Curable resin composition and cured product

Abstract

To provide a curable resin composition which can form a coating film having excellent dry etching resistance and excellent heat-curing properties.SOLUTION: A curable resin composition comprising at least one of the following polymers: (1) a polymer having a structure derived from a polymerizable monomer (A1) that has at least one selected from an alicyclic structure and an aromatic ring structure, and has a cyclic ether group; and (2) a polymer having a structure derived from a polymerizable monomer (A2) having a cyclic ether group, and a structure derived from a polymerizable monomer (B) having at least one selected from the alicyclic structure and the aromatic ring structure.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable resin composition. More specifically, the present invention relates to a curable resin composition from which a cured product suitable for a resist underlayer film or the like can be obtained.

Background Art

[0002] In recent years, with the increasing integration and speed of LSIs, finer and finer pattern processing has been required. In photolithography using ArF excimer laser light (193 nm), by utilizing the optical properties of process materials and improving process equipment, it has become possible to exceed the inherent resolution limit derived from the wavelength of the light source.

[0003] In the field of photoresists, various methods for forming finer wiring patterns have been developed, and one of them is the multilayer resist method. In the multilayer resist method, one or more layers called a resist underlayer film, an antireflection film, etc. are formed on a substrate, and then a resist pattern by ordinary photolithography is formed thereon. Next, the wiring pattern is processed and transferred to the substrate by dry etching. In the technology of the multilayer resist method, one of the important members is the resist underlayer film. The resist underlayer film is required to have low viscosity, high dry etching resistance, low light reflectivity, etc.

[0004] Also, in the multilayer resist method, in order to prevent film loss and film roughness of the resist underlayer film during coating of the upper-layer photoresist, the resist underlayer film is cured by heating after being coated on the substrate. Therefore, the resist underlayer film is required to exhibit good curing reactivity during heating and high solvent resistance. Also, in order to prevent device contamination, it is required that no outgas is generated during heat curing and no film loss occurs.

[0005] Recently, further miniaturization has been required, and accordingly, the aspect ratio of the resist pattern has increased, so the concern about the collapse of the resist pattern has been growing. Therefore, in the resist underlayer film, high substrate adhesion is required to suppress the collapse of the resist pattern (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] In order to enable further miniaturization, a curable resin composition having high dry etching resistance, good reactivity (high solvent resistance), low volatility during heating, and high substrate adhesion is required. An object of the present invention is to provide a curable resin composition capable of obtaining a coating film having good dry etching resistance and heat curability.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that by using a polymer having a predetermined structure in a curable resin composition, the dry etching resistance and heat curability of the resulting cured product can be improved, and thus the present invention has been completed.

[0009] That is, the present invention relates to a curable resin composition containing at least one of the following polymers (1) and (2). (1) A polymer containing a structure derived from a polymerizable monomer (A1) having at least one of an alicyclic structure and an aromatic ring structure and a cyclic ether group (2) A polymer containing a structure derived from a polymerizable monomer (A2) having a cyclic ether group and a structure derived from a polymerizable monomer (B) having at least one of an alicyclic structure and an aromatic ring structure The present invention also relates to a cured product of the above composition or a resist underlayer film.

Effects of the Invention

[0010] According to the present invention, a curable resin composition capable of obtaining a coating film having good dry etching resistance and heat curability can be provided.

Modes for Carrying Out the Invention

[0011] Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention. In the present specification, “(meth)acrylate” means one or both of acrylate and methacrylate.

[0012] The curable resin composition of the present invention contains at least one of the following polymers (1) and (2). (1) A polymer (1) containing a structure derived from a polymerizable monomer (A1) having at least one of an alicyclic structure and an aromatic ring structure and a cyclic ether group (2) A polymer (2) containing a structure derived from a polymerizable monomer (A2) having a cyclic ether group and a structure derived from a polymerizable monomer (B) having at least one of an alicyclic structure and an aromatic ring structure By including at least one of the above polymers (1) and (2), a curable resin composition capable of obtaining a coating film having good dry etching resistance and heat curability can be obtained. In particular, by using the polymer (1) and / or the polymer (2), it is possible to achieve both dry etching resistance and heat curability of the resin alone.

