C, preferably 50 to 120 ° C, and the polymerization time is preferably 10 minutes to 20 hours, more preferably 30 minutes to 6 hours.

The polymerization reaction of the above compound (a1) and the compound (a2) and preferably the unsaturated compound containing the compound (a3) is preferably such that the polymerization conversion ratio is 90% by weight or more, more preferably 93% by weight or more. Preferably it is 95% by weight or more. The polymerization conversion ratio herein means the total weight of the polymer [A] obtained by the polymerization reaction for the compound (a1), the compound (a2), the compound (a3), the polymerization initiator and the chain transfer agent which are supplied to the polymerization reaction. The ratio of weight. When the polymerization conversion ratio is within the above range, the solution containing the polymer [A] obtained by the polymerization reaction is not supplied to the modulating radiation-sensitive linear resin composition, and the film reduction by heating during the formation of the coating film can be minimized. It is preferred not to affect the radiation sensitivity of the sensitive radiation linear resin composition and the heat resistance of the resulting interlayer insulating film or microlens.

The polymerization reaction of the above compound (a1) and the compound (a2) and preferably the unsaturated compound containing the compound (a3) is carried out in the presence of the above polythiol compound, and a preferable polymerization conversion ratio can be easily obtained.

The above-described excellent effects of the polythiol compound are the effects first discovered by the inventors of the present invention.

[B] component

The component [B] used in the present invention produces carboxylic acid by irradiation with radiation As the 1,2-quinonediazide compound having a function, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core") and a 1,2-naphthoquinonediazidesulfonic acid halide can be used.

Examples of the above-mentioned mother core include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkane, and other mother nucleus.

Specific examples of these, wherein the trihydroxybenzophenone is, for example, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone or the like; and tetrahydroxybenzophenone has, for example, 2 , 2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2, 3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc.; pentahydroxybenzophenone For example, 2,3,4,2',6'-pentahydroxybenzophenone, etc.; hexahydroxybenzophenone such as 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxybenzophenone, etc.; (polyhydroxyphenyl)alkane such as bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxybenzene) Methane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-dual ( 2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1- [4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethenyl]bisphenol, 4,4',4"-time Tris, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobifluorene -5,6,7,5',6',7'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan, etc.; Other parent cores are, for example, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman, 2-[double {(5-isopropyl) 4--4-(2-hydroxyphenyl)-1-methylethyl}-4,6-di Hydroxyphenyl)-1-methylethyl]-3-(1-(3-{1-(4-hydroxyphenyl)-1-methylethyl}-4,6-dihydroxyphenyl)- 1-methylethyl)benzene, 4,6-bis{1-(4-hydroxyphenyl)-1-methylethyl}-1,3-dihydroxybenzene.

It is also possible to use 1,2-naphthoquinonediazidesulfonate amide which changes the ester bond of the above-exemplified parent core to a guanamine bond, for example, 2,3,4-trihydroxybenzophenone-1,2 - Naphthoquinone diazide-4-sulfonic acid decylamine and the like.

Among these, the nucleus is preferably 2,3,4,4'-tetrahydroxybenzophenone, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methyl Ethylethyl]phenyl]heptylene]bisphenol, 4,4',4"-ethylidenetriol.

Further, the 1,2-naphthoquinonediazidesulfonic acid halide is preferably 1,2-naphthoquinonediazidesulfonic acid chloride, and specific examples thereof are 1,2-naphthoquinonediazide-4-sulfonic acid chloride. And 1,2-naphthoquinonediazide-5-sulfonic acid chloride, of which 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferably used.

The condensation reaction is preferably a number of moles of OH groups in the phenolic compound or the alcoholic compound, preferably 1,0 to 85 mol%, more preferably 50 to 70 mol% of 1,2-naphthoquinone. Bismuth sulfonic acid halide.

The condensation reaction can be carried out using a known method.

These components (B) may be used alone or in combination of two or more.

The use ratio of the component [B] is 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of the polymer [A]. [B] into When the ratio is less than 5 parts by weight, the difference in solubility between the irradiated portion and the unirradiated portion of the radiation to be the aqueous solution of the developer is small, and patterning may be difficult, and the resulting interlayer insulating film or microlens may be obtained. The heat resistance or solvent resistance is not good. Further, when the ratio of the component [B] exceeds 100 parts by weight, the solubility in the above-mentioned aqueous alkali solution in the radiation irradiated portion is not good, and development is difficult.

Other ingredients

The sensitive radiation linear resin composition of the present invention contains the above-mentioned polymers [A] and [B] as essential components, but may contain [C] a thermosensitive acid generating compound if necessary, and [D] has at least one ethylenic unsaturation. A polymerizable compound of a double bond, an epoxy resin other than the polymer [A], a surfactant of [F], a [G] a bonding aid, and the like. However, the sensitive radiation linear resin composition of the present invention contains a solution supply modulation of the polymer [A] obtained by the polymerization of the compound (a1) and the compound (a2) and preferably the unsaturated compound obtained by the compound (a3). When the linear resin composition is sensitive to radiation, the compound (a1), the compound (a2) and the compound other than those which are carried in the composition together with the polymer [A], which remain in the solution without containing the unreacted unsaturated compound, Any one or more of a3) is preferred.

The above [C] thermosensitive acid generating compound can be used to improve the heat resistance or hardness of the obtained interlayer insulating film or microlens. Specific examples thereof include sulfonium salts of sulfonium salts, benzothiazolium salts, ammonium salts, phosphonium salts and the like.

