WO2003056391A1

WO2003056391A1 - Radiation-sensitive resin composition and process for formation of patterns

Info

Publication number: WO2003056391A1
Application number: PCT/JP2002/013520
Authority: WO
Inventors: Junji Kodemura; Hirokazu Higashi
Original assignee: Zeon Corporation
Priority date: 2001-12-27
Filing date: 2002-12-25
Publication date: 2003-07-10
Also published as: KR100907820B1; TW200302399A; KR20040077694A; JPWO2003056391A1; TWI307823B; JP4179164B2

Abstract

A radiation-sensitive resin composition comprising an alicyclic olefin resin having acid groups, an acid generator, a crosslinking agent, and a solvent, wherein when the olefin resin has a weight-average molecular weight of less than 10000, the index C1 represented by the specific relationship (1) is 300 or above, while when it has a weight-average molecular weight of 10000 or above, the index C2 represented by the specific relationship (2) is 120 or above.

Description

Description Radiation-sensitive resin composition and pattern forming method

The present invention relates to a radiation-sensitive resin composition, and more particularly, to a radiation-sensitive resin composition whose solubility in a developer, which is an alkaline solution, is changed by irradiation with actinic radiation such as a particle beam or an electron beam. About things. The radiation-sensitive resin composition of the present invention forms a resin film, on which a pattern can be formed by photolithography. The radiation-sensitive resin composition of the present invention is suitable as a resin material for forming a resin film for electronic components such as a protective film, a planarizing film, and an electric insulating film. Background art

Electronic components such as liquid crystal display elements, integrated circuit elements, and solid-state image sensors, and color filters for liquid crystal displays, etc. have protective films to prevent their deterioration and damage, and flatten element surfaces and wiring. A flattening film, an electric insulating film for maintaining electric insulation, and the like are provided. In addition, a thin film transistor type liquid crystal display element or an integrated circuit element is provided with an interlayer insulating film in order to insulate between wirings arranged in layers.

A resin film for electronic components having various functions is used for the protective film, the flattening film, the inter-brows insulating film, and the like. Conventionally, a thermosetting resin material such as an epoxy resin has been widely used as a resin material for forming a resin film for electronic components.

However, if a thermosetting resin material conventionally known as a material for forming electronic components is used, a resin film having sufficient flatness may not be obtained. Therefore, there has been a demand for the development of a new resin material for forming a radiation-sensitive insulating film that enables fine pattern jungling. In recent years, as the density of wirings and devices has increased, low dielectric properties have also been required for these resin materials. In response to such a requirement, for example, a norbornene-based monomer having an ester group such as a methoxycarbonyl group is subjected to ring-opening polymerization, the obtained ring-opened polymer is hydrogenated, and then the hydrogenated product is hydrolyzed. A radiation-sensitive resin composition using an alkali-soluble cyclic polyolefin resin obtained by decomposing to convert an ester group into a carboxyl group has been proposed (Japanese Patent Application Laid-Open No. 10-3073888, and Japanese Unexamined Patent Publication No. 11-5252754). This radiation-sensitive resin composition is a resin composition containing the above-described soluble polycyclic resin, an acid generator (for example, a quinonediazide compound), and a crosslinking agent. More specifically, in these publications, as the alkali-soluble cyclic polyolefm resin, 8-methyl-18-methoxycarbonyltetracyclo is used.

[... 4 4 0 I 2 '5 1 7.' 1 0] - 3- dodecene ring-opening (co) polymer hydrogenated added Caro was formed by hydrolysis resin is used.

However, as a result of investigations by the present inventors, a resin film obtained by using the radiation-sensitive composition described in the above publication has a dielectric constant, water absorption, flatness, transparency, solvent resistance, heat-resistant dimensional stability, and the like. Was relatively good, but it was found that the resolution and the remaining film ratio were inferior, and it was difficult to obtain a good pattern shape. Disclosure of the invention

An object of the present invention is a radiation-sensitive resin composition containing an alicyclic olefin resin having an acidic group, an acid generator, a crosslinking agent, and a solvent, and has a low dielectric constant, heat resistance, flatness, and transparency. An object of the present invention is to provide a radiation-sensitive resin composition which is not only excellent in solvent resistance and solvent resistance, but also excellent in resolution and residual film ratio, has good resilience and can give a fine pattern shape.

Another object of the present invention is to provide a method for forming a pattern using a radiation-sensitive resin composition having such excellent properties.

It is a further object of the present invention to provide a resin film having such a pattern formed thereon and use of the resin film as a resin film for electronic components.

The present inventors have conducted intensive studies to achieve the above object, and as a result, have an acidic group. By controlling the weight average molecular weight, molecular weight distribution, the number of carbon atoms in the structural unit, and the ratio of acidic groups in the alicyclic resin within a specific range to reduce the solubility in an alkali developer, the unirradiated part is obtained. It was found that a strong radiation-suppressing effect was obtained with the above method, and as a result, a radiation-sensitive resin composition having excellent resolution, remaining film ratio, and pattern shape was obtained. The present invention has been completed based on these findings.

Thus, according to the present invention, there is provided a radiation-sensitive resin composition comprising (A) an alicyclic resin having an acidic group, (B) an acid generator, (C) a crosslinking agent, and (D) a solvent. (A) When the weight average molecular weight of the alicyclic olefin resin having an acidic group is less than 10,000, the following formula (1)

(MW) ⁰⁵ X (AC) ⁷

C 1 = X 10 ⁵ (1)

(AG) ⁶ X (MWD) ²

(Where MW is the weight average molecular weight, AC is the average number of carbon atoms per structural unit, AG is the number of moles of acidic groups in all structural units, and MWD is the molecular weight distribution. )

If the index C 1 is 300 or more and the weight average molecular weight is 10,000 or more, the following formula (2)

(MW) ⁰⁵ X (AC) ²

C 2 = X 10 ³ (2)

(AG) ² X (MWD) ³

(The meaning of each symbol in the formula is the same as in formula (1).)

The radiation-sensitive resin composition is characterized in that the index C 2 represented by the formula (1) is 120 or more.

Further, according to the present invention, a resin film is formed on a substrate using the radiation-sensitive resin composition, and active radiation is irradiated in a pattern from above the resin film to form a latent image on the resin film. It is difficult to form a pattern by forming a turn and then bringing the resin film into contact with a developer to make the pattern visible.

Further, according to the present invention, there are provided a resin film on which a pattern is formed by the above method, and use of the resin film as a resin film for an electronic component. BEST MODE FOR CARRYING OUT THE INVENTION

The radiation-sensitive resin composition of the present invention contains (A) an alicyclic resin having an acidic group, (B) an acid generator, (C) a crosslinking agent, and (D) a solvent. In the radiation-sensitive resin composition of the present invention, when the weight average molecular weight of the alicyclic resin having an acidic group is less than 10,000, the following formula (1)

(MW) ° " ⁵ X (AC) ⁷

C 1 = X 10 ⁵ (1)

(AG) ⁶ X (MWD) ²

^{(MW) ° - 5 X (} AC) 2

C 2 = X 10 ³ (2)

(AG) ² X (MWD) ³

(The meaning of each symbol in the formula is the same as in formula (1).)

An index having an index C 2 of 120 or more is used.

The index C1 is 300 or more, preferably 400 or more, more preferably 500 or more, and particularly preferably 600 or more. The index C2 is at least 120, preferably at least 150, more preferably at least 200, particularly preferably at least 250. Weight average molecular weight, average number of carbons per structural unit (hereinafter simply referred to as “average carbon number”), mol% of acidic groups in all structural units (hereinafter referred to as “acidic group ratio”), and molecular weight distribution This is an element that affects the solubility of the alicyclic resin having a group in an alkaline developer. The present inventors differ in the degree of influence of these elements on solubility in an alkaline developer when the weight average molecular weight of the alicyclic resin having an acidic group is 100,000. I found that.

In the present invention, the solubility of an alicyclic olefin resin having an acidic group in an alkali developing solution is determined by an index C l represented by the formula (1) when the weight average molecular weight is less than 1000, The case where the weight average molecular weight is 1000 or more is determined by the index C2 represented by the formula (2).

In the present invention, the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and the value rounded off to the nearest 10 is an effective figure. If the cycloaliphatic resin having an acidic group does not dissolve in tetrahydrofuran, use chloroform or cyclohexane.

