TWI489203B - Positive radiation-sensitive composition, interlayer insulation film, and method for producing the same - Google Patents

Description

Positive type radiation linear composition, interlayer insulating film and forming method thereof

The present invention relates to a positive-type radiation-sensitive composition suitable as a material for forming an interlayer insulating film of a display element such as a liquid crystal display element (LCD) or an organic EL display element (OLED), an interlayer insulating film formed of the composition, and A method of forming the interlayer insulating film.

In the display element, an interlayer insulating film is generally provided for the purpose of insulating the interconnects arranged in a layered manner. A radiation-sensitive composition is widely used as a material for forming an interlayer insulating film because it is preferable that the number of steps for obtaining a necessary pattern shape of the composition is small and that it has sufficient flatness.

Further, the interlayer insulating film of the display element must form a pattern of contact holes for wiring. Since the negative-type composition is difficult to form a contact hole having an aperture of a practical use level, a positive-type radiation-sensitive composition is widely used in forming an interlayer insulating film of a display element (refer to Japanese Laid-Open Patent Publication No. 2001-354822).

On the other hand, an acrylic resin is mainly used as a component of the radiation sensitive composition used for forming the interlayer insulating film. On the other hand, attempts have been made to use a polyoxyalkylene-based material which is more excellent in heat resistance and transparency than an acrylic resin as a component of a radiation-sensitive composition (refer to Japanese Laid-Open Patent Publication No. 2000-1648, JP-A-2006-- Bulletin No. 178436).

A display element such as a TFT-type liquid crystal display element using such an interlayer insulating film as such a display element is produced by a step of forming a transparent electrode film on an interlayer insulating film and then forming a liquid crystal alignment film thereon. In this case, the interlayer insulating film is exposed to high temperature conditions in the formation step of the transparent electrode film, or exposed to the resist stripping liquid used for forming the electrode pattern, so resistance to them must be required. Further, in the developing step of the interlayer insulating film, if the developing time is slightly excessive than the optimum time, the developer penetrates between the pattern and the substrate, and peeling easily occurs, so the development time must be strictly controlled. In addition, in recent years, display devices using display elements such as TFT-type liquid crystal display elements have a tendency to increase in size, increase in brightness, high precision, high-speed response, and thinness, so that they are used to form an interlayer insulating film. The high radiation sensitivity of the radiation-sensitive composition and the low dielectric constant and high transmittance of the formed interlayer insulating film are also currently increasing, requiring high performance.

Due to the widespread use of large-screen televisions in recent years and the demand for reduction in manufacturing costs, the size of substrate glass used in the production of substrates with color filters has also increased. Therefore, in the coating step of the radiation sensitive composition when the interlayer insulating film is formed on the substrate, it is difficult to employ a spin coating method which is widely used at present. Therefore, in order to apply a large-sized glass substrate, a so-called slit coating method in which a radiation-sensitive composition is sprayed from a slit-shaped nozzle can be used instead of the spin coating method. Such a slit coating method has an advantage of reducing the amount of the radiation-sensitive composition required for coating as compared with the spin coating method, and also contributes to reducing the manufacturing cost of the display element. In the slit coating method, the substrate is adhered to the coating stage by vacuum suction, and the coating film is swept in a predetermined direction from the coating nozzle to form a coating film on the substrate. After the coating film is formed, by raising the support pin hidden in the hole for vacuum suction, the substrate is lifted from the coating table and transported to the next step. In this series of steps, unevenness in formation of fine concavities and convexities due to pores for vacuum adsorption may occur on the coating film, which may become an obstacle to achieving high level of flatness required as a property of the interlayer insulating film.