Specific examples of the above phosphonium salt include an alkyl phosphonium salt, a benzyl phosphonium salt, a dibenzyl phosphonium salt, a substituted benzyl phosphonium salt, and the like.

Specific examples of these are alkyl sulfonium salts such as 4-ethenyl phenyl dimethyl hexafluoroantimonate, 4-ethyl methoxy phenyl dimethyl hexafluoro arsenate, dimethyl- 4-(Benzyloxycarbonyloxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(phenylene)醯oxy)phenylphosphonium hexafluoroarsenate, dimethyl-3-chloro-4-ethenyloxyphenylphosphonium hexafluoroantimonate, etc.; benzylsulfonium salt such as benzyl-4-hydroxybenzene Methyl hydrazine hexafluoroantimonate, benzyl-4-hydroxyphenylmethyl sulfonium hexafluorophosphate, 4-ethoxycarbonylphenylbenzylmethyl hexafluoroantimonate, benzyl-4- Methoxyphenylmethylhydrazine hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethyl Hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, etc.; dibenzyl phosphonium salt such as dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate , dibenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, 4-acetoxyphenyl dibenzyl hexafluoroantimonate, dibenzyl-4-methoxy Hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylphosphonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-tert-butylphenylhydrazine Hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, etc.; substituted benzyl sulfonium salt such as p-chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate Citrate, p-nitrobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, p-nitrobenzyl-3- Methyl-4-hydroxyphenylmethylhydrazine hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, o-chlorobenzyl-3-chloro- 4-hydroxyphenylmethyl hexafluoroantimonate or the like.

A specific example of the above benzothiazolium salt is 3-benzylbenzothiazolium hexafluorophosphate Citrate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, 3-(p-methoxybenzyl)benzothiazolium hexafluoroantimonate Benzylbenzothiazolium oxalate such as 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate or 3-benzyl-5-chlorobenzothiazolium hexafluoroantimonate.

Among these, it is preferred to use a phosphonium salt and a benzothiazole, especially 4-ethyloxyphenyl dimethyl hexafluoroarsenate, benzyl-4-hydroxyphenylmethyl hexafluoroantimonic acid. Salt, 4-acetoxyphenylbenzylmethylphosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, 4-ethyloxyphenylbenzylphosphonium hexafluorophosphate Citrate, 3-benzylbenzothiazolium hexafluoroantimonate.

These commercially available products include, for example, San-Aid SI-L85, the same SI-L110, the same SI-L145, the same SI-L150, the same SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.), and the like.

When the ratio of the component [C] is 100 parts by weight of the polymer [A], it is preferably used in an amount of 20 parts by weight or less, more preferably 5 parts by weight or less. When the amount used exceeds 20 parts by weight, in the coating film forming step, precipitates may be precipitated to affect the formation of the coating film.

The polymerizable compound having at least one ethylenically unsaturated double bond of the above component [D] may, for example, be a monofunctional (meth) acrylate, a difunctional (meth) acrylate or a trifunctional (meth) acrylate.

The above monofunctional (meth) acrylates are, for example, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxy butyl A (meth) acrylate, 2-(meth) propylene methoxyethyl 2- hydroxy propyl phthalate or the like. These commercially available products include, for example, Aronix M-101, M-111, and M-114 (East Asian synthesis). (share) system, KAYARAD TC-110S, TC-120S (manufactured by Nippon Kayaku Co., Ltd.), Viscoat 158, and 2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the above difunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexane diol di(meth) acrylate, and 1,9-nonanediol di(meth) acrylate. Ester, polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenoxymethanol diacrylate, bisphenoxyethanol oxime diacrylate, and the like. Commercial products such as these are: Aronix M-210, the same M-240, the same M-6200 (manufactured by East Asia Synthetic Co., Ltd.), KAYARAD HDDA, the same HX-220, and the same R-604 (Nippon Chemical Co., Ltd.) Manufacturing), Viscoat 260, 312, and 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the above trifunctional or higher (meth) acrylate include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris((meth)acryloxyethyl)phosphate. Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc., and commercially available products such as Aronix M-309, M-400, and M-405 , with M-450, with M-7100, with M-8030, with M-8060 (East Asia Synthetic (stock) system), KAYARAD TMPTA, with DPHA, with DPCA-20, with DPCA-30, with DPCA-60, It is the same as DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat 295, Tsing 300, Tsing 360, GPT, TPA, and K. (Manufactured by Osaka Organic Chemical Industry Co., Ltd.).

These preferably use a trifunctional or higher (meth) acrylate, which Particularly preferred are trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate.

These monofunctional, difunctional or trifunctional or higher (meth) acrylates may be used singly or in combination. When the ratio of the component [D] is 100 parts by weight based on the polymer [A], it is preferably used in an amount of 50 parts by weight or less, more preferably 30 parts by weight or less. The sensitive radiation linear resin composition of the present invention contains the component [D] in the above ratio, and the heat resistance and surface hardness of the obtained interlayer insulating film or microlens can be improved. When the amount used exceeds 50 parts by weight, in the step of forming a coating film of the radiation sensitive linear resin composition on the substrate, the coating film may be rough.