[0013] (Polymer (1) and Polymer (2)) In the present invention, the "polymerizable monomer" means a compound having a polymerizable unsaturated group. Examples of the polymerizable unsaturated groups possessed by the polymerizable monomer (A1), the polymerizable monomer (A2), and the polymerizable monomer (B) include C═C-containing groups such as (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamino group, vinyl group, vinyl ether group, allyl group, styryl group, and maleimide group. Among these, due to the easy availability of raw materials and good polymerization reactivity, (meth)acryloyl group, (meth)acryloyloxy group, and vinyl group are preferred. Also, the number of polymerizable unsaturated groups possessed by the polymerizable monomer may be one or two or more.

[0014] The polymerizable monomer (A1) is preferably a compound represented by the following general formula (A1-1). [Chemical formula] (In the general formula (A1-1), R 11 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L 11 is a divalent linking group containing at least an arylene group, and Z is an epoxy group, an oxetanyl group, an alkyloxetanyl group having 4 to 10 carbon atoms, or an epoxycycloalkyl group having 5 to 10 carbon atoms.)

[0015] In the general formula (A1-1), examples of the alkyl group having 1 to 6 carbon atoms for R 11 include a methyl group and an ethyl group. R 11 is preferably a hydrogen atom or a methyl group. L 11 is a divalent linking group containing an arylene group. For example, a group consisting only of an arylene group, a group formed by combining an arylene group with one or more selected from an alkylene group and an ether bond (-O-) can be mentioned. L 11 is preferably a divalent linking group composed of a combination of an arylene group, an ether bond, and an alkylene group.

[0016] L 11Examples of the arylene group include arylene groups having 6 to 18 carbon atoms, and arylene groups having 6 to 14 carbon atoms are preferred. The arylene group may be a monocyclic group or a condensed ring group. Specific examples of the arylene group include a phenylene group, a naphthylene group, and the like. L 11 Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms. The alkylene group may be linear, branched, or cyclic. L 11 The alkylene group and the arylene group may further have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, and the like.

[0017] Examples of the alkyloxetanyl group having 4 to 10 carbon atoms for Z include a 3-methyloxetanyl group, a 3-ethyloxetanyl group, a 2-methyloxetanyl group, and a 2-ethyloxetanyl group. Examples of the epoxycycloalkyl group having 5 to 10 carbon atoms include a 3,4-epoxycyclohexyl group, a 3-methyl-3,4-epoxycyclohexyl group, a 2,5-epoxycyclohexyl group, a 4,5-epoxycyclooctyl group, a 3,4-epoxycyclooctyl group, a 2,3-epoxycyclopentyl group, and a 3,4-epoxycyclopentyl group. Z is preferably an epoxy group.

[0018] Specific examples of the compound represented by the general formula (A1-1) include, for example, 4-vinylbenzyl glycidyl ether, 2-[(4-ethenylphenoxy)methyl]oxirane, 2-(4-ethenylphenoxy)oxirane, 2-[2-(4-ethenylphenyl)ethyl]oxirane, 3-[(4-ethenylphenoxy)methyl]oxetane, 2-[[4-(1-methylethenyl)phenoxy]methyl]oxirane, 2-[(4-ethenylphenoxy)methyl]oxetane, 2-[[4-(2-propenyl)phenoxy]methyl]oxirane, 2-[(3-ethenylphenyl)methyl]oxirane, 3-[(4-ethenyl-2-methylphenoxy)methyl]oxetane, 2-(4-ethenylphenoxy)tetrahydrofuran. The polymerizable monomer (A1) can be produced by a known method, and a commercially available product may also be used.

[0019] The polymerizable monomer (A2) having a cyclic ether group is preferably a compound represented by the following general formula (A2-1).

[0020]

Chemical formula

[0021] R 12 Specific examples of the alkyl group having 1 to 6 carbon atoms of are the same as those of the above R 11 . L 12 Examples of the divalent linking group of include a group selected from an alkylene group, an arylene group, or a combination of two or more selected from an alkylene group, an arylene group, and an ether bond (-O-). L 12 Examples of the alkylene group and arylene group of are the same as those of the above L 11 . L 12 is preferably a single bond. Examples of Z are the same as those of Z in the general formula (A1-1) above.

[0022] Specific examples of the compound represented by the general formula (A2-1) include epoxy group-containing (meth)acrylate compounds such as glycidyl (meth)acrylate, glycidyl ether of 4-hydroxybutyl (meth)acrylate, and epoxycyclohexylmethyl (meth)acrylate; oxetanyl group-containing (meth)acrylate compounds such as (3-ethyloxetan-3-yl)methyl acrylate; and mono(meth)acrylate compounds of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether.