The upper limits of the index C1 and the index C2 are not particularly limited, but are generally 100,000 or less, preferably 500,000 or less, more preferably 300,000 or less. It is preferably 150 or less. The upper limit of the index C 1 is often around 100,000. The upper limit of the index C 2 is often around 500.

Index C 1 and Index C 2 (hereinafter sometimes collectively referred to as “index C i J”) Alicyclic resin having an acidic group that satisfies the above-mentioned conditions has low solubility in Al developing solution. Therefore, the resin film obtained by using the radiation-sensitive resin composition containing the alicyclic olefin resin having such an acidic group has the same characteristics as the active radiation-irradiated part. The difference in solubility between the unirradiated portion and the developer is sufficiently large, and a good resolution and residual film ratio can be obtained.

An alicyclic resin having an acidic group having an index C i in the range described above was obtained. In order to calculate the index C i, the weight average molecular weight, the average number of carbon atoms per structural unit, the mole% of acidic groups in all structural units, and the molecular weight distribution, which are elements of the formulas (1) and (2), for which the index C i is calculated It can be controlled by the production conditions of the alicyclic resin having an acidic group.

In the present invention, the molecular weight distribution of the alicyclic resin having an acidic group is a dispersity represented by a weight average molecular weight Z number average molecular weight (Mw / M n). The number average molecular weight is a value in terms of polystyrene measured by GPC as in the case of the weight average molecular weight. The weight-average molecular weight is usually 50,000 to 200,000, and preferably 100, in terms of excellent properties such as low dielectric constant, low water absorption, solvent resistance, resolution, remaining film ratio, and pattern shape. It is from 0 to 1500, more preferably from 10000 to less than 10000. Therefore, it is most preferable to use an alicyclic olefin having an acidic group having a weight average molecular weight to which the formula (1) is applied.

The method for controlling the weight average molecular weight is not particularly limited, and for example, a method using a molecular weight modifier described later may be employed. Further, a plurality of types of resins having different weight average molecular weights may be mixed, and the weight average molecular weight of the mixed resin may be adjusted to a target weight average molecular weight.

The method for controlling the molecular weight distribution is not particularly limited. For example, the molecular weight distribution is 3.3 or less, preferably 3.0 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. In order to obtain a resin having a narrow molecular weight, for example, a known catalyst is used to adjust reaction conditions such as temperature and time, or an organic ruthenium compound having a neutral electron-donating ligand described later is used as a main component. The method of ring-opening polymerization using the catalyst described above is suitably adopted.

The average number of carbon atoms is calculated by the sum of the product of the number of carbon atoms other than the carbon atoms constituting the acidic group and the ratio of each structural unit contained in each structural unit constituting the resin. Here, the ratio of each structural unit is a value (mol) based on 1 mol of the total of the structural units constituting the resin. Therefore, for example, in the case of a resin in which the structural unit (I) having 12 carbon atoms and the structural unit (II) having 6 carbon atoms excluding the carbon constituting the polar group exist in a molar ratio of 1: 1. In this case, the average number of carbons per structural unit is calculated as 12 X 0.5 + 6 X 0.5 = 9.

The ratio of the acidic group is the ratio (mol%) of the structural unit having the acidic group to all the structural units.

The method for controlling the average number of carbon atoms and the ratio of acidic groups is not particularly limited, and may be performed, for example, by adjusting the type and amount of a monomer used in producing a resin.

The (A) alicyclic olefin resin having an acidic group used in the present invention is a polymer having a structural unit derived from an alicyclic structure-containing olefin monomer (hereinafter, referred to as an “alicyclic olefin monomer”). It is. The polymer may contain a structural unit other than a structural unit derived from an alicyclic olefin monomer. The acidic group may be any group capable of generating a proton in water, and specific examples thereof include a phenolic hydroxyl group, a carboxyl group (that is, a hydroxycarbonyl group), a dicarboxylic anhydride residue, a sulfonic acid residue, and phosphorus. Acid residues and the like. Among these, a carboxyl group and a dicarboxylic anhydride residue are preferred. Such an acidic group may be present in a structural unit derived from an alicyclic olefin monomer, or may be present in a structural unit other than a structural unit derived from an alicyclic olefin monomer. The proportion of acid groups, and the low dielectric constant of the resin is obtained, since the easy to control the solubility in an alkali developing solution of the resin, usually 2 0-8 0 mole ^_0/0, preferably 3 0-7 5 mole ^_0/0, more preferably 3 0-7 0 mol ^_0/0. The alicyclic resin having an acidic group may have a polar group other than the acidic group, such as a hydroxyl group or an ester group.

The alicyclic structure contained in the alicyclic olefin monomer may be monocyclic or polycyclic (condensed polycyclic, bridged ring, combination of these, etc.). From the viewpoints of mechanical strength and heat resistance, it is preferably polycyclic. Although the number of carbon atoms constituting the alicyclic structure is not particularly limited, it is usually in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15, Thereby, various properties such as heat resistance and pattern formability are highly balanced. The proportion of the structural unit derived from the alicyclic olefin monomer in the alicyclic olefin resin is appropriately selected according to the purpose of use, but is usually 30 to 100% by weight, preferably 50 to 10% by weight. 0% by weight, more preferably in the range of 70 to 100% by weight. If the proportion of the structural unit derived from the alicyclic olefin monomer is too small, the heat resistance is poor, which is not preferable.

Examples of the alicyclic olefin resin include a ring-opening (co) polymer of an ω alicyclic olefin monomer and a hydrogenated product thereof, (ii) an addition (co) polymer of an alicyclic olefin monomer, iii) an addition copolymer of an alicyclic olefin monomer and a bull compound, (iv) a monocyclic cycloalkene (co) polymer, (V) an alicyclic * diazine (co) polymer, (vi) At least one resin selected from the group consisting of a butyl-based alicyclic hydrogen (co) polymer and a hydrogenated product thereof, and (vii) an aromatic olefin (co) polymer having an aromatic ring hydrogenated product may be mentioned. Can be.

As the alicyclic olefin resin, a hydrogenated product of a ring-opening (co) polymer of an alicyclic olefin monomer is preferable. The alicyclic resin is more preferably a hydrogenated product of a ring-opening (co) polymer of a norbornene-based monomer. As the norbornene-based monomer, tetracyclododecenes described later are preferable.

The alicyclic resin having an acidic group can be synthesized by modifying the alicyclic resin with a compound having an acidic group. Further, an alicyclic olefin resin having an acidic group is an addition copolymer of an alicyclic olefin monomer having an acidic group and an alicyclic olefin monomer having no acidic group, and a ring-opening copolymer. It can be synthesized as a union or a hydrogen additive thereof. Further, an alicyclic olefin resin having an acidic group includes an alicyclic olefin monomer having an ester group such as a methoxycarbol group and a monomer having no ester group as necessary (for example, It can be synthesized by hydrolyzing a copoly (co) polymer, a ring-opening (co) polymer, or a hydrogenated product thereof with a cyclic olefin monomer or a vinyl monomer. Hereinafter, these points will be described in more detail. In the following description, for the sake of simplicity, both polymerization and copolymerization will be referred to as “polymerization”, and both the polymer and the copolymer will be described. It is described as “polymer”.

The method for obtaining the alicyclic olefin resin having an acidic group is not particularly limited. For example, a monomer capable of being copolymerized with an alicyclic olefin monomer having no acidic group, if necessary, may be used. Addition polymerization or ring-opening polymerization together with the polymer, and then hydrogenation of the unsaturated bond portion as necessary to synthesize an alicyclic olefin resin having no acidic group, and this alicyclic olefin resin is synthesized. In the presence of a radical initiator, acrylic acid, methacrylic acid, α-ethylacrylic acid, 2-hydroxyxethyl (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, endocis-bicyclo [2.2.1] 5_2,3-dicarboxylic acid, methyl-endocis-bicyclo

[2.2.1] Unsaturated carboxylic acid compounds such as heptose 5-ene-1,2,3-dicarboxylic acid, esters or amides thereof; maleic anhydride, maleic anhydride, buturic succinic anhydride, It can be synthesized by the method (I) of modifying with an acidic group-containing compound such as an unsaturated carboxylic anhydride such as tetrahydrophthalic anhydride or citraconic anhydride. The alicyclic olefin resin having an acidic group can be obtained by a method (方法) in which an alicyclic olefin monomer having no acidic group is copolymerized with an alicyclic olefin monomer having an acidic group. Can be. In this case, the type of polymerization includes addition polymerization and ring-opening polymerization, and after polymerization, hydrogenation may be performed if necessary. In the method (I), as the alicyclic olefin resin having no acidic group, aromatic resins such as styrene, α-methinolestyrene, di-no-le-benzene, bininole-naphthalene, and vinyl / leto / leene are used. An aromatic ring of a polymer obtained by addition polymerization of olefin may be hydrogenated to form a structural unit identical to a structural unit derived from an alicyclic olefin monomer. The alicyclic olefin resin may be obtained by copolymerizing an alicyclic olefin monomer and a monomer copolymerizable therewith. In the method (I), if a copolymerizable monomer having an acidic group is used, an alicyclic resin having an acidic group can be directly obtained.