The epoxy resin other than the polymer [A] of the above [E] component is not particularly limited as long as it does not affect the compatibility. Preferred is bisphenol A type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy Resin, heterocyclic epoxy resin, glycidyl methacrylate, (co)polymerized resin, and the like. Among them, a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, a glycidyl ester type epoxy resin, and the like are preferable.

The use ratio of the component [E] is preferably 30 parts by weight or less based on 100 parts by weight of the polymer [A]. The sensitive radiation linear resin composition of the present invention contains the component [E] in this ratio, and the heat resistance and surface hardness of the obtained interlayer insulating film can be improved. When the ratio exceeds 30 parts by weight, when a coating film of a radiation sensitive linear resin composition is formed on a substrate, the film thickness of the coating film may be uneven.

The polymer [A] may also be referred to as "epoxy resin", but the component [A] is different from the component [E] in terms of alkali solubility. The component [E] is alkali-insoluble.

In order to improve the coatability of the sensitive radiation linear resin composition of the present invention, a surfactant of the component [F] may be used. As the [F] surfactant which can be used, for example, a fluorine-based surfactant, a polyoxyn-based surfactant, and a nonionic surfactant can be used.

Specific examples of the fluorine-based surfactant include, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,2,2,2-tetrafluorooctyl Hexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol di(1,1,2,2,3,3-hexafluoropentyl)ether, octapropylene glycol (1,1,2,2-tetrafluorobutyl)ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl)ether, sodium perfluorododecylsulfonate, 1 , 1,2,2,3,3,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc., in addition to halothane Sodium benzenesulfonate; fluoroalkoxyethyl ether; fluoroalkylammonium iodonium, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethylene; perfluoroalkyl alkoxylate; fluoroalkyl ester Wait. Commercial products such as: BM-1000, BM-1100 (manufactured by BM Chemie), Megafac F142D, F172, F173, F183, F178, F191, F471 (Daily Ink Chemical Industry) (Stock) manufacturing), Fulorad FC-170C, FC-171, FC-430, FC-431 (manufactured by Sumitomo 3M (share)), Surflon S-112, same S-113, same S-131, same as S-141 Same as S-145, same S-382, same SC-101, same SC-102, same SC-103, same SC-104, same SC-105, same SC-106 (made by Asahi Glass), F -TOP EF301, the same 303, the same 352 (new Akita Chemicals Co., Ltd.) Wait.

The above polyoxo-based surfactants are, for example, DC-3PA, DC-7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (Dongli) .Dowcorning.Silicone (manufactured by Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Japan Co., Ltd.), etc.

As the nonionic surfactant, for example, a polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether or polyoxyethylene fluorenyl group can be used. Polyoxyethylene aryl ether such as phenyl ether; polyoxyethylene dialkyl ester such as polyoxyethylene dilauryl ester or polyoxyethylene distearyl ester; (meth)acrylic copolymer Polyflow No. 57, 95 (total Rong company oleochemical industry (manufacturing) and so on.

These surfactants may be used singly or in combination of two or more.

When the amount of the [F] surfactant is 100 parts by weight of the polymer [A], it is preferably used in an amount of 5 parts by weight or less, more preferably 0.1 to 2 parts by weight. When the amount of the surfactant used is more than 5 parts by weight, when the coating film is formed on the substrate, the film of the coating film may be easily formed.

In order to improve the adhesion of the resulting interlayer insulating film or microlens to the substrate, the [G] adhesion aid may be used in the sensitive radiation linear resin composition of the present invention. Such a [G] adhesion aid may be a functional decane coupling agent such as a reaction having a carboxyl group, a methacryl oxime group, an isocyanate group, an epoxy group or the like. A decane coupling agent for a sexual substituent. Specific examples include, for example, trimethoxymethyl decyl benzoic acid, γ-methyl propyloxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, and γ-isocyanate propyl. Triethoxy decane, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. The amount of the [G] adhesion aid to the polymer [A] is preferably 20 parts by weight or less, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the polymer [A]. When the amount of the adhesion aid used exceeds 20 parts by weight, development may be liable to occur in the development step.

Sensitive radiation linear resin composition

The radiation sensitive linear resin composition of the present invention is prepared by uniformly mixing the above components [A] and [B] and the other components optionally added as described above. The sensitive radiation linear resin composition of the present invention is dissolved in a suitable solvent and used in a solution state. For example, a mixture of the polymers [A] and [B] and any other components added in a predetermined ratio can be used to prepare a radiation sensitive linear resin composition in a solution state.

The solvent used for the preparation of the radiation sensitive linear resin composition of the present invention is one which can uniformly dissolve the components of the polymers [A] and [B] and the other components added as described above, and does not react with the respective components.

Such a solvent is, for example, the same solvent as that exemplified for the solvent used for the production of the above polymer [A].

In such a solvent, for example, an alcohol, a glycol ether, or the like can be used from the viewpoints of solubility of each component, reactivity with each component, and easiness of formation of a coating film. Ethylene glycol alkyl ether, ester and diethylene glycol. Particularly preferred among them are benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, digan Alcohol ethyl methyl ether, diglyme, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethyl ethoxy propionate.

In order to improve the in-plane uniformity of the solvent and the film thickness, a high boiling point solvent may be used in combination. High-boiling solvents which can be used in combination are, for example, N-methylformamide, N,N-dimethylformamide, N-methylanilinamide, N-methylacetamide, N,N-dimethyl B. Indoleamine, N-methylpyrrolidone, dimethylhydrazine, benzyl ether, dihexyl ether, acetamylacetone, isophorone, caproic acid, heptanoic acid, 1-octanol, 1-nonanol, acetic acid Benzyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylethylene glycol diethyl ether acetate, and the like. Preferred among them are N-methylpyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide.