Under the circumstances, it has been strongly desired to develop a positive-type radiation linear composition of a polyorganosiloxane which can form heat resistance, transparency, solvent resistance and low dielectric which are generally required as an interlayer insulating film. It is excellent in electrical properties and has a high level of flatness (film thickness uniformity) without coating unevenness, and has high radiation sensitivity and large development margin (allowable range of development time for forming a good pattern) ).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-1648

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-178436

The present invention has been made in view of the above problems, and an object thereof is to provide a positive-type radiation-sensitive composition of a polyorganosiloxane, which can be formed to have excellent heat resistance, transparency, solvent resistance, and low dielectric properties. And an interlayer insulating film having high flatness (film thickness uniformity) without uneven coating, and having high radiation sensitivity and large development margin; and providing an interlayer insulating film formed of the composition, and A method of forming the interlayer insulating film.

The present invention has been made in order to solve the above problems, and is a positive radiation sensitive composition comprising:

[A] a nonoxyl polymer,

[B] quinone diazide, and

[C] includes (c1) a compound represented by the following formula (1), (c2) a compound represented by the following formula (2), and (c3) a polymerizable group having a group represented by the following formula (3); A copolymer of a polymerizable unsaturated compound of an unsaturated compound.

CH ₂ =CR ¹ COO─C _α H _2α ─C _β F _2β+1 (1)

In the formula (1), R ¹ is a hydrogen atom or a methyl group, α is an integer of 0 to 6, and β is an integer of 1 to 20.

CH ₂ =CR ² COO─(C _γ H _2γ ─O) _a ─R ³ (2)

In the formula (2), R ² is a hydrogen atom or a methyl group, R ³ is an alkyl group having 1 to 12 carbon atoms, γ is 2 or 3, and a is a repeating unit number, and the number average thereof is 1 to 30.

In the formula (3), R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group having 1 to 20 carbon atoms, a phenyl group or a group represented by the following formula (4), b It is an integer from 0 to 3.

In the formula (4), R ⁹ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 20 carbon atoms or a phenyl group, and c is an integer of 0 to 3.

The positive-type radiation-sensitive linear composition has positive radiation-sensing characteristics, and further contains a copolymer [C] component formed of a monomer having a specific structure in addition to the above [A] and [B] components. An insulating film having excellent properties such as heat resistance, transparency, solvent resistance, and low dielectric property is satisfactorily formed, and an interlayer insulating film having high flatness (film thickness uniformity) without uneven coating is formed. In addition, the positive-type radiation-radiating composition has excellent radiation sensitivity and development margin.

In the positive radiation sensitive composition, the [C] copolymer preferably further comprises (c4) an alkane having 1 to 8 carbon atoms in addition to the compound (c1), the compound (c2) and the compound (c3). A copolymer of a polymerizable unsaturated compound of a polymerizable unsaturated compound. Thereby, the affinity of the [C] copolymer for other components and the solvent can be improved, and the film thickness uniformity of the obtained interlayer insulating film can be further improved.

In the positive radiation sensitive composition, the [C] copolymer preferably further comprises (c5) in one molecule in addition to the compound (c1), the compound (c2), the compound (c3) and the compound (c4). A copolymer of a polymerizable unsaturated compound having a polymerizable unsaturated compound having two or more unsaturated bonds. Thereby, the film thickness uniformity and strength of the obtained interlayer insulating film can be improved, and general properties such as heat resistance can be improved.

In the positive radiation sensitive resin composition, the compound (c1) is a compound represented by the following formula (5), and the compound (c2) is a compound represented by the following formula (6).

The [C] copolymer is preferably 25 to 35 mass% of the compound (c1), 20 to 30 mass% of the compound (c2), 15 to 20 mass% of the compound (c3), and 25 to 35 mass% of the compound (c4), and A copolymer of a polymerizable unsaturated compound composed of 1 to 5 mass% of the compound (c5).

CH ₂ =CR ¹ COOC ₂ H ₄ C _β F _2β+1 (5)

In the formula (5), R ¹ is the same as defined in the above formula (1). β is an integer from 1 to 8.

CH ₂ =CR ² COO(C ₂ H ₄ O) _a R ³ (6)

In the formula (6), R ² and R ³ are the same as defined in the above formula (2), and the number average of the number of repeating units a is 4 to 12.