[0023] The polymerizable monomer (A2) can be produced by a known method, and a commercially available product may be used. Examples of commercially available products of the polymerizable monomer (A2) include SR-378 (manufactured by Sartomer Co., Ltd.), which is a commercially available product of glycidyl acrylate; Light Ester G (manufactured by Kyoeisha Chemical Co., Ltd.), Brenmer G (manufactured by Nippon Oil & Fats Co., Ltd.), SR-379 (manufactured by Sartomer Co., Ltd.), OXE-10, OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and Cyclomer M100 (manufactured by Daicel Corporation), which are commercially available products of glycidyl methacrylate.

[0024] The polymerizable monomer (B) having at least one of an alicyclic structure and an aromatic ring structure is preferably a compound represented by the following general formula (B-1).

[0025]

Chemical formula

[0026] R 21 Specific examples of the alkyl group having 1 to 6 carbon atoms of R are the same as those of R described above. 11 It is the same as above. L 21 Examples of L are the same as those of L described above. 12 It is the same as above.

[0027] As the aromatic group of X, an aryl group having 6 to 18 carbon atoms is preferable, and an aryl group having 6 to 14 carbon atoms is more preferable. Further, the aryl group is a monocyclic or condensed ring, preferably a monocyclic or condensed ring having 2 to 8 condensed rings, and more preferably a monocyclic or condensed ring having 2 to 4 condensed rings. Specifically, a phenyl group, a naphthyl group, an anthracenyl group, etc. are exemplified. Examples of the alicyclic hydrocarbon group include a dicyclopentanyl group, an isobornyl group, an adamantyl group, etc.

[0028] Specific examples of the compound represented by the general formula (B-1) include benzyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, hydroxyadamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, etc.

[0029] The polymerizable monomer (B) can be produced by a known method. Also, a commercially available product may be used as the polymerizable monomer (B). The polymerizable monomer (B) may be used alone or in combination of two or more kinds.

[0030] The polymer (1) is obtained by polymerizing a polymerization component containing the above-described polymerizable monomer (A1). In the present invention, the "polymerization component" means a component constituting a polymer, and does not include a solvent, a polymerization initiator, etc. that do not constitute the polymer. The polymer (1) may contain a structural unit of a polymerizable monomer other than the polymerizable monomer (A1) as long as the effects of the present invention are not impaired. In the polymer (1), the content of the structure derived from the polymerizable monomer (A1) is, for example, 50% by mass or more, 70% by mass or more, 90% by mass or more, 95% by mass or more with respect to the whole polymer (1). It may be substantially 100% by mass. When it is substantially 100% by mass, the polymer (1) may contain a structure derived from inevitable impurities.

[0031] The polymer (2) is obtained by polymerizing a polymerization component containing the above-described polymerizable monomer (A2) and the polymerizable monomer (B). In the polymerization of the polymer (2), the blending amount of the polymerizable monomer (B) can be appropriately set. For example, it is 10 to 300 parts by mass, preferably 15 to 250 parts by mass, more preferably 30 to 200 parts by mass, still more preferably 30 to 150 parts by mass, and particularly preferably 50 to 140 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A2).

[0032] The polymer (2) may contain a structural unit of a polymerizable monomer other than the polymerizable monomer (A2) and the polymerizable monomer (B) as long as the effects of the present invention are not impaired. For example, it may contain a structural unit derived from the polymerizable monomer (A1). In the polymer (2), the total content of the structures derived from the polymerizable monomers (A2) and (B) is, for example, 50% by mass or more, 70% by mass or more, 90% by mass or more, 95% by mass or more with respect to the whole polymer (2). It may be substantially 100% by mass. When it is substantially 100% by mass, the polymer (2) may contain a structure derived from inevitable impurities.

[0033] In the polymer (1) and the polymer (2), the content of each polymerization unit can be controlled by adjusting the blending amount of the polymerizable monomer in the polymerization component. The ratio of the structure derived from each polymerizable monomer in the polymer is a value calculated from the mass ratio of each polymerizable monomer to the total amount of the polymerization components used.

[0034] In one embodiment, polymer (1) and polymer (2) do not contain fluorine atoms. In one embodiment, polymer (1) and polymer (2) do not contain silicon atoms.