When the solvent of the sensitive radiation linear resin composition of the present invention is used in a high boiling point solvent, the amount of the high boiling point solvent used is 50% by weight or less, preferably 40% by weight or less, and more preferably 30% by weight or less, based on the total solvent. When the amount of the high-boiling solvent used exceeds the ratio, the film uniformity, sensitivity, and residual film ratio of the coating film may be affected.

When the sensitive radiation linear resin composition of the present invention is prepared in a solution state, the ratio of components other than the solvent (i.e., the total amount of the polymer [A], [B] component and any other components added) occupied by the solution (hereinafter, This value is called "solids concentration" and can be arbitrarily set for the purpose of use or the desired film thickness, usually 5 to 50% by weight, ideally 10 to 40 weights. The amount % is more preferably 15 to 35% by weight.

The composition solution prepared above was used after being filtered using a micropore filter having a pore size of 0.2 μm or the like.

Interlayer insulating film, microlens formation

Next, a method of forming the interlayer insulating film and the microlens of the present invention using the sensitive radiation linear 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 of (1) forming a coating film of the sensitive radiation linear resin composition of the present invention on a substrate, and (2) irradiating the radiation. a step of irradiating at least a portion of the coating film, (3) a developing step, and (4) a heating step.

(1) Step of forming a coating film of the sensitive radiation linear resin composition of the present invention on a substrate

In the step (1) above, the composition solution of the present invention is applied onto the surface of the substrate, and it is preferred to remove the solvent by prebaking to form a coating film of the radiation sensitive linear resin composition.

The types of substrates that can be used include, for example, a glass substrate, a ruthenium-based plate, and a substrate on which various metals are formed.

The coating method of the composition solution is not particularly limited, and for example, a spray coating method, a roll coating method, a spin coating method, or a slit die coating method (Slit Die) can be used. Various methods such as Coat), a bar coating method, and an inkjet method are particularly preferred as a spin coating method or a slit die coating method. The conditions for prebaking vary depending on the type of each component and the ratio of use. For example, 60~110°C, 30 seconds~15 minutes.

The film thickness of the formed coating film is a value of prebaking, for example, 3 to 6 μm when the interlayer insulating film is formed, and 0.5 to 3 μm when the microlens is formed.

(2) a step of irradiating radiation to at least a portion of the coating film

In the step (2) above, at least a portion of the coating film formed as described above illuminates the radiation. When at least a portion of the coating film illuminates the radiation, for example, by irradiating the radiation through a reticle having a predetermined pattern.

The radiation used at this time is, for example, ultraviolet rays, far ultraviolet rays, X-rays, charged particle rays, and the like.

The ultraviolet rays are, for example, g-ray (wavelength: 436 nm), i-ray (wavelength: 365 nm), or the like. The far ultraviolet rays are, for example, a KrF excimer laser or the like. The X-rays are, for example, synchrotron radiation or the like. The charged particle beam has, for example, an electron beam or the like.

Among them, ultraviolet rays are preferable, and those containing g rays and/or i rays are particularly preferable.

The amount of exposure when forming the interlayer insulating film is preferably from 50 to 1,500 J/m ² , and the amount of exposure when forming the microlens is preferably from 50 to 2,000 J/m ² .

(3) Development step

In the step (3), the coating film irradiated with the radiation wire as described above is subjected to development treatment using a developing solution, and the radiation irradiated portion is removed to obtain a pattern. Coating film (patterned film).

For the developer used in the development treatment, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, and di-n-butyl can be used. Propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, hexahydropyridine, 1,8-diazabicyclo[5.4.0 An aqueous solution of a base (basic compound) such as 7-undecene or 1,5-diazabicyclo[4.3.0]-5-decane. The pH of the alkaline aqueous solution is preferably from 10 to 16, particularly preferably from 11 to 15. An aqueous solution of an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant, or various organic solvents in which the composition of the present invention is dissolved may be used as a developing solution.

As the developing method, a suitable method such as a stirring method, a dipping method, a shaking dipping method, a spraying method, or the like can be used. The development time at this time varies depending on the composition of the sensitive radiation linear resin composition of the present invention, the composition of the developer, and the development method employed, and is usually 30 to 120 seconds.

(4) Heating step

After the development step (3) as described above, it is preferable to perform a cleaning treatment using, for example, a running water cleaning, more preferably a full-emissive (post-exposure) radiation of a high-pressure mercury lamp, for the pattern-shaped film obtained, for the film. After the 1,2-naphthoquinonediazide compound remaining in the decomposition treatment, the film is subjected to heat treatment (post-baking treatment) by a heating means such as a hot plate or an oven, and the film is subjected to a hardening treatment. The exposure amount in the above post-exposure step is desirably 2,000 to 5,000 J/m ² . The sintering temperature of this hardening treatment is, for example, 120 to 250 °C. The heating time varies depending on the type of the heating machine. For example, when the heat treatment is performed on a hot plate, the heating time is 5 to 30 minutes, and when the oven is heated, the heating time is 30 to 90 minutes. In this case, a stage baking method of a heating step of 2 or more times or the like can be used.