As the method (II), in particular, in the presence of a catalyst mainly composed of an organic ruthenium compound having a neutral electron donating ligand, an alicyclic olefin having no polar group is used. The monomer and the alicyclic olefin monomer having a polar group are subjected to ring-opening metathesis copolymerization, and if necessary, the substituent is further modified by hydrolysis or the like to obtain an alicyclic olefin resin having a narrow molecular weight distribution. Can be The catalyst used in this method is a catalyst mainly composed of an organic ruthenium compound to which a neutral electron-donating ligand is coordinated. The neutral electron donating ligand constituting the organic ruthenium compound is a ligand having a neutral charge when separated from the central metal ruthenium. As the organic ruthenium compound, a compound in which an anionic ligand having a negative charge when separated from ruthenium can be used. In this case, a counter anion may be present, and an anion that forms an ion pair with a ruthenium cation may be included as a counter ion.

Specific examples of the monomer used for obtaining the alicyclic resin are shown below.

Examples of the alicyclic olefin monomer having no acidic group include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and 5-methyl-bicyclo [2.2.1] heptone. 2-ene, 5,5-dimethyl-bicyclo [2.2.1] heptoh 2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2 2.1) Heptot-2-ene, 5-hexyl-1-bicyclo [2.2.1] Hept-12-ene, 5-octyl-bicyclo [2.2.1] Hept-2-ene , 5-octadecyl-bicyclo [2.2.1] heptoe 2-ene, 5-ethylidene-d-bicyclo [2.2.1] hept-12-ene, 5-methylidene-bicyclo [2.2] 1] Hept-1-ene, 5-vinyl-1-cyclo [2.2.1] Hept-12-ene, 5-propenyl-bicyclo [2.2.1] Hept-2-ene, 5 — Methoxy-carbinyl-rubicyclo [2.2.1] hep 1-2-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, 5-methyl-1-5-methoxycarbo-2 / lebicyclo [2.2.1] hept-2-ene, 5 —Ethoxycarbonyl-2-loop cyclo [2.2.1] —Heptoh-2-ene, bicyclo [2.2.1] hept-1-5—enyl-1-2-methylpropionate, bicyclo [2.2.1] hept One five Nyl-1-methyloctanate, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) -bicyclo [2.2.1] hept-2-ene , 5-hydroxy-i-propylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxy-bicyclo [2.2.1] hept-12-ene, bicyclo [2.2.1] ] Hept-1-ene-5,6-dicarboxylic acid imide, 5-cyclopentinolebicyclo [2.2.1] Hept-12-ene, 5-cyclohexynolebicyclo [2.2.1] Hept-2-ene, 5-cyclohexenyl-bicyclo [2.2.1] hept-12-, 5-phenyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3, 7-gen (common name: dicyclopentadiene), tricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3-ene, tricyclo [4 . 4.0. I ² ' ⁵ ] Index 3, 7-Gen, Tricyclo [4.4.0. I ² ' ⁵ ] Index 3, 8-Gen, Tricyclo [4. 4.0. I ² ' ⁵ ] Index 1 3-E down, tetracyclo ^{[7. 4. 0. I 10 '.} 13 0 2' 7] trideca one 2, 4, 6- 1 1 Tetoraen (aka: 1, 4-methano one 1, 4, 4 a, 9 a- tetrahydrofluorene), tetracyclo ^{[8. 4. 0. I 11 '.} 14 0 2' 8] Tetoradeka 3, 5, 7, 12 1 1 tetraene (also known as 1, 4-methano one 1, 4 , 4 a, 5, 10, 10 hexa hydro anthracenyl down to a _), tetracyclo ^{^{[4. 4. 0. I 2 '5}} I 7.' 10] Dodeka 3- E emissions (trivial name: tetracyclododecene ), 8-Methyl-tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] Dode force 3-ene, 8-ethyl-tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ^'10] de de force one 3-E down, 8-methylidene one tetracyclo ^{_{[4. 4. 0. I 2' 5}} ! 7.10] dodeca - ₃ one E down, 8-Echiriden one tetracyclo [4. 4.0.

I ² ' ^5. I ⁷ ' ¹⁰ ] Dode force 3-ene, 8-Biel-tetracyclo [4.4.0. I ² ' ^5. I ⁷ ' ¹⁰ ] Dode force 3-ene, 8-Propenyl-tetracyclo [4.4.0. I ² ' ^5. I ⁷ ' ¹⁰ ] Dodeca 3-ene, 8-Methoxycarbonyl-tetracyclo mouth [4.4.0. I ² ' ⁵ . I ⁷ ^'10] Dodeka 3 E down, 8-methyl-one 8-main Toki Shikarubo two Lou tetracyclo ^{^{[4. 4. 0. I 2' 5}} . I 7 '10] Dodeka 3- E 4-hydroxymethyl monotetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] dode 3-one, 8-hydroxycanoleponyl tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ^'10] dodecane force one 3-E down, 8-cyclopentyl rule tetracyclo ^{^{[4. 4. 0. I 2' 5}} . I 7 '10] dodecane force one 3-E down, 8- Cyclohexinole-tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] Dodeca 3-ene, 8-cyclohexenyl-tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ^'10] Dodeka 3 E down, 8-phenylene Rutetora cyclo ^{^{[4. 4. 0. I 2' 5}} . I 7 '10] dodecane force one 3-E down, pentacyclo [6.5.1. ^{^{^{I 3 '6. 0 2'}}} 7. 0 9 '13] Pentade force one 3, 10-Zhen, Pentashiku port ^{^{[7. 4. 0. I 3' 6}} . l 10 '13. 0 2' 7] Pentade force one 4, 11 Jen, 5-phenylene Rubishikuro [2.2.1] Heputo 2 E down, tetracyclo ^{^{[6. 5. 0. I 2 '5}} . 0 8' 13] trideca one 3, 8, 10, 12 Tetraene (1, 4 - methanol 1, 4, 4 a, 9 a- also referred tetrahydrofluorene), Tetorashi black [6.6.2 0.1 ² '. ⁵ 1 ^8' ^13] tetradeca one 3, 8, 10, Norbornene-based monomers such as 12-tetraene (also called 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene); cyclobutene, cyclopentene, cyclohexene , 3,4-Dimethycyclopentene, 3-Methyl / lecyclohexene, 2- (2-Methyl ^^ butyl) -1-cyclohexene, Cyclooctene, 3a, 5,6,7a-Tetrahydro-1,4 7-Methanol 1H-Monocyclic cycloalkenes such as indene and cycloheptene; Bulcyclohexenes and Bulcyclohexanes; Bul-based alicyclic hydrocarbon-based monomers; Alicyclic conjugated monomer And the like.