[0035] The polymerization methods of polymer (1) and polymer (2) are not particularly limited, and they can be produced by solution polymerization method, bulk polymerization method, emulsion polymerization method, etc. based on polymerization mechanisms such as radical polymerization method, cationic polymerization method, and anionic polymerization method. For example, in the case of the radical polymerization method, a polymer can be produced by charging a polymerizable monomer mixture into an organic solvent and adding a general-purpose radical polymerization initiator.

[0036] As the polymerization initiator, various ones can be used, for example, peroxides such as t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, and diacyl peroxide, azo compounds such as azobisisobutyronitrile, dimethyl azobisisobutyrate, and phenylazotriphenylmethane, and metal chelate compounds such as Mn(acac)3. If necessary, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, or a thiol compound having a coupling group such as γ-mercaptopropyltrimethoxysilane may be used as an additive such as a chain transfer agent.

[0037] Examples of organic solvents include alcohol solvents such as ethanol, isopropyl alcohol, n-butanol, iso-butanol, tert-butanol, etc.; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, etc.; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, etc.; monocarboxylic acid ester solvents such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, etc.; polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc.; ether solvents such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, etc.; solvents of propylene glycol and its esters such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, etc.; halogen solvents such as 1,1,1-trichloroethane, chloroform, etc.; cyclic ether solvents such as tetrahydrofuran, dioxane, etc.; aromatic solvents such as benzene, toluene, xylene, etc.; fluorinated solvents such as perfluorooctane, perfluorotri-n-butylamine, etc. These solvents can be used alone or in combination of two or more.

[0038] Polymer (1) and polymer (2) may be block copolymers or random copolymers, but random copolymers are preferred. Also, they may be free radical copolymers or living copolymers, but free radical copolymers are preferred.

[0039] The polymer (1) and the polymer (2) are preferably random copolymers. For example, in the case of the polymer (2) containing the polymerizable monomer (A2) and the polymerizable monomer (B) as polymerization components, it is preferably a copolymer in which the structure derived from the polymerizable monomer (A2) and the structure derived from the polymerizable monomer (B) are randomly arranged.

[0040] In the present invention, preferably, the polymer (1) and the polymer (2) do not contain a block structure. For example, in the case of the polymer (2), preferably, it does not contain a block copolymer in which a block of the structure derived from the polymerizable monomer (A2) and a block of the structure derived from the polymerizable monomer (B) are linked, and more preferably, it does not contain a block of the structure derived from the polymerizable monomer (A2) and / or a block of the structure derived from the polymerizable monomer (B). The production of block polymers generally requires a metal catalyst, and the resulting block polymers inevitably contain metal impurities. In nanometer-order lithography, even trace amounts of metal impurities may affect the resist performance. On the other hand, since the curable resin composition of the present invention does not require a metal catalyst for production and does not contain metal impurities, it is possible to avoid adverse effects on the resist performance. In addition, the production of block copolymers is generally complicated to manage. Specifically, if the monomer that becomes the second block is introduced when the polymerization rate of the first block is low, there is a risk that the block formation will be insufficient. On the other hand, if the monomer that becomes the second block is introduced when the polymerization rate of the first block is high, deactivation of the active terminal may occur, and there is a risk that the polymerization reaction will not proceed sufficiently. In addition, measures to prevent the mixing of polymerization deactivating substances such as oxygen that interfere with block formation are also required. The curable resin composition of the present invention is excellent also in that the production management is not complicated.

[0041] The weight average molecular weight (Mw) of the polymer (1) and the polymer (2) is preferably in the range of 2,000 to 80,000, and more preferably in the range of 3,000 to 50,000. The weight average molecular weight of the polymer is measured by the method described in the examples.

[0042] In addition to the polymers (1) and (2) described above, the curable resin composition of the present invention may contain various additives such as a solvent, other resins, surfactants, dyes, fillers, crosslinking agents, dissolution accelerators, etc. For example, by dissolving at least one of the polymers (1) and (2) in a solvent, a resist composition for coating is obtained. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone; alcohols such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, and decanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane; alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether; esters such as ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, and butyl lactate; monocarboxylic acid esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, and butyl 2-methoxypropionate; cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate; propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; halogenated hydrocarbons such as trichloroethylene, Freon solvents, HCFC, and HFC.Fully fluorinated solvents such as perfluorooctane, aromatics such as toluene and xylene; polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone can be mentioned. These solvents may be used alone or in combination of two or more.