Thus, a pattern-shaped film corresponding to the intended interlayer insulating film or microlens can be formed on the surface of the substrate.

The interlayer insulating film and the microlens formed as described above are excellent in adhesion, heat resistance, solvent resistance, transparency, and the like by the following examples.

Interlayer insulating film

The interlayer insulating film of the present invention formed as described above is excellent in adhesion to a substrate, is excellent in solvent resistance and heat resistance, has high transmittance, and has a low dielectric constant, and is suitable for an interlayer insulating film of an electronic component.

Microlens

The microlens of the present invention formed as described above is excellent in adhesion to a substrate, is excellent in solvent resistance and heat resistance, has high transmittance, and has a good melt shape, and is suitable for a microlens of a solid-state imaging device.

The shape of the microlens of the present invention is a semiconvex lens shape as shown in Fig. 1(a).

[Examples]

Hereinafter, the present invention will be more specifically described by way of Synthesis Examples and Examples, but the present invention does not This is limited to the following embodiments.

Synthesis example of polymer [A] Synthesis Example 1

7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether were placed in a flask equipped with a cooling tube and a stirrer. Next, 15 parts by weight of methacrylic acid, 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ]nonane-8-yl methacrylate, 5 parts by weight of 4-methylpropenylmorpholine, and methacrylic acid shrinkage were added. After 50 parts by weight of glyceride, 10 parts by weight of styrene, and 3 parts by weight of pentaerythritol tetrakis(3-hydrothiopropionate) were subjected to nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-1].

The copolymer [A-1] had a polystyrene-equivalent weight average molecular weight (Mw) of 12,000 and a molecular weight distribution (Mw/Mn) of 3.0. The polymer concentration of the obtained polymer solution was 34.8% by weight.

Synthesis Example 2

8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 172 parts by weight of diethylene glycol ethyl methyl ether were placed in a flask equipped with a cooling tube and a stirrer. Next, 12 parts by weight of methacrylic acid, 50 parts by weight of glycidyl methacrylate, 3 parts by weight of N-cyclohexylmethyleneimine, and (3-ethyloxycyclobutane-3-yl)methyl group were added. After 13 parts by weight of the acrylate, 10 parts by weight of α-methyl-p-hydroxystyrene, and 3 parts by weight of pentaerythritol tetrakis(3-hydrothiopropionate) were subjected to nitrogen substitution, stirring was started slowly. Increase the temperature of the solution to After reaching 70 ° C at 70 ° C, after 20 minutes, 60 parts by weight of a 20% by weight solution of N-cyclohexylmethyleneimine in diethylene glycol ethyl methyl ether was added to the flask using a funnel for 40 minutes. Inside. After completion of the dropwise addition, the mixture was further kept at 70 ° C for 4 hours to obtain a polymer solution containing the copolymer [A-2].

The copolymer [A-2] had a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 and a molecular weight distribution (Mw/Mn) of 2.8. The polymer concentration of the obtained polymer solution was 33.1% by weight.

Synthesis Example 3

8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 184 parts by weight of diethylene glycol ethyl methyl ether were placed in a flask equipped with a cooling tube and a stirrer. Next, 15 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 1 part by weight of N-phenylmaleimide, 20 parts by weight of tetrahydrofurfuryl methacrylate, and p-vinylbenzyl After 15 parts by weight of benzyl-2,3-epoxypropyl ether and 3 parts by weight of trimethylolpropane tris(3-hydrothiopropionate) were subjected to nitrogen substitution, stirring was started slowly. After the temperature of the solution was raised to 70 ° C and reached 70 ° C, 15 parts by weight of a 20% by weight solution of N-cyclohexylmethyleneimine in diethylene glycol ethyl methyl ether was added dropwise over 20 minutes. Inside the flask. Similarly, at the time of 40 minutes and 60 minutes, 15 parts by weight of a 20% by weight solution of N-cyclohexylmethyleneimine in diethylene glycol ethyl methyl ether was added dropwise to the flask, and added 60 minutes later. After completion, the mixture was further kept at 70 ° C for 4 hours to obtain a polymer solution containing the copolymer [A-3].

The copolymer [A-3] had a polystyrene-equivalent weight average molecular weight (Mw) of 9,800 and a molecular weight distribution (Mw/Mn) of 2.7. The resulting polymer The polymer concentration of the solution was 33.4% by weight.

Synthesis Example 4

8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether were placed in a flask equipped with a cooling tube and a stirrer. Next, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 50 parts by weight of glycidyl methacrylate, 15 parts by weight of N-(4-hydroxyphenyl)methacrylamide, and dipentaerythritol hexa(3-hydrogen) were added. After 3 parts by weight of the thiopropionate was substituted with nitrogen, 5 parts by weight of 1,3-butadiene was added, and stirring was started slowly. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-4].

The copolymer [A-4] had a polystyrene-equivalent weight average molecular weight (Mw) of 8,900 and a molecular weight distribution (Mw/Mn) of 3.0. The polymer concentration of the obtained polymer solution was 32.9% by weight.

Comparative Synthesis Example 1

8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether were placed in a flask equipped with a cooling tube and a stirrer. Next, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of (3-ethyloxycyclobutane-3-yl)methacrylate, and tricyclo [ 5.2.1.0 ^2,6 ] 20 parts by weight of decane-8-yl methacrylate and 4 parts by weight of α-methylstyrene dimer, after nitrogen substitution, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [a-1].