By using such a [C] copolymer, as a function of a surfactant having a high surface tension and low performance, even when the ratio of the copolymer is small, the surface smoothness of the coating film can be improved, and the formed interlayer can be further improved. Film thickness uniformity of the insulating film.

The [A] siloxane polymer of the positive-type radiation-sensitive composition is preferably a hydrolysis-condensation product of the hydrolyzable decane compound represented by the following formula (7).

(R ¹² ) _x ─Si─(OR ¹³ ) _4-x (7)

In the formula (7), R ¹² is a non-hydrolyzable organic group having 1 to 20 carbon atoms, R ¹³ is an alkyl group having 1 to 4 carbon atoms, and x is an integer of 0 to 3.

In the positive-type radiation-sensitive composition, by using the hydrolysis-condensation product of the hydrolyzable decane compound represented by the above formula (7) as the [A] siloxane polymer, the radiation sensitivity and the development margin can be further improved.

The positive-type radiation-sensitive composition preferably further contains a [D] heat-sensitive acid generator or a heat-sensitive base generator. By using such a thermosensitive acid or alkali generating agent, the condensation reaction of the component [A] in the heating step after development of the positive-type radiation-sensitive composition can be further promoted, and the heat resistance and solvent resistance of the obtained cured film can be further improved. .

The positive-type radiation-sensitive composition preferably further contains [E] a dehydrating agent. As described above, by further containing a dehydrating agent, the storage stability of the positive-type radiation-sensitive composition can be improved.

Further, a method of forming an interlayer insulating film for a display element of the present invention includes:

(1) a step of forming a coating film of the positive-type radiation-sensitive composition on a substrate,

(2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation,

(3) a step of developing the coating film irradiated with radiation in the step (2), and

(4) a step of heating the coating film developed in the step (3).

In this method, the above-described positive-type radiation-sensitive linear composition having excellent radiation sensitivity and development margin is used, and a pattern is formed by radiation-sensitive exposure, development, and heating, whereby fine and delicate can be easily formed. An interlayer insulating film is used for the display element of the pattern. Further, the generally required properties of the interlayer insulating film thus formed, that is, all of the properties of heat resistance, transparency, solvent resistance, and low dielectric property are excellent in balance, and have a high level of unevenness in coating unevenness. Sex.

Effect of the invention

As described above, the positive-type radiation-sensitive composition of the present invention can form heat-resistant, transparent, solvent-resistant, and low-quality properties by containing the components [A], [B], and [C] described above. The dielectric properties are generally required, and at the same time, there is an interlayer insulating film having a high level of flatness without coating unevenness. In addition, the positive-type radiation linear composition exhibits excellent radiation sensitivity and development margin.

Form for implementing the invention

The positive radiation sensitive composition of the present invention contains [A] a decane polymer, [B] quinonediazide compound, and [C] a copolymer formed of a monomer having a specific structure, and may optionally contain other The component ([D] sensible acid generator or sensible base generator, etc.) is selected.

[A] component: a siloxane polymer,

The siloxane polymer of the component [A] is not particularly limited as long as it is a polymer having a decane bond. This [A] component forms a cured product by self-condensation. When a [D] sensible acid generator or a sensible alkali generator described later as an optional component is added to the positive susceptibility radiation composition, an acidic active substance or a basic active substance is produced by heating, which becomes a catalyst. Further promotes the self-condensation of the [A] component.

The oxime polymer as the component [A] is preferably a hydrolysis condensate of the hydrolyzable decane compound represented by the above formula (7). The "hydrolyzable decane compound" described in the present application generally means that it can be hydrolyzed by heating at a temperature ranging from room temperature (about 25 ° C) to about 100 ° C in the presence of no catalyst and excess water. A decane compound of a hydrolyzable group of a stanol group, or a decane compound having a hydrolyzable group capable of forming a oxirane condensate. On the other hand, the "non-hydrolyzable group" means a group which stably exists without hydrolysis or condensation under such hydrolysis conditions.