Examples of alicyclic olefin monomers having a hydroxycarboxy group as an acidic group include 5-hydroxycarbonylbicyclo [2.2.1] heptoh-2-ene and 5-hydroxycarbonylmethylbicyclo [2.2.1]. 2.1. 1-hept-1-ene, 5, 6-dihydroxycarbonylbicyclo [2.2.1] hept-12-, 5-methyl-5-hydroxycanolebonylbicyclo [2. 2.1] Heptot-2-ene, 5-Methyl-1,5,6-dihydroxycarbonylbicyclo [2.2.1] Heptot 2_ 5, 5-hydroxycarbonyl 5-cyclohydroxymethylbicyclo

[2.2.1] bicycloheptene derivatives hept one 2-E emissions; 5-hydroxy Shikarubo two Rutetorashikuro ^{[4. 4. 0. I 2 '.} 5 I 7' 10] dodecane force one 3-E down, 5-hydroxy-carbonylation methyl tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] Dodeka 3 E emissions, 5, 6 dihydric Dorokishikarubo two Rutetorashikuro [4. 4. 0. I ² ' ^5. I ⁷ ^'10] dodecane force one 3-E down, 5-methyl-one 5-arsenide Dorokishikarubo two Rutetorashikuro ^{^{[4. 4. 0. I 2' 5}} . I 7 '10] dodecane force one 3- E emissions, 5-methyl-5, 6 dihydric Dorokishikarubo two Rutetorashikuro ^{^{[4. 4. 0. I 2 '5}} . 1 7' 1 °] Dodeka 3 E down, 5- hydroxycarboxylic carbonyl one 5-hydroxycarbonylmethyl Tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] Dode force 3-ene; 8-hydroxycarbol tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] Dode power 3-ene, 8-hydroxycarbonyl Chill tetracyclo ^{^{[4. 4. 0. I 2 '5}} . 1 7' 10] dodecane force one 3-E down, 8, 9-dihydroxy carbonylation Rutetorashikuro ^{[4. 4, 0. I 2 '} 5. I ⁷ ^'10] Dodeka 3 E down, 8-methyl-one 8-hydroxycarboxylic isobornyl tetracyclo ^{^{[4. 4. 0. I 2' 5}} . I 7 '10] dodecane force one 3-E down, 8- main chill one 8, 9 dihydric Dorokishikarubo - Rutetorashikuro ^{^{[4. 4. 0. I 2 '5}} 1 7 -. 10] Dodeka 3 E down, 8-hydroxycarboxylic carboxymethyl Nino rate 8 arsenide Dorokishikaruboyu methyl tetracyclo [ 4.4.0. I ² ' ^5. I ⁷ ' ¹⁰ ] Tetracyclododecene derivatives such as doden-1-ene; 11-hydroxycarboxyhexa [6.6.1 I ^{^{^{. 3 '. 6 l 10'}}} 13 0 2 '7 0 9.' 14] - heptadecyl force one 4-E down, Kisashikuro to 11 one hydroxycarbonylmethyl ^{[6. 6. 1. I 3 '.} 6 I 10' ^13. 0 2. 7. 09. 14] Heptade force—4-en, 11, 12—dihydroxy To carbonyl Kisashikuro ^{^{[6. 6. 1. I 3 '6}} I 10.' 13 0 2 '7 0 9.' 14.] Heputadeka 4 - E down, Kisashikuro to 1 1-methyl-1 1-hydroxycarboxylic carbonyl [6 ^{^{. 6. 1. I 3 '. 6}} 110. 13 02. 7 o 9' 14] heptadeca one 4-E down, 1 l Mechinore - 1 1, Kisashikuro [6.6.1 to 12-dihydroxy Kano levo sulfonyl ^{^{^{. I 3 '6. 1 1}}} 0, 1 3. 0 2. 7 o 9' 14] Heputadeka 4 E down, 1 l-hydroxy carbonylation Lou Kisashikuro to 1 1-hydroxycarbonylmethyl ^{^{[6. 6. 1. I 3 '6}} 1 10.' 1 3 0 2. 7 0 9 ' Putadesen derivative conductor 1 Tsu to f Kisashikuro such heptadeca _ 4 E emissions; etc. Can be mentioned.

Examples of the alicyclic olefin monomer having a dicarboxylic anhydride residue bonded as an acidic group include bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride and 5-methylbicyclo [2.2.1] Heputo 2 E down one 5, bicycloheptene derivatives such as 6-dicarboxylic anhydride, tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] Dodeka 3 E down one 8, 9-dicarboxylic acid anhydride, 8 Mechirutetorashi black ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] tetracyclododecene, such Dodeka 3 E down one 8, 9 Jikanorebon anhydride Derivative, hexacyclo [6. 6. 1. I ³ '6! 10, 13 ₀ 2.7 o ⁹ ' ^{1 4} ] —Heptadeca 4-one-11,12-dicarbonic anhydride, 11-methylhexacyclo [6. 6. 1. I ³ ' ⁶ . ^{^{^{I 10 '. 13 0 2'}}} 7 0 9 '14] Heputadeka 4 E down -. 1 1, can be given Putadesen derivative to f Kisashiku port such as 12-dicarboxylic anhydride.

The alicyclic olefin monomers can be used alone or in combination of two or more.

Monomers that can be copolymerized with the alicyclic olefin monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methylene / l-butene, 3-methylenol 1 —Pentene, 3-—Echinolene 1—Pentene, 4-Methynole 1—Pentene, 4-Methynole 1—Hexene, 4,4-Dimethinole 1—Hexene, 4,4—Dimethyl 1—Pentene, 4-Echinolé 1 —Hexene, 3-ethyl-11-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. Ethylene or α-olefin; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene And the like. These monomers can be used alone or in combination of two or more. As a method for adjusting the weight average molecular weight of the alicyclic olefin polymer, for example, at the time of ring-opening polymerization of the alicyclic olefin, a molecular weight modifier such as a bullet compound or a gen compound is added to the total amount of the monomer. A method of adding about 1 to 10 mol% is exemplified. When the amount of the molecular weight modifier used is small, a polymer having a relatively high weight average molecular weight is obtained, and when it is large, a polymer having a relatively low weight average molecular weight is obtained.

Vinyl compounds used as molecular weight regulators include c-olefin compounds such as 1-butene, 11-pentene, 1-hexene and 1-octene; styrene compounds such as styrene and vinyltoluene; Ether compounds such as sodium butynyl vinyl ether and aryl daricidyl ether; halogen compounds such as aryl chloride; oxygen-containing compounds such as aryl acetate, aryl alcohol and glycidyl methacrylate; acrylamide and the like A nitrogen-containing vinyl compound; Examples of the gen compounds include 1,4-pentagen, 1,5-hexadiene, 1,6-hexadiene, 2-methynole-1,4-pentadiene, and 2,5-dimethyl-1,5-hexadiene. Non-conjugated diene compounds; ^: Gen compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene ; Of these, α-olefin compounds such as 1-hexene are particularly preferred.

Examples of the alicyclic olefin resin obtained using such a monomer include a ring-opened polymer of an alicyclic olefin monomer and a hydrogenated product thereof, and an addition polymer of an alicyclic olefin monomer. , An addition polymer of an alicyclic olefin monomer and a Bürich compound, a monocyclic cycloalkene polymer, an alicyclic conjugated gen polymer, a butyl-based alicyclic hydrocarbon polymer and a hydrogenated product thereof, and an aromatic compound And aromatic ring hydrogenated products of olefin polymers. Among these, a ring-opened polymer of an alicyclic olefin monomer and a hydrogenated product thereof, an addition polymer of an alicyclic olefin monomer, and an addition polymer of an alicyclic olefin monomer and a vinyl compound Aromatic olefin polymer aromatic ring hydrogenated is preferred In particular, a hydrogenated product of a ring-opened polymer of an alicyclic olefin monomer is preferred.

The alicyclic resin may be used alone or in combination of two or more.

The acid generator (B) used in the present invention is a compound that generates an acid upon irradiation with actinic radiation. There is no particular limitation on the type of acid generated, and in order to obtain a positive pattern, a compound having a weakly acidic group such as a carboxyl group or a phenolic hydroxyl group is preferable, and a compound such as a quinonediazidesulfonic acid ester compound is particularly preferable. Compounds that generate an acid by a suitable carboxyl group are preferred.

The method for producing the quinonediazide sulfonic acid ester compound is not particularly limited, and is carried out according to a conventional method. Quinonediazide sulfonic acid halide, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4-hydroxyphenyl) methane 1,1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (2,5- Dimethyl-1-hydroxyphenyl) -1-phenylpropane, novolak resin, pheno Obtained by reacting a phenolic compound having at least one phenolic hydroxyl group, such as an oligomer obtained by co-polymerizing a polyol with dicyclopentadiene (Japanese Patent No. 3909911). be able to.