The copolymer [a-1] had a polystyrene-equivalent weight average molecular weight (Mw) of 7,900 and a molecular weight distribution (Mw/Mn) of 2.4. The polymer concentration of the obtained polymer solution was 31.6% by weight.

The polymerization conversion ratio of each of the above synthesis examples was calculated from the weight of each component supplied with radical polymerization and the polymer concentration of the obtained polymer solution according to the following formula. The results are shown in Table 1.

Polymerization conversion ratio (% by weight) = polymer concentration (% by weight) of the polymer solution × total of the input amounts of the respective components (including the solvent) (g) Total of the amounts of the components of the solvent (g) × 100

The polymer concentration (% by weight) of the polymer solution is a small amount of the prepared polymer solution taken from a known weight of the aluminum dish. After weighing, the weight of the polymer solution is obtained, and then heated on a hot plate at 180 ° C. After the solvent was removed, the weight of the polymer was determined by weight measurement, and these values were obtained by (weight of the polymer 重量 weight of the polymer solution × 100).

Example 1

[Preparation of sensitive radiation linear resin composition]

The polymer [A]: the solution containing the copolymer [A-1] synthesized in the above Synthesis Example 1 is converted into an amount corresponding to 100 parts by weight of the copolymer [A-1] contained in the solution, and the component [B]. :4,4'-[1-(4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl)ethylidene]bisphenol (1.0 mol) and 1,2-naphthalene 30 parts by weight of condensate (B-1) of quinonediazide-5-sulfonic acid chloride (2.0 mol) and 5 parts by weight of γ-glycidoxypropyltrimethoxydecane of (G) adhesion aid After mixing, diethylene glycol ethyl methyl ether was added, and the solid content concentration was 30% by weight, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a solution (S-1) of a radiation-sensitive linear resin composition.

Examples 2 to 12 and Comparative Examples 1 to 3

[Preparation of sensitive radiation linear resin composition]

A solution (S-2) of the radiation-sensitive linear resin composition was prepared in the same manner as in Example 1 except that the amounts described in Table 2 were used for the types of the polymers [A] and [B]. S-12) and (s-1)~(s-3).

The description of the components [B] of Examples 2, 5, 8, and 11 and Comparative Example 2 indicates that two kinds of 1,2-naphthoquinonediazide compounds were used in combination.

Example 13

Polymer [A]: a solution containing the copolymer [A-1] synthesized in the above Synthesis Example 1 is equivalent to 100 parts by weight of the copolymer [A-1] (solid) And (F) surfactant: 0.2 parts by weight of SH-28PA (manufactured by Toray Dow Cornig Co., Ltd.) and 5 parts by weight of γ-glycidoxypropyltrimethoxydecane of [G] adhesion aid Mixing, adding diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate, the solvent composition is diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate = 6 / 4 (weight ratio), to make solid After the concentration was 20% by weight, it was filtered through a membrane filter having a pore size of 0.2 μm to prepare a solution (S-13) of a radiation-sensitive linear resin composition.

In Table 2, the abbreviation of the component means the following compound.

(B-1): 4,4'-[1-(4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl)ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) condensate (B-2): 4,4',4"-ethylidene trisphenol (1.0 mol) and 1, a condensate of 2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) (B-3): 2,3,4,4'-tetrahydroxybenzophenone (10 mol) and 1, 2-naphthoquinonediazide-5-sulfonate (2.44 mole) (F-1): SH-28PA (manufactured by Toray Dow Cornig Co., Ltd.) (G-1): γ-glycidoxypropane Trimethoxy decane

Examples 14 to 26 and Comparative Examples 4 to 6

<Performance evaluation of interlayer insulating film>

Using the sensitive radiation linear resin composition prepared above, various characteristics of the interlayer insulating film were evaluated as follows.

[Evaluation of sensitivity]

In Examples 14 to 25 and Comparative Examples 4 to 6, the composition shown in Table 3 was applied onto a ruthenium substrate by a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film thickness. 3.0 μm coating film. Example 26 was applied by a slit die coater, and the solvent was removed under a reduced pressure of 0.5 Torr, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. The prepared coating film was exposed to a PLA-501F exposure machine (ultra-high pressure mercury lamp) made of Canon with a patterned pattern mask having a predetermined pattern, and the exposure time was changed, and the developer was used as the concentration of Table 3, respectively. An aqueous solution of tetramethylammonium hydroxide was developed at 25 ° C for 80 seconds and developed by stirring. Then, it was washed with running water for 1 minute using ultrapure water, and after drying, a pattern was formed on the ruthenium substrate. At this time, the minimum exposure amount required to completely dissolve the spatial pattern of the line of 3.0 μm and the gap (1:1) was measured. This value is the sensitivity, as shown in Table 3.

[Evaluation of development safety factor]

In Examples 14 to 25 and Comparative Examples 4 to 6, the composition shown in Table 3 was applied onto a ruthenium substrate by a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film thickness. 3.0 μm coating film. Example 26 After coating with a slit die coater, the solvent was removed under a reduced pressure of 0.5 Torr, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. For the obtained coating film, a PLA-501F exposure machine (ultra-high pressure mercury lamp) made of Canon was used to pass the above-mentioned "sensitivity" through a mask having a space pattern of a line and a gap (1:1) of 3.0 μm. The exposure amount of the value of the sensitivity measured by the evaluation was subjected to exposure, and a tetramethylammonium hydroxide aqueous solution having a concentration of the developer shown in Table 3 was used, and the development time was changed at 25 ° C to carry out a stirring method. Then, it was washed with running water for 1 minute using ultrapure water, and after drying, a pattern was formed on the ruthenium substrate. At this time, the development time required for the line width to be 3.0 μm was the optimum development time, as shown in Table 2. The time until peeling of the line pattern of 3.0 μm was measured when the development was continued from the optimum development time, and the development safety factor is shown in Table 3. When the value is 30 seconds or longer, it indicates that the development safety factor is good.