[0043] The curable resin composition of the present invention can be suitably used for compositions for lithography, compositions for forming a resist underlayer film, etc. The curable resin composition can be made into a cured product by heating, drying, etc., if necessary. When the curable resin composition of the present invention is used for a resist underlayer film (BARC film) application, the above-described polymer (1) and / or polymer (2), and further, if necessary, various additives such as a solvent, other resins, a surfactant, a dye, a filler, a crosslinking agent, and a dissolution accelerator can be added to obtain a composition for a resist underlayer film. Further, the curable resin composition of the present invention can also be made into a composition for lithography.

[0044] The composition for lithography or the composition for a resist underlayer film can be prepared by blending the above components and mixing them using a stirrer or the like. Further, when the composition for a resist underlayer film contains a filler or a pigment, it can be adjusted by dispersing or mixing it using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill.

[0045] To form a resist underlayer film from the composition for a resist underlayer film, for example, the above-described composition for a resist underlayer film is applied onto an object for performing photolithography such as a silicon substrate, dried under a temperature condition of 100 to 200°C, and then further heat-cured under a temperature condition of 250 to 400°C. Next, a resist pattern is formed by performing a normal photolithography operation on this underlayer film, and a resist pattern by a multilayer resist method can be formed by performing a dry etching treatment with a halogen-based plasma gas or the like.

Examples

[0046] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples. It should be noted that the present invention is not limited to the following Examples.

[0047] The measurement conditions of GPC for the resins obtained in the following Examples and Comparative Examples are as follows. [GPC Measurement Conditions] Measuring device: "Empower3 Advanced Polymer Chromatography" manufactured by Waters Column: "ACQUITY APC XT45 4.6mmΦ×150mm" manufactured by Waters + "ACQUITY APC XT200 4.6mmΦ×75mm" manufactured by Waters Detector: Differential refractometer (RID) Data processing: Measurement conditions: Column temperature 40°C Developing solvent Tetrahydrofuran (THF) Flow rate 0.6 mL / min Measurement method: Polystyrene standard method

[0048] Example 1 (Preparation of curable resin composition (A-1)) 35.5 g of glycidyl methacrylate, 55.6 g of isobornyl methacrylate, and 6.4 g of 2,2'-azobis(isobutyric acid) dimethyl were charged into a four-necked flask equipped with a thermometer, a condenser, and a stirrer, and dissolved in 97.5 g of methyl isobutyl ketone as a reaction solvent. After dissolution, the mixture was stirred and reacted under reflux at 80°C for 8 hours using a mantle heater. After the reaction, the solvent was distilled off under reduced pressure from the resin solution, and vacuum drying was performed to obtain a resin. The weight average molecular weight (Mw) of the resin obtained by the GPC method was 11,486. 2.00 g of the obtained resin was dissolved in 8 g of propylene glycol monomethyl ether acetate, and precision filtration was performed using a 0.1 μm PTFE disk filter to obtain a curable resin composition (A-1).

[0049] Example 2 (Preparation of curable resin composition (A-2)) The resin and the curable resin composition (A-2) were obtained in the same manner as in Example 1, except that the charged amounts of the starting materials were 32.7 g of glycidyl methacrylate, 51.1 g of isobornyl methacrylate, 11.7 g of 2,2'-azobis(isobutyric acid) dimethyl, and 95.6 g of methyl isobutyl ketone as the reaction solvent. The Mw of the obtained resin was 5,858.

[0050] Example 3 (Preparation of curable resin composition (A-3)) The resin and the curable resin composition (A-3) were obtained in the same manner as in Example 1, except that the charged amounts of the starting materials were 17.1 g of glycidyl methacrylate, 26.4 g of benzyl methacrylate, 3.0 g of 2,2'-azobis(isobutyric acid) dimethyl, and 139.6 g of methyl isobutyl ketone as the reaction solvent. The Mw of the obtained resin was 7,885.

[0051] Example 4 (Preparation of curable resin composition (A-4)) The resin and the curable resin composition (A-4) were obtained in the same manner as in Example 1, except that the charged amounts of the starting materials were 14.2 g of glycidyl methacrylate, 22.0 g of 1-naphthylmethyl acrylate, 2.5 g of 2,2'-azobis(isobutyric acid) dimethyl, and 116.2 g of methyl isobutyl ketone as the reaction solvent. The Mw of the obtained resin was 9,487.