In the hydrolysis reaction of the hydrolyzable decane compound represented by the above formula (7), a part of the hydrolyzable group may remain in an unhydrolyzed state. Further, the "hydrolyzed condensate of a hydrolyzable decane compound" as used herein means a hydrolysis condensate formed by reaction and condensation between a stanol group of a part of a hydrolyzed decane compound.

Examples of the non-hydrolyzable organic group having 1 to 20 carbon atoms represented by R ¹² include unsubstituted or having a carbon number of 1 to 12 or a vinyl group, a (meth) acrylonitrile group or an epoxy group. The group is substituted with one or more alkyl groups, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and the like. They may be linear, branched or cyclic, and when the same molecular memory is in a plurality of R ¹² , it may be a combination thereof. In addition, R ¹² may contain a structural unit having a hetero atom. Examples of such a structural unit include an ether, an ester, a thioether, and the like.

Specific examples of the alkyl group having 1 to 4 carbon atoms represented by the above R ¹³ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and a butyl group. Among these R ¹³ , a methyl group and an ethyl group are preferred from the viewpoint of easiness of hydrolysis. Further, the subscript x is an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0 or 1, and most preferably 1. When x is an integer of 0 to 2, the hydrolysis and the condensation reaction are more easily carried out, and as a result, the rate of the hardening reaction by the self-condensation of the [A] component becomes larger, and the heat resistance of the obtained interlayer insulating film can be further improved. And solvent resistance.

The hydrolyzable decane compound represented by the above formula (7) includes a decane compound substituted with four hydrolyzable groups, a decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, and two a non-hydrolyzable group and two hydrolyzable group-substituted decane compounds, a decane compound substituted with three non-hydrolyzable groups and one hydrolyzable group, or a mixture thereof.

Specific examples of the hydrolyzable decane compound represented by the above formula (7) include tetramethoxy decane and tetraethoxy decane, respectively, as the decane compound substituted with four hydrolyzable groups. Tetrabutoxydecane, tetraphenoxydecane, tetrabenzyloxydecane, tetra-n-propoxydecane, tetraisopropoxydecane, etc.; substituted as a non-hydrolyzable group and three hydrolyzable groups The decane compound may, for example, be chlorotrimethoxydecane, methyltrimethoxydecane, methyltriethoxydecane, methyltriisopropoxydecane, methyltributoxydecane or ethyltrimethoxy. Decane, ethyltriethoxydecane, ethyltriisopropoxydecane, ethyltributoxydecane, butyltrimethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, ethylene Trimethoxy decane, vinyl triethoxy decane, vinyl tri-n-propoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-methyl propylene methoxy propyl triethyl Oxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxyl Triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl triethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy a decane compound or the like; as a decane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, dichlorodimethoxydecane, dimethyldimethoxydecane, diphenyldi a methoxy decane, a dibutyl dimethoxy decane, etc.; as a decane compound substituted by three non-hydrolyzable groups and one hydrolyzable group, trichloromethoxy decane, tributyl methoxy group Decane, trimethyl methoxy decane, trimethyl ethoxy decane, tributyl ethoxy decane, and the like.

Among the hydrolyzable decane compounds represented by the above formula (7), a decane compound substituted with four hydrolyzable groups and a decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups are preferable. A decane compound substituted with a non-hydrolyzable group and three hydrolyzable groups. Specific examples of the preferred hydrolyzable decane compound include tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, methyl triisopropoxy decane, and methyl tributoxide. Base decane, phenyltrimethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, ethyltriisopropoxydecane, ethyltributoxydecane, butyltrimethoxydecane, gamma - glycidoxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane. These hydrolyzable decane compounds may be used alone or in combination of two or more.