The esterification rate of the quinonediazidesulfonic acid ester compound is defined by the ratio of the hydrogen atom of the phenolic hydroxyl group of the phenolic compound to the quinonediazidesulfonic acid residue. The esterification rate is usually 20 to 100 mol. / _0, favored properly 4 0-1 0 0 mole ^_0/0, more preferably 5 0-1 0 0 mole ^_0/0, most preferably rather 6 0-1 0 0 mol%. If the esterification ratio is too low, the effect of suppressing the dissolution of the unexposed portions (unirradiated portions) is low, and the resolution and the residual film ratio are likely to decrease. Examples of the acid generator include ionic salts such as diaryldonium salts, triarylsulfonium salts, and phenyldiazonium salts, imidosulfonate derivatives, tosylate compounds, carbonate compounds of benzyl derivatives, and triazine derivatives. Halogenated organic halogen compounds, _α , _α'- bis (sulfonyl) diazomethane compound, α-carbonyl-ct-sulfonyldiazomethane compound, sulfone compound, organic phosphorus ester compound, organic acid amide compound, A compound that generates a relatively strong acid, such as an organic imide compound, can be used, whereby a negative pattern can be formed.

The amount of the acid generator is usually 0.5 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the alicyclic resin having an acidic group. To 30 parts by weight. If the amount of the acid generator is too small, the residual film ratio and the resolution may be deteriorated. Conversely, if the amount is too large, the heat resistance and the light transmittance may be reduced.

The crosslinking agent of the component (C) used in the present invention has an action of forming a crosslinked structure between the alicyclic olefin resins by reacting with the alicyclic olefin resin. Is a compound having a reactive group of Examples of the reactive group include an amino group, a carboxyl group, a hydroxyl group, an epoxy group, an isocyanate group, and a butyl group.

Specific examples of the crosslinking agent include aliphatic polyamines such as hexamethylene diamine; aromatic polyamines such as 4,4'-diaminodiphenyl ether and diaminodiphenyl sulfone; 2,6-bis (4 ' Azidobenzal) Azide compounds such as cyclohexanone, 4,4'-diazidodiphenylsulfone; polyamides such as nitrobenzene, polyhexamethylene diamine terephthalamide, and polyhexamethylene isophthalamide; N, N, Ν ', N ', N r, melamines such as melamine (hexa § Bruno record carboxymethyl into) one; Ν, Ν ', Ν, Ν - Darikoruuriru such (tetra- alkoxymethyl) glycol © Lil Attalays such as ethylene glycol di (meth) acrylate and epoxy acrylate resins Compounds; isocyanate compounds such as hexamethylene diisocyanate polyisocyanate, isofolone diisocyanate polyisocyanate, and tolylene diisocyanate polyisocyanate; hydrogenated diphenylmethane diisocyanate Polyisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norporanane; 1,3,4-trihydroxycyclohexane; containing alicyclic structure Examples of the epoxy compound or resin are given below. These may be used alone or as a mixture of two or more.

Among these crosslinking agents, N-alkoxymethylated melamine ゃ N-alkoxymethylated glycoluril is preferred from the viewpoint of heat resistance. These compounds are PL-117, PL-117, UFR65, CYMEL300, CYMEL303 (all manufactured by Mitsui Cytec), BX-400. It is easily available as a commercial product such as 0, 2-stroke rack MW-30, MX290 (above, manufactured by Sanwa Chemical Co., Ltd.). From the viewpoint of improving the adhesion of the resin film formed from the radiation-sensitive resin composition to a substrate or the like, it is preferable to use an isocyanate-based compound as the crosslinking agent.

The amount of the crosslinking agent is usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, and most preferably 100 to 70 parts by weight, based on 100 parts by weight of the alicyclic resin. Preferably it is 20 to 50 parts by weight. If the amount of the cross-linking agent used is too large or too small, the heat resistance, electric properties, and water absorption are likely to be insufficient.

The solvent of the component (D) used in the present invention is suitable for dissolving or dispersing the above-mentioned components, and those generally used as a solvent for the radiation-sensitive resin composition can be used. Examples of such a solvent include alcohols such as methanol, ethanol, propanol, butanol, _3- methoxy- ₃ -methylbutanol; cyclic ethers such as tetrahydrofuran and dioxane; methyl celloso / levacetate, ethinoreseroso Cerro Seo Norev Este les such as / rev acetate, ethylene glycol Honoré mono-methylol Honoré ether Honoré, ethylene glycol mono ethyl Honoré et Tenore, ethylene glycol Honoré monopropyl ether, les, ethylene glycol Honoré mono _t Petit / Leate / Le, Propylene Glycolate / Lemonoethinoleate / Le, Propylene Glycol Monopropyl Ether, Propylene Glycol Monobutyl Ether, Ethylene Glycolate Monomethyle / Leetheneole, Diethylene Glycoleone Monoethylate, Dipropylene Glycol ethers such as dalicol monomethyl ether; propylene dalicol alkyl ether acetates such as propylene glycol propyl ether acetate; aromatic hydrocarbons such as benzene, toluene, xylene; methylethyl ketone, cyclohexanone Ketones such as, 2-heptanone, 4-hydroxy 4-methyl-12-pentanone; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-12-methylpropionate, 2-hydroxy — Ethyl 2-methylpropionate, Ethyl ethoxyacetate, Ethyl hydroxyacetate, Methyl 2-hydroxy-13-methylbutanoate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, 3-Ethoxypropionic acid Esters such as ethyl, 3-ethoxymethyl propionate, ethyl acetate, butyl acetate, and ethyl lactate; N-methylformamide, N, N-dimethylformamide, N-methyl-1-pyrrolidone, N-methylacetamide And aprotic polar solvents such as N, N-dimethylacetamide, dimethylsulfoxide, and γ-butyllactone; and the like. These solvents are used in an amount sufficient to uniformly dissolve or disperse each component.

The radiation-sensitive resin composition of the present invention contains a nonionic surfactant such as polyoxyethylene lauryl ether or polyoxyethylene dilaurate for the purpose of preventing striation (after coating streaks) and improving developability; Fluorinated surfactants, such as Shin-Akita Kaseisha's EFTOP series, Dainippon Ink and Chemicals' Megafac series, Sumitomo 3LEM's Florado series, and Asahi Glass's Asahiguard series; Various surfactants, such as silane-based surfactants such as V-Leganosiloxane Polymer II series; acrylic acid copolymer-based surfactants such as Polyflow series manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd .; The surfactant is used in an amount of 100 parts by weight based on the solid content (components other than the solvent) of the radiation-sensitive resin composition. Usually, it is used in an amount of 2 parts by weight or less, preferably 1 part by weight or less, if necessary.

The radiation-sensitive resin composition of the present invention may be added with a functional silane coupling agent such as γ-glycidoxypropyltrimethoxysilane as an adhesion aid for the purpose of improving the adhesion to the substrate. Good. The amount of the adhesion promoter is usually 20 parts by weight or less, preferably 0.05 to 0.5 parts by weight, more preferably 1 to 0 parts by weight, based on 100 parts by weight of the alicyclic olefin resin having an acidic group. It is 10 parts by weight.

Further, the radiation-sensitive resin composition of the present invention may contain a sensitizer, an antistatic agent, a storage stabilizer, an antifoaming agent, a pigment, a dye, and the like, if necessary.

The components described above are mixed according to a conventional method, and dissolved or dispersed in a solvent to prepare a radiation-sensitive resin composition. The solid concentration of the prepared radiation-sensitive resin composition of the present invention is not particularly limited, but is usually 5 to 40% by weight.

The prepared radiation-sensitive resin composition is preferably a homogeneous solution. In this case, use a filter or the like of about 0.2 to 1 / zm to remove foreign substances and then use the composition. Is preferred.

The radiation-sensitive resin composition of the present invention can be used for a device such as a display device or an integrated circuit device, a protective film such as a color filter for a liquid crystal display, a flattening film for flattening the device surface or wiring, and an electric insulating property. Of various resin films for electronic components, such as insulating films (for example, including interlayer insulating films and solder resist films, which are electric insulating films for thin transistor-type liquid crystal display devices and integrated circuit devices) to maintain It is suitable as.

The radiation-sensitive resin composition of the present invention is applied on a substrate to form a resin film, and active radiation is irradiated in a pattern from above the resin film to form a latent image pattern on the resin film. By bringing the resin film having the latent image pattern into contact with the developer, the pattern can be made obvious.