[0052] Example 5 (Preparation of curable resin composition (A-5)) The resin and the curable resin composition (A-5) were obtained in the same manner as in Example 1, except that the charged amounts of the starting materials were 79.9 g of 4-vinylbenzyl glycidyl ether, 5.6 g of 2,2'-azobis(isobutyric acid) dimethyl, and 85.5 g of methyl isobutyl ketone as the reaction solvent, and after dissolution, the mixture was stirred and reacted at 80 °C under reflux for 16 hours using a mantle heater. The Mw of the obtained resin was 8,549.

[0053] Example 6 (Preparation of curable resin composition (A-6)) The resin and the curable resin composition (A-6) were obtained in the same manner as in Example 5, except that the charged starting materials were 17.1 g of 4-vinylbenzyl glycidyl ether, 15.5 g of benzyl methacrylate, 4.6 g of 2,2'-azobis(isobutyric acid) dimethyl, and 104.6 g of methyl isobutyl ketone as the reaction solvent. The Mw of the obtained resin was 6,145.

[0054] Example 7 (Preparation of curable resin composition (A-7)) The resin and the curable resin composition (A-7) were obtained in the same manner as in Example 5, except that the charged starting materials were 41.9 g of 4-vinylbenzyl glycidyl ether, 37.7 g of 1-naphthylmethyl acrylate, 5.6 g of 2,2'-azobis(isobutyric acid) dimethyl, and 85.1 g of methyl isobutyl ketone as the reaction solvent. The Mw of the obtained resin was 13,568.

[0055] Comparative Example 1 (Preparation of curable resin composition (A-8)) The resin and the curable resin composition (A-8) were obtained in the same manner as in Example 5, except that the charged starting materials were 75.1 g of methyl methacrylate, 5.3 g of 2,2'-azobis(isobutyric acid) dimethyl, and 80.4 g of propylene glycol monomethyl ether acetate as the reaction solvent. The Mw of the obtained resin was 12,430.

[0056] Comparative Example 2 (Preparation of curable resin composition (A-9)) The resin and the curable resin composition (A-9) were obtained in the same manner as in Example 1, except that the charged starting materials were 92.4 g of glycidyl methacrylate, 6.5 g of 2,2'-azobis(isobutyric acid) dimethyl, and 98.9 g of propylene glycol monomethyl ether acetate as the reaction solvent. The Mw of the obtained resin was 14,452.

[0057] Comparative Example 3 (Preparation of curable resin composition (A-10)) The resin and the curable resin composition (A-10) were obtained in the same manner as in Example 1, except that the starting materials were charged with 35.2 g of benzyl methacrylate, 2.5 g of 2,2'-azobis(isobutyric acid) dimethyl, and 113.1 g of propylene glycol monomethyl ether acetate as the reaction solvent. The Mw of the obtained resin was 10,765.

[0058] Comparative Example 4 (Preparation of curable resin composition (A-11)) A curable resin composition (A-11) was obtained in the same manner as in Example 1, except that EPICLON N-680 (manufactured by DIC Corporation) was used as the resin.

[0059] Comparative Example 5 (Preparation of curable resin composition (A-12)) A curable resin composition (A-12) was obtained in the same manner as in Example 1, except that EPICLON HP-7200 (manufactured by DIC Corporation) was used as the resin.

[0060] [Evaluation] Using the curable resin compositions prepared in the examples and comparative examples, dry etching resistance, volatility (remaining film characteristics during heating), heat curability (solvent resistance of the heat-cured film), and substrate adhesion were evaluated.

[0061] (1) Dry etching resistance The obtained curable resin composition was applied onto a 5-inch diameter silicon wafer using a spin coater, and then heated on a hot plate at 100 °C for 60 seconds in an atmosphere with an oxygen concentration of 20 vol% to obtain a silicon wafer with a resist underlayer film. The formed resist underlayer film was etched using an etching apparatus (manufactured by Samco: RIE-200NL) under the conditions of CF4 (CF4: 89 sccm, pressure: 2.0 Pa, RF power: 100 W, treatment time: 180 seconds). The film thickness before and after the etching treatment was measured to calculate the etching rate and evaluate the dry etching resistance. The evaluation criteria are as follows. ○: When the etching rate is 75 nm / min or less ×: When the etching rate exceeds 75 nm / min The evaluation results are shown in Tables 1 and 2.