[Evaluation of shrinkage rate during hardening]

In Examples 14 to 25 and Comparative Examples 4 to 6, the composition shown in Table 3 was applied onto a ruthenium substrate by a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a film thickness. 3.0 μm coating film. Example 26 was applied by a slit die coater, and the solvent was removed under a reduced pressure of 0.5 Torr, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. The film thickness (T1) of the coating film obtained at this time was measured. The obtained coating film was exposed to a cumulative exposure amount of 3,000 J/m ² without passing through a pattern mask by a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon, and was 220 ° C in a clean oven. The ruthenium substrate was heated for 1 hour to thicken the coating film, and the film thickness (t1) of the cured film was measured, and the film thickness change rate {|t1-T1|/T1} × 100 [%] of the hardening was calculated. The results are shown in Table 3. When the value is 10% or less, it means that the shrinkage rate at the time of hardening is good.

Since the film formed by the evaluation of the shrinkage rate at the time of hardening does not need to be patterned, the radiation irradiation step and the development step are omitted, and evaluation is performed only by the coating film forming step, the post-baking step, and the heating step.

[Evaluation of Solvent Resistance]

In Examples 14 to 25 and Comparative Examples 4 to 6, the composition shown in Table 3 was applied onto a crucible substrate by a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film. . Example 26 was applied by a slit die coater, and the solvent was removed under reduced pressure of 0.5 Torr, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film. The obtained coating film was exposed to a cumulative exposure amount of 3,000 J/m ² without passing through a pattern mask by a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon, and was 220 ° C in a clean oven. The tantalum substrate was heated for 1 hour to obtain a cured film having a film thickness of 3.0 μm. The film thickness (T2) of the coating film obtained at this time was measured. The ruthenium substrate on which the cured film was formed was immersed in a dimethyl sulfoxide having a temperature controlled at 70 ° C for 20 minutes, and then the film thickness (t2) of the cured film was measured, and the film thickness change rate by the immersion was calculated {|t2 -T2|/T2}×100 [%]. The results are shown in Table 3. When the value is 5% or less, the solvent resistance is good.

Since the film formed by the evaluation of the solvent resistance does not need to be patterned, the radiation irradiation step and the development step are omitted, and only the coating film forming step, the post-baking step, and the heating step are evaluated.

[Evaluation of heat resistance]

A cured film was formed in the same manner as the evaluation of the solvent resistance described above, and the film thickness (T3) of the obtained cured film was measured. After the cured film substrate was additionally baked at 240 ° C for 1 hour in a clean oven, the film thickness (t3) of each of the cured films was measured, and the film thickness change rate by the additional baking was calculated {|t3-T3|/T3 }×100 [%]. The results are shown in Table 3. When the value is 5% or less, the heat resistance is good.

[Evaluation of Transparency]

A cured film was formed on the glass substrate in the same manner except that the glass substrate "Corning 7059 (manufactured by Corning)" was used instead of the above-mentioned substrate in the evaluation of the solvent resistance. The light transmittance of the glass substrate having the cured film was measured by a spectrophotometer "150-20 double beam (manufactured by Hitachi, Ltd.)" at a wavelength in the range of 400 to 800 nm. The lowest transmittance values at this time are shown in Table 3. When the value is 90% or more, the transparency is good.

Examples 27 to 38 and Comparative Examples 7 to 9

<Performance evaluation of microlenses>

Using the sensitive radiation linear resin composition prepared above, various characteristics of the microlens were evaluated as follows. The evaluation of the solvent resistance, the evaluation of the heat resistance, and the evaluation of the transparency can be referred to the results of the performance evaluation of the above interlayer insulating film.

[Evaluation of sensitivity]

The composition shown in Table 4 was applied onto a ruthenium substrate using a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a 2.0 μm coating film. For the obtained coating film, the NSR1755i7A NJ1755i7A reduction projection exposure machine (NA=0.50, λ=365 nm) was made through a pattern mask having a predetermined pattern, and the exposure time was changed for exposure, and the concentrations of Table 4 were respectively used. The developing solution of the tetramethylammonium hydroxide aqueous solution was stirred and developed at 25 ° C for 1 minute. It is then washed and dried with water to form a pattern on the crucible substrate. At this time, the minimum exposure amount required for the gap pattern of the 0.8 μm line and the gap pattern (1:1) to be 0.8 μm was measured. This value is the sensitivity, as shown in Table 4.

[Evaluation of development safety factor]

The composition shown in Table 3 was applied onto a ruthenium substrate using a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a 2.0 μm coating film. The obtained coating film was reduced by a NIKON NSR1755i7A projection exposure machine (NA=0.50, λ=365 nm) through a pattern mask having a predetermined pattern, and the feeling measured by the above [Evaluation of Sensitivity] was measured. After exposure of the exposure amount of the degree, the developing solution of the tetramethylammonium hydroxide aqueous solution of the concentration of Table 4 was used, and the development time was changed at 25 ° C, and developed by a stirring method. It is then washed with water, dried, and patterned on a crucible substrate. The development time required to determine the gap pattern of the 0.8 μm line gap pattern (1:1) to be 0.8 μm is the optimum development time, as shown in Table 4. After the optimum development time was measured and the development was continued, the time until the pattern of 0.8 μm was peeled off (developing safety factor) was shown as Table 4 as the development safety factor.