The method for forming a resin film on a substrate is a method in which the radiation-sensitive resin composition of the present invention is applied to the surface of the substrate and dried to form a resin film directly on the substrate. The radiation-sensitive resin composition of the present invention is applied to at least one surface of a support such as a resin film such as a resin film, a polypropylene film, or a polyethylene film, and dried to form a resin film on the support. A method may be used in which a resin film with a coating is overlaid on a substrate. When the resin film with the support is superimposed on the substrate, it is preferable to heat and press using a pressing machine such as a pressure laminator, a pressure press, a vacuum laminator, a vacuum press, and a roll laminator. The temperature at the time of heat compression is usually 30 to 250 ° C, preferably 70 to 200 ° C, the compression force is usually 10 kPa to 20 MPa, preferably 1 OO kPa to OMPa, and the compression time is usually The duration is 30 seconds to 5 hours, preferably 1 minute to 3 hours. At the time of thermocompression bonding, it is desirable to adjust the pressure of the atmosphere to usually 10 OkPa to 1 Pa, preferably 40 kPa to 10 Pa.

As a method of applying the radiation-sensitive resin composition of the present invention to a substrate surface or a support, various methods such as a spray method, a roll coating method, and a spin coating method can be employed. Next, the obtained coating film is dried by heating to obtain a lusterless film having no fluidity. The heating conditions for forming the resin film directly on the substrate surface vary depending on the type and blending ratio of each component, but are usually about 60 to 120 ° for about 10 to 600 seconds. In a method in which a radiation-sensitive resin composition is applied to the surface of a substrate and dried to form a resin film directly on the substrate, heating for drying is generally performed using a pre-baking method. U.

The obtained resin film is irradiated with actinic radiation to form a latent image pattern on the resin film. The type of the actinic radiation is not particularly limited, and examples thereof include ultraviolet rays, far ultraviolet rays, X-rays, electron beams, and proton beam rays. Of these, visible rays and ultraviolet rays are preferable. The radiation dose for irradiation can be arbitrarily set depending on the type and thickness of the resin film. The pattern may be formed by a method of irradiating actinic radiation through a mask or a method of directly drawing with an electron beam or the like.

After irradiation, the exposed part is removed by bringing the luster film having the latent image pattern on the substrate into contact with the developing solution, and the latent image pattern is revealed (developed). Before development Heating (PEB treatment: Post Ex posure Bake) can be performed if necessary. By performing the PEB treatment, development residues such as unnecessary resin components which should be dissolved and removed in the developer can be reduced. It is preferable that the alicyclic resin has an alkali-soluble polar group, particularly an acidic group, because the outflow by the developer becomes easier.

The developer is generally an aqueous solution in which an alkali compound is dissolved in water. Examples of the alkali compound include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; and primary amines such as ethylamine and n-propylamine. Secondary amines such as getylamine and di-n-propylamine; tertiary amines such as triethylamine, methylethylamine and Ν-methylpyrrolidone; alcoholamines such as dimethylethanolamine and triethanolamine; tetramethylamine. Quaternary ammonium salts such as ammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and choline; pyrrole, pyridin, 1,8-diazabicyclo [5.4.0 ] 7-en, 1, 5-j Bicyclo [4.3.2 0] cyclic amines, such as nona one 5-E down; Hitoshigakyo is up. These alkali compounds can be used alone or in combination of two or more.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the developer.

As the developer, the irradiated portion of the resin film formed using the radiation-sensitive resin composition is dissolved at a rate of 1 μπιΖ min or more, and the unirradiated portion of the resin film is dissolved at a rate of 0.5 μπιΖ min or less. It is preferable to dissolve it, so that particularly excellent resolution and residual film ratio can be obtained. From this point of view, in the case of using a radiation-sensitive resin composition of the present invention, as the developer, the concentration is 0.01% to 1. 0 wt%, preferably 0.1 to 0.8 wt ⁰ It is desirable to use an aqueous solution of / ₀ tetramethylammonium hydroxide. The development time is usually 30 to 180 seconds. The method of contacting the developer with the resin film having a latent image pattern is not particularly limited, and for example, a paddle method, a spray method, a dipping method, or the like can be employed. Although the development temperature is not particularly limited, it is usually 15 to 35, preferably 20 to 30 :.

Thus, a resin film having a target pattern is formed on the substrate. After forming a pattern on the resin film by development, if necessary, the substrate and the rinsing liquid are brought into contact with each other in a usual manner to remove unnecessary development residues remaining on the substrate, the back surface of the substrate, and the edge of the substrate. be able to. The substrate in contact with the rinsing liquid is usually dried with compressed air or compressed nitrogen to remove the rinsing liquid on the substrate. If necessary, the entire surface of the patterned resin film can be irradiated with actinic radiation.

After forming a pattern on the resin film of the substrate, the resin film can be cured by heating (postbaking: Postbak) if necessary. The heating method is performed by a heating device such as a hot plate and an oven. The heating temperature is usually 150 to 250, preferably 180 to 220.The heating time is, for example, when using a hot plate, usually 5 to 60 minutes, when using an oven. Usually, it is 30 to 90 minutes. Post baking is preferably performed in a low-oxygen atmosphere, specifically, an atmosphere having an oxygen concentration of 10 ppm or less.

As described in detail above, a resin film is formed on a substrate using the radiation-sensitive resin composition of the present invention, and active radiation is irradiated in a pattern from above the resin film to form a latent image pattern on the resin film. Then, a pattern is formed on the resin film by a pattern forming method in which the pattern is exposed by bringing the resin film into contact with a developer. The resin film on which the pattern is formed is suitably used as a resin film for electronic components such as a protective film, a planarizing film, and an interlayer insulating film. Example

Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples and Examples. In each case Parts and percentages are by weight (weight basis) unless otherwise specified.

[Synthesis example 1]

8-Hydroxycarbonyltetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] — Dodeca 3-ene 70 parts, tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ 30 parts of dodeca-3-ene, 10 parts of 1-hexene, 1,3-dimesitylimidazolidine-12-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.04 parts, tetrahydrofuran 400 The part was charged into a nitrogen-substituted glass pressure-resistant reaction vessel, heated to 70 ° C. and stirred for 2 hours to obtain a reaction solution. It was confirmed by gas chromatography that no monomer remained in the reaction solution. The obtained reaction solution was poured into a large amount of n-hexane to precipitate a solid. The obtained solid was washed with n-hexane and dried under reduced pressure at 100 ° C. for 18 hours to obtain a ring-opening metathesis copolymer as a white solid.

100 parts of this ring-opening metathesis copolymer, 400 parts of tetrahydrofuran, and 5 parts of palladium Z-carbon (10% palladium) as a hydrogenation catalyst were added to an autoclave equipped with a stirrer, and hydrogen pressure was 1.0 MPa, 60 ° C. For 8 hours. After the reaction solution is filtered, it is coagulated and dried in a large amount of n-hexane as described above, and an alicyclic olefin resin having an acidic group having a hydrogenation rate of 100% (determined by iH-NMR spectrum) ( Polymer a) was obtained.

[Synthesis example 2]

8-Hydroxycarbonyltetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] — 78 parts of dodeca-3-ene, tetracyclo [4. 4. 0. I ² ' ⁵ . 1 ⁷ · ¹⁰ ]-Hydrogenation rate 100% in the same manner as in Synthesis Example 1 except that the amount of 3-deene was changed to 22 parts and the amount of 1-hexene was changed to 8 parts. An alicyclic olefin resin (polymer b) having an acidic group was obtained.

[Synthesis example 3]

8-hydroxy-carbonylation Rutetorashikuro ^{^{[4. 4. 0. I 2 '5}} I 7.' 10] -. 71 parts of de-deca one 3-E down, tetracyclo ^{^{[4. 4. 0. I 2 '5}} I 7 ^'10] - de de An alicyclic olefin resin having an acid group with a hydrogenation rate of 100% was prepared in the same manner as in Synthesis Example 1 except that the amount of 3-ene was changed to 29 parts and the amount of 11-hexene was changed to 20 parts.

(Polymer c) was obtained.

[Synthesis example 4]

8-hydroxy-carbonylation Rutetorashikuro ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] dodecane force one 3-E down the 76 parts, tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I 7 ^'10] dodecane force one 3 _ E down the 24 parts, except for changing the respective 8 parts hexene, in the same manner as in synthesis example 1, alicyclic with hydrogenation rate of 100% of the acid groups The formula resin (polymer d) was obtained.

[Synthesis example 5]

In the method disclosed in Synthesis Example 5 of JP-A-11-52574, the temperature at the time of catalyst input was changed from 6 O to 80, and the polymerization holding temperature was changed from 8 Ot to 110 ° C. Other than the above, an alicyclic olefin resin having an acidic group (polymer e) having a hydrogenation rate of 100% and a hydrolysis rate of 75% was obtained according to the method described in Synthesis Example 5 of the publication. Specifically, polymer e was synthesized by the following method.