The conditions for hydrolyzing and condensing the hydrolyzable decane compound represented by the above formula (7) are such that at least a part of the hydrolyzable decane compound represented by the above formula (7) is hydrolyzed, and the hydrolyzable group is converted into a stanol group. The condensation reaction is not particularly limited, and an example can be carried out as follows. The water used for the hydrolysis and condensation of the hydrolyzable decane compound represented by the above formula (7) is preferably water purified by a method such as a reverse osmosis membrane treatment, an ion exchange treatment, or a distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of the water to be used is preferably 0.1 to 3 mol, more preferably 0.3 to 2 mol, based on 1 mol of the hydrolyzable group (-OR ¹³ ) of the hydrolyzable decane compound represented by the above formula (7). An amount of 0.5 to 1.5 mol. By using this amount of water, the reaction rate of hydrolysis and condensation can be optimized.

The solvent which can be used for the hydrolysis and condensation of the hydrolyzable decane compound represented by the above formula (7) is not particularly limited, and usually, the same solvent as that used in the preparation of the positive-type radiation-sensitive composition described later can be used. Solvent. Preferable examples of such a solvent include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid. Esters. Among these solvents, Tejia diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or 3-methoxy Methyl propyl propionate.

The hydrolysis and condensation reaction of the hydrolyzable decane compound represented by the above formula (7) is preferably carried out on an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidity). Ion exchange resin, various Lewis acid), alkali catalyst (for example, ammonia, primary amine, secondary amine, tertiary amine, pyridine and other nitrogen-containing compounds; basic ion exchange resin; hydroxide such as sodium hydroxide; potassium carbonate It is carried out in the presence of a catalyst such as a carbonate; a carboxylate such as sodium acetate; various Lewis bases; or an alkoxide (for example, zirconium alkoxide, titanium alkoxide or aluminum alkoxide). For example, aluminum tetraisopropoxide can be used as the alkane alumina. The amount of the catalyst to be used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1 mol, per mol of the monomer of the hydrolyzable decane compound from the viewpoint of promoting hydrolysis and condensation reaction.

The reaction temperature and reaction time in the hydrolysis and condensation of the hydrolyzable decane compound represented by the above formula (7) can be appropriately set. For example, the following conditions can be employed. The reaction temperature is preferably from 40 to 200 ° C, more preferably from 50 to 150 ° C. The reaction time is preferably from 30 minutes to 24 hours, more preferably from 1 to 12 hours. By selecting such a reaction temperature and reaction time, the hydrolysis and condensation reaction can be carried out most efficiently. In the hydrolysis and condensation, a hydrolyzable decane compound, water, and a catalyst may be added in one portion of the reaction system to carry out a single-step reaction; or a hydrolyzable decane compound, water, and a catalyst may be added to the reaction system in several portions. Multi-step hydrolysis and condensation reactions. Further, after the hydrolysis and condensation reaction, a dehydrating agent is added, followed by evaporation to remove water and the produced alcohol from the reaction system. The dehydrating agent used in this stage generally is dehydrated or completely removed by adsorption or inclusion of excess water, or is removed by evaporation, so that the component [E] added later added to the positive-type radiation-sensitive composition is not included. Within the scope of dehydrating agents.

The molecular weight of the hydrolysis-condensation product of the hydrolyzable decane compound represented by the above formula (7) can be measured by a number average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) using tetrahydrofuran as a mobile phase. Further, the number average molecular weight of the hydrolysis condensate is usually preferably a value in the range of 5.0 × 10 ² to 1.0 × 10 ⁴ , more preferably a value in the range of 1.0 × 10 ³ to 5.0 × 10 ³ . When the value of the number average molecular weight of the hydrolysis-condensation product is 5.0 × 10 ² or more, the film formability of the coating film of the positive-type radiation-sensitive composition can be improved. On the other hand, when the value of the number average molecular weight of the hydrolysis-condensation product is 1.0 × 10 ⁴ or less, the radiation sensitivity of the radiation-sensitive composition can be prevented from being lowered.