[Formation of microlenses]

The composition shown in Table 4 was applied onto a ruthenium substrate using a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a 2.0 μm coating film. For the prepared coating film via a point with 4.0 μm. The pattern mask of the 2.0 μm gap pattern is reduced by the NIKON NSR1755i7A projection exposure machine (NA=0.50, λ=365 nm), and is exposed to the sensitivity value measured by the above [[Evaluation of Sensitivity]. The amount of exposure was measured, and the developing solution of the tetramethylammonium hydroxide aqueous solution having the developer concentration evaluated in the sensitivity of Table 4 was used, and the mixture was developed by stirring at 25 ° C for 1 minute. It is then washed with water and dried to form a pattern on the substrate. Then, exposure was performed using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon (Stock) to make the cumulative exposure amount 3,000 J/m ² . Then, it was heated at 160 ° C for 10 minutes using a hot plate, and then heated at 230 ° C for 10 minutes to melt the pattern to form a microlens.

The size of the bottom of the formed microlens (the surface that contacts the substrate) And the cross-sectional shape is shown in Table 4. The size of the bottom of the microlens exceeds 4.0 μm, and when it is less than 5.0 μm, it indicates good. When the size exceeds 5.0 μm, the adjacent lenses are in contact with each other, which is not preferable. The cross-sectional shape is as shown in the pattern diagram shown in Fig. 1. When the shape of the semi-convex lens of (a) is good, it is not good, and if it is abbreviated as the shape of (b).

Effect of invention

The sensitive radiation linear resin composition of the present invention has high radiation sensitivity and excellent development safety factor, and can easily form a heat-resistant pattern-like film (interlayer insulating film or microlens).

The interlayer insulating film of the present invention formed from the above composition is excellent in solvent resistance and heat resistance, has high transmittance, and has a low dielectric constant. Therefore, it can be suitably used as an interlayer insulating film for electronic parts.

Further, the microlens of the present invention formed from the above composition is excellent in solvent resistance and heat resistance, and has high transmittance and good melt shape. Therefore, it can be suitably used as a microlens such as a solid-state imaging device.

Fig. 1 is a schematic view showing the sectional shape of a microlens.

Claims (10)

A sensitive radiation linear resin composition comprising: [A] a polymer and [B] a 1,2-quinonediazide compound, wherein the polymer of the above [A] has the group selected from a carboxyl group and a carboxylic anhydride group. a group of at least one of the groups, a group selected from at least one of an epoxy group and an oxocyclobutyl group, and an n-valent group represented by the following formula (1), (In the formula (1), R ^I is a methylene group or a C 2 to 10 alkyl group or an alkyl methylene group, a Y system single bond, -CO-, -O-CO- ^* (but with "*" The link key is associated with R ^I ) or -NHCO- ^* (but with the "*" link and R ^I ), n is an integer from 2 to 10, and X is one or more. The n-valent hydrocarbon group having 2 to 70 carbon atoms of the ether bond, or n is 3, and X is a trivalent group represented by the following formula (2), and "+" represents a linkage bond, (In the formula (2), each of the R ^II groups is independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and "*" each represents a linking bond). The sensitive radiation linear resin composition of claim 1, wherein Y in the above formula (1) is -O-CO- ^* (but a "*" linkage is attached to the R ^I bond). A sensitive radiation linear resin composition comprising: [A] a polymer and [B] 1,2-quinonediazide compound, wherein the [A] polymer system will contain (a1) selected from the group consisting of unsaturated carboxylic acids And at least one of the group consisting of unsaturated carboxylic anhydrides, and (a2) an unsaturated compound containing at least one unsaturated group selected from the group consisting of an epoxy group and an oxocyclobutyl group, in the following formula (8) ) In the presence of (X in, X, Y, R ^I and n lines of formula (8) with each patent scope of formula (1) of the first item 1, Y, R ^I and n are synonymous) of the compound represented by, the radical Copolymerization income. The sensitive radiation linear resin composition of claim 3, wherein Y in the above formula (8) is -O-CO- ^* (but a "*" linkage is attached to the R ^I bond). The sensitive radiation linear resin composition according to any one of claims 1 to 4, which is used for the production of an interlayer insulating film. A method for producing an interlayer insulating film, comprising the steps of: (1) forming a coating film of a radiation-sensitive linear resin composition of claim 5 on a substrate, and (2) a step of irradiating at least a portion of the coating film with radiation, (3) a developing step, and (4) a heating step. An interlayer insulating film characterized by the method of claim 6 of the patent application. The sensitive radiation linear resin composition according to any one of claims 1 to 4, which is used for the manufacture of a microlens. A method for producing a microlens, comprising the steps of: (1) forming a coating film of a radiation sensitive linear resin composition of claim 8 on a substrate, and (2) coating the coating on the substrate. At least a portion of the film is irradiated with radiation, (3) a developing step, and (4) a heating step. A microlens characterized by the method of claim 9 of the patent application.