8-methyl-one 8-main-butoxycarbonyl tetracyclo ^{^{[4. 4. 0. I 2 '5}} . 1 7' 10] -3- dodecene 250 parts, 180 parts of 1-hexene, and 750 parts of toluene was purged with nitrogen The reaction vessel was charged and heated to 80 ° C. This, Toryechiruaru Miniumu (1.5 mol Z 1) toluene solution 0.62 parts _{_{of, tert- C 4 H 5 OH /}} CH 3 OH in modified _{_{_{(tert _C 4 H 9 OHZCH 3}}} OH / W = 0. 35/0. 3Z 1; molar ratio) was WC 1 ₆ solution (concentration 0.05 Moruno 1) 3.7 parts was added and heating for 3 hours stirring at 1 1 0, to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 90%.

4,000 parts of the obtained polymer solution was put in an autoclave, and 30.48 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] was added thereto, and the hydrogen gas pressure was increased to 100 kg / cm ² , The mixture was stirred with heating at a reaction temperature of 165 ° C for 3 hours. After cooling the obtained reaction solution, the hydrogen gas was released to obtain a hydrogenated polymer solution. Hydrogen thus obtained The added polymer was poured into a large amount of methanol to solidify the polymer. The hydrogenation rate of the hydrogenated polymer thus obtained was substantially 100%. 100 parts of the obtained hydrogen-added polymer, 100 parts of N-methyl-1-pyrrolidone, 500 parts of propylene glycol, and 84.5 parts of potassium hydroxide (concentration: 85%) were placed in a reactor. The mixture was heated and stirred at 90 ° C for 1.5 hours. The obtained reaction solution was poured into a large amount of a mixed solution of water, tetrahydrofuran and hydrochloric acid to coagulate the hydrolyzate. The coagulated polymer was washed with water and dried to obtain a polymer e as a hydrolyzed polymer. The hydrolysis rate of the obtained hydrolyzed polymer was 75%.

[Synthesis example 6]

An alicyclic olefin resin having an acid group having a hydrogenation rate of 100% and a hydrolysis rate of 75% (Polymer f) was prepared in the same manner as in Synthesis Example 5 except that the polymerization holding temperature was changed from 110 ° C to 100 ° C. ).

[Synthesis example 7]

An alicyclic olefin resin having an acid group having a hydrogenation rate of 100% and a hydrolysis rate of 75% (polymer g) was prepared in the same manner as in Synthesis Example 5 except that the polymerization holding temperature was changed from 110¾ to 90. ).

[Comparative Synthesis Example 1]

According to the method disclosed in Synthesis Example 5 of JP-A-1 1-52574, JP-8 - methyl-8-methoxy-carbonylation Rutetorashikuro ^{[4. 4. 0. I 2 '.} 5 1 7' 1 °] de Ring-opening polymerization of dextran-3-ene was performed to obtain a ring-opened polymer having a weight average molecular weight of 17,000. Then, after hydrogenation of the obtained ring-opened polymer, a hydrolysis reaction was carried out for 1.5 hours to obtain an alicyclic olefin resin having an acidic group having a hydrogenation rate of 100% and a hydrolysis rate of 75% (polymer h) was obtained.

[Comparative Synthesis Example 2]

8-hydroxy-carbonylation Rutetorashikuro ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] dodecane force 90 parts of an 3-E down, tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I 7 ^'10] dodecane force one 3-E down the 10 parts, except for changing each 9 parts hexene, synthesis example 1 In the same manner as in the above, an alicyclic olefin resin (polymer i) having an acidic group and having a hydrogenation rate of 100% and a hydrolysis rate of 75% was obtained.

Table 1 shows the physical properties of the polymers a to i obtained in the above synthesis examples.

In Table 1, the meanings of the symbols in the column of the copolymerization ratio are as follows.

TCDC: 8-hydroxycarbonyltetracyclo [4. 4. 0. I ² ' ^5. ¹⁷ ' ¹ °] Repeating unit derived from 3-hydroxy

T CD: Tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] Repeat unit derived from 3-Dene

TCDE: 8-methyl-8-main Tokishikarubo two Rutetorashikuro [4. 4. 0. 1 2 '. 5 I 7' 10] dodecane force one 3-E emissions from repeating units.

[Example 1]

For 100 parts of the polymer a obtained in Synthesis Example 1, 550 parts of cyclohexanone, 1,1,3-Tris (2,5-dimethyl-14-hydroxypheninole) -13-pheninolepropane (1 ^^) and 1,2-naphthoquinonediazide as 1,2-quinonediazide compounds 20 parts by weight of a condensate with sulfonic acid chloride (1.9 mol), 25 parts of CYME L300 as a cross-linking agent, 5 parts of _y -glycidoxypropyl ^^ trimethoxysilane as an adhesion promoter, Megafac F as a surfactant 172 [manufactured by Dainippon Ink and Chemicals, Inc.] After mixing and dissolving 0.05 parts, the mixture is filtered through a polytetrafluoroethylene filter having a pore size of 0.45 / zm, and the radiation-sensitive photosensitive resin composition solution is used. Was prepared.

This solution was spin-coated on a silicon substrate, a glass substrate, and a silicon oxide film substrate with a step of 1 / zm (hereinafter referred to as “stepped substrate”), and then hot-plated at 9 for 2 minutes. By pre-baking above, a coating film having a thickness of 3. 膜厚 μπι was formed. A mask having a predetermined pattern was placed on the obtained silicon substrate with a coating film, and irradiated with ultraviolet light having a wavelength of 365 nm and a light intensity of 5 mW cm ² in air for 40 seconds. Next, development processing was performed at 25 for 60 seconds using a 0.3% aqueous solution of tetramethylammonium. Thereafter, rinsing treatment was performed for 1 minute with ultrapure water to form a thin film having a positive pattern.

Thereafter, the entire surface was irradiated with ultraviolet light having a light intensity of 5 mWZ cm ² at 365 nm for 60 seconds. The silicon substrate, glass substrate, and silicon oxide film substrate with a 1 μπι step formed with this pattern were each heated on a hot plate at 200 ° C for 30 minutes to obtain a post-base of the pattern and coating film. Then, a silicon substrate, a glass substrate, and a stepped substrate on which a pattern-like thin film was formed were obtained.

[Examples 2 to 7]

Polymer b (Example 2), polymer c (Example 3), polymer d (Example 4), polymer e (Example 5), polymer f (Example 6), polymer 1 g instead of polymer a A silicon substrate, a glass substrate, and a stepped substrate on which a patterned thin film was formed were obtained in the same manner as in Example 1 except that (Example 7) was used.

[Comparative Examples 1 and 2] In the same manner as in Example 1 except that Polymer h (Comparative Example 1) and Polymer i (Comparative Example 2) were used instead of Polymer a, a silicon substrate on which a patterned thin film was formed, a glass substrate, and A stepped substrate was obtained.

[Evaluation]

Each of the silicon substrates obtained above had a film thickness after heating in an oven at 220 ° C for 60 minutes of 95% or more of the film thickness before heating, and was confirmed to be excellent in heat-resistant dimensional stability. Was.

Each of the glass substrates obtained above was analyzed using a UV-visible-near-infrared spectrophotometer (V-570) manufactured by JASCO Corporation, and the minimum light transmittance (t) at a wavelength of 400 to 800 nm was 90%. %, Which was excellent, and it was confirmed that the transparency was excellent.

When the steps were measured with a contact-type film thickness measuring device, each of the stepped substrates obtained above was less than 0.1 / zm, and it was confirmed that the substrates had high flatness.

In addition to these evaluations, the dielectric constant and water absorption of the alicyclic olefin resin (polymers a to i) used in each example, and the solvent resistance, resolution, and residue measured using the glass substrate obtained above. The film ratio and the pattern shape were evaluated by the following methods. Table 2 shows the results.

(1) Relative permittivity:

The relative dielectric constant (ε) at 1 MHz (room temperature) was measured according to JIS C 6481 and evaluated according to the following criteria.

A: ε <2.60,

Β: 2.60≤ε <2.70,

C: 2.70≤ε <2.80,

D: ε≥2.80.