[0062] (2) Volatility (residual film characteristics during heating) The obtained curable resin composition was applied onto a 5-inch diameter silicon wafer using a spin coater, and then heated at 100 °C for 60 seconds on a hot plate in an atmosphere with an oxygen concentration of 20 vol% to produce a silicon wafer with a resist underlayer film. Next, this was heated (hard baked) at 250 °C for 600 seconds in a hot plate, and the volatility was evaluated from the film thickness change before and after the hard bake. The evaluation criteria are as follows. ○: When the residual film ratio is 80% or more ×: When the residual film ratio is less than 80% The evaluation results are shown in Tables 1 and 2.

[0063] (3) Heat curability (solvent resistance of the heat-cured film) The silicon wafer with the cured product after the hard bake prepared in the above volatility (residual film characteristics during heating) test was immersed in propylene glycol monomethyl ether acetate for 60 seconds, and then heated and dried at 100 °C for 60 seconds on a hot plate. The heat curability was evaluated from the film thickness change in this process. The evaluation criteria are as follows. ○: When the residual film ratio is 80% or more ×: When the residual film ratio is less than 80% The evaluation results are shown in Tables 1 and 2.

[0064] (4) Substrate adhesion The obtained curable resin composition was applied onto a 10 cm square non-alkali glass substrate using a spin coater, and then heated at 100 °C for 60 seconds on a hot plate in an atmosphere with an oxygen concentration of 20 vol% to produce a glass substrate with a resist underlayer film. An aluminum stud and the resist underlayer film were joined using an adhesive. After standing at 23 °C for 24 hours, the stud was pulled at a speed of 1.6 MPa / second using a coating film adhesion tester manufactured by All Good Co., and the load at the time of peeling was measured. The evaluation results are shown in Tables 1 and 2.

[0065]

Table 1

[0066]

Table 2

[0067] From Table 1 and Table 2, it can be confirmed that the cured product obtained from the curable resin composition of the present invention has high dry etching resistance, low volatility during heating, good heat curability (high solvent resistance), and high substrate adhesion.

Claims

1. A curable resin composition containing at least one of the following polymers (1) and (2). (1) A polymer containing a structure derived from a polymerizable monomer (A1) having at least one of an alicyclic structure and an aromatic ring structure and a cyclic ether group (2) A polymer containing a structure derived from a polymerizable monomer (A2) having a cyclic ether group and a structure derived from a polymerizable monomer (B) having at least one of an alicyclic structure and an aromatic ring structure

2. The curable resin composition according to claim 1, wherein the polymerizable monomer (A1) is a compound represented by the following general formula (A1-1). 【Chemical 4】 (In the general formula (A1-1), R １１ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L １１ is a divalent linking group containing at least an arylene group, Z is an epoxy group, an oxetanyl group, an alkyloxetanyl group having 4 to 10 carbon atoms, or an epoxycycloalkyl group having 5 to 10 carbon atoms.)

3. The curable resin composition according to claim 1, wherein the polymerizable monomer (A2) is a compound represented by the following general formula (A2-1). 【Chemical Formula 5】 (In the general formula (A2-1), R １２ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L １２ is a single bond or a divalent linking group, Z is an epoxy group, an oxetanyl group, an alkyloxetanyl group having 4 to 10 carbon atoms, or an epoxycycloalkyl group having 5 to 10 carbon atoms.)

4. The curable resin composition according to claim 1, wherein the polymerizable monomer (B) is a compound represented by the following general formula (B-1). 【Chemical Formula 6】 (In the general formula (B-1), R ２１ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L ２１ is a single bond or a divalent linking group, X is an aromatic group or an alicyclic hydrocarbon group.)

5. The curable resin composition according to claim 1, wherein the content of the structure derived from the polymerizable monomer (B) in the polymer of (2) is 30 to 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A2).

6. The curable resin composition according to any one of claims 1 to 5, which is a composition for lithography.

7. The curable resin composition according to any one of claims 1 to 5, which is a composition for forming a resist underlayer film.

8. A resist underlayer film which is a cured product of the composition for forming a resist underlayer film according to claim 7.

9. A cured product of the curable resin composition according to any one of claims 1 to 5.

Images