(2) Water absorption:

The water absorption (w) was measured according to JIS C6481, and evaluated according to the following criteria. A: w <0.05%,

B: 0.05% ≤w <0.07%, C: 0.07% ≤w <0.1%,

D: 0.1% ≤w.

(3) Solvent resistance:

The glass substrate on which the patterned thin film was formed was immersed in dimethyl sulfoxide at 70 ° C for 30 minutes, and the film thickness change rate (S) was measured and evaluated according to the following criteria.

A: 10%> S,

B: 10% ≥S,

C: A state in which the swelling is large and the film is peeled off from the substrate, and the rate of change in film thickness cannot be measured.

(4) Resolution:

Observe the patterned thin film formed on the glass substrate with a scanning electron microscope to find the minimum pattern dimension (W) where the line'and space is formed with a line width of 1: 1. Evaluation was based on criteria.

A: W ≤ 5 μm,

B: 5 μm <W≤10 m,

C: 10 μm <W≤15 // m,

D: W> 15 μπι.

(5) Remaining film ratio:

Developed with a 0.3 wt% aqueous solution of tetramethylammonium hydroxide (25 ° C) for 1 minute, and measured the film thickness of the unexposed area before and after development using a contact-type film thickness meter. . The film thickness after development (film thickness before development) X I 00 was defined as the residual film ratio (R), and evaluated according to the following criteria.

A: R≤ 95%,

B: 93≤R <95%,

C: 90% ≤R <93%,

D: 85% ≤R <90%,

E: R <85%.

(6) Pattern shape: The cross section of the line and space after pattern jung was observed with a scanning electron microscope, and evaluated according to the following criteria.

A: a rectangular shape with no residue derived from the radiation-sensitive resin composition and without shape collapse; B: a slight tailing at the interface between the luster pattern and the substrate;

C: Development residue exists in the space. Table 2

From the results shown in Table 2, the radiation-sensitive resin compositions of the present invention (Examples 1 to 7) maintain the characteristic balance of relative dielectric constant, water absorption resistance, heat-resistant dimensional stability, flatness, and solvent resistance. It can be seen that excellent resolution, remaining film ratio, and pattern shape can be achieved while maintaining the same. In particular, when an alicyclic resin (polymers a and b) having an acidic group having a weight average molecular weight of less than 10,000, a molecular weight distribution of 2.0 or less, and an index C1 of 600 or more is used (Examples 1 and 2). It can be seen that excellent resolution and residual film ratio can be obtained.

Also, 8-arsenide Dorokishikarubo two Rutetorashikuro ^{^{[4. 4. 0. I 2 '5}} 1 7.' 1 °] - Dodeka 3 E emissions from repeating units and tetracyclo of ^{^{[4. 4. 0. I 2 '5}} . I ⁷ · ¹⁰ ]-When using alicyclic olefin resins (polymers a to d) having a repeating unit derived from 3-dene (Examples 1 to 4), excellent water absorption resistance It can be seen that On the other hand, when an alicyclic olefin resin having a low index Ci as described in JP-A-11-52574 and JP-A-10-307388 was used (Comparative Example 1). And 2), the relative permittivity, water absorption and solvent resistance are slightly inferior, and the resolution, residual film ratio and pattern shape are inferior. Industrial applicability

According to the present invention, it is possible to obtain a radiation-sensitive resin composition having properties suitable for forming an electrical insulating film, and also having excellent resolution, residual film ratio, and pattern shape. The resin film formed using the radiation-sensitive resin composition of the present invention and the resin film formed with a pattern include, for example, electronic elements such as semiconductor elements, light emitting diodes, and various memories; hybrid ICs, MCMs, and prints. It can be suitably used as a resin film for various electronic components such as an overcoat material for a wiring board; an interlayer insulating film of a multilayer circuit board; an insulating layer of a liquid crystal display.

Claims

The scope of the claims

1. In a radiation-sensitive resin composition containing (A) an alicyclic resin having an acidic group, (B) an acid generator, (C) a crosslinking agent, and (D) a solvent, (A) an acidic group When the weight-average molecular weight of the alicyclic olefin resin having is less than 10,000, the following formula (1)

(MW) ⁰⁵ X (AC) ⁷

C 1 = X 10 ⁵ (1)

(AG) ⁶ X (MWD) ²

(MW) ^a5 X (AC) ²

C 2 = X 10 ³ (2)

(AG) ² X (MWD) ³

(The meaning of each symbol in the formula is the same as in formula (1).)

A radiation-sensitive resin composition, wherein an index C 2 represented by the formula: is 120 or more.

2. The radiation-sensitive resin composition according to claim 1, wherein the weight-average molecular weight of the (A) alicyclic resin having an acidic group is in the range of 500 to 20,000.

3. The radiation-sensitive resin group according to claim 1, wherein the acidic group is a phenolic hydroxyl group, a carboxyl group, a dicarboxylic anhydride residue, a sulfonic acid residue, or a phosphoric acid residue. Adult.

4. The radiation-sensitive resin composition according to claim 3, wherein the acidic group is a carboxyl group.

5. When the alicyclic resin is

Ring-opening (co) polymer of ω alicyclic olefin monomer and hydrogenated product thereof,

(Addition (co) polymer of alicyclic olefin monomer,

(ϋυ an addition copolymer of an alicyclic olefin monomer and a vinyl compound,

(iv) a monocyclic cycloalkene (co) polymer,

(V) an alicyclic conjugated diene (co) polymer,

(vi) Bull-based alicyclic hydrocarbon (co) polymer and hydrogenated product thereof, and

(vii) Aromatic ring hydrogenated product of aromatic olefin (co) polymer

2. The radiation-sensitive resin composition according to claim 1, which is at least one resin selected from the group consisting of:

6. The radiation-sensitive resin composition according to claim 5, wherein the alicyclic olefin resin is a hydrogenated product of a ring-opening (co) polymer of an alicyclic olefin monomer.

7. The radiation-sensitive resin composition according to claim 6, wherein the alicyclic resin is a hydrogen additive of a ring-opening (co) polymer of a norbornene-based monomer.

8. The radiation-sensitive resin composition according to claim 7, wherein the norbornene-based monomer is a tetracyclododecene.

9. The radiation-sensitive resin composition according to claim 1, wherein the (A) alicyclic olefin resin having an acidic group is a resin obtained by modifying an alicyclic olefin resin with a compound having an acidic group.

10. (A) An alicyclic olefin resin having an acidic group is an addition copolymer or ring-opening copolymer of an alicyclic olefin monomer having an acidic group and an alicyclic olefin monomer having no acidic group. 2. The radiation-sensitive resin composition according to claim 1, which is a polymer or a hydrogenated product thereof.

1 1. (A) Addition of an alicyclic olefin resin having an ester group to an alicyclic olefin monomer having an ester group and, if necessary, a monomer having no ester group.

2. The radiation-sensitive resin composition according to claim 1, which is obtained by hydrolyzing a (co) polymer, a ring-opening (co) polymer, or a hydrogenated product thereof.

12. The radiation-sensitive resin composition according to claim 1, wherein the molecular weight distribution of the (A) alicyclic resin having an acidic group is 3.3 or less.

13. The radiation-sensitive resin composition according to claim 1, wherein the proportion of the structural unit having an acidic group in the (A) alicyclic resin having an acidic group is 20 to 80 mol%.

14. The radiation-sensitive resin according to claim 1, wherein the (A) alicyclic resin having an acidic group has a weight average molecular weight of less than 10,000, a molecular weight distribution of 2.0 or less, and an index C1 of 600 or more. Composition.

15. The radiation-sensitive resin composition according to claim 1, wherein the acid generator (B) is a quinonediazidesulfonic acid ester.

16. The radiation-sensitive resin composition according to claim 1, wherein (C) the crosslinking agent is a compound having at least two reactive groups.

1 7. Using the radiation-sensitive resin composition according to any one of claims 1 to 16 Forming a resin film on the substrate, irradiating the resin film with actinic radiation from above the resin film to form a latent image pattern on the resin film, and then contacting the resin film with the developer. A pattern forming method that makes a pattern visible.

1 8. Developer concentration 0.0 1% to 1. 0 wt ^_0/0 The pattern formation method of claim 1 7 wherein the tetramethylammonium Niu Muhidorokishido aqueous.

1 9. A resin film having a pattern formed by the method according to claim 17.

20. Use of the resin film formed with the pattern according to claim 19 as a resin film for an electronic component.