[B] component: quinonediazide compound

The component [B] is a quinonediazide compound which generates a carboxylic acid by irradiation with radiation. The positive-type radiation-sensitive composition containing such a quinonediazide compound has positive-type radiation characteristics of the exposed portion which is removed in the step of radiation irradiation by a developing step. As the quinonediazide compound as the component [B], a compound obtained by esterifying a compound having a phenolic hydroxyl group constituting a mother nucleus and a naphthoquinonediazide sulfonium halide is preferably used. Examples of the compound having a phenolic hydroxyl group include a compound in any case where the ortho and para positions of the phenolic hydroxyl group are independently hydrogen or a substituent represented by the following formula (8).

In the formula, R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group or a substituted phenyl group. In addition, a ring may be formed by two or three of R ¹⁴ , R ¹⁵ and R ¹⁶ .

In the substituent represented by the above formula (8), when R ¹⁴ , R ¹⁵ and R ¹⁶ are an alkyl group having 1 to 10 carbon atoms, the alkyl group may or may not be substituted. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-hexyl group, cyclohexyl group, n-heptyl group, and n-octyl group. Base, trifluoromethyl, 2-carboxyethyl. Examples of the substituent of the substituted phenyl group include a hydroxyl group and the like. Further, examples of the ring which can be formed by two or three of R ¹⁴ , R ¹⁵ and R ¹⁶ include a cyclopentane ring, a cyclohexane ring, an adamantane ring and an anthracene ring.

Examples of the compound having a phenolic hydroxyl group include a group of compounds represented by the following formulas (9) and (10).

As another example of the compound having a phenolic hydroxyl group, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene] Phenol, 1,1,1-tris(p-hydroxyphenyl)ethane, etc.

As the naphthoquinonediazidesulfonium halide, 4-naphthoquinonediazidesulfonium halide or 5-naphthoquinonediazidesulfonium halide can be used. The ester compound (naphthoquinone diazide compound) obtained from the 4-naphthoquinonediazide compound is suitable for i-line exposure because it has absorption in the i-line (wavelength 365 nm) region. Further, the ester compound (naphthoquinone diazide compound) obtained from the 5-naphthoquinonediazide compound is suitable for exposure over a wide range of wavelengths because of absorption in a wide range of wavelength regions. It is preferred to select an ester compound obtained from a 4-naphthoquinonediazidesulfonium halide or an ester compound obtained from a 5-naphthoquinonediazidesulfonium halide according to the wavelength of exposure. As a particularly preferred quinonediazide compound, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene] A condensate of phenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol).

The molecular weight of the quinonediazide compound is preferably from 300 to 1,500, more preferably from 350 to 1200. When the molecular weight of the quinonediazide compound is 300 or more, the transparency of the formed interlayer insulating film can be maintained high. On the other hand, when the molecular weight of the quinonediazide compound is 1,500 or less, the reduction in pattern formation energy of the positive-type radiation-sensitive composition can be suppressed.

These [B] components may be used alone or in combination of two or more. The amount of the component [B] in the positive radiation sensitive composition is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the component [A]. When the amount of the component [B] is 5 to 100 parts by mass, the difference in solubility between the irradiated portion and the unirradiated portion of the irradiated solution as the developing solution can be made large, and the pattern formation performance is good, and the obtained interlayer is obtained. The solvent resistance of the insulating film is also good.

[C] component: a copolymer formed from a monomer having a specific structure

The component [C] is a copolymer containing at least a structural unit derived from the polymerizable compound (c1), the polymerizable compound (c2), and the polymerizable compound (c3) having the above specific structure. In the positive-acting radiation-linear composition, the copolymer [C] functions as a surfactant having a high surface tension and a high performance, and the interlayer insulating film can be remarkably improved even when the substance is used in a small proportion. Surface flatness.

In the positive-acting radiation-sensitive composition, the copolymer [C] preferably further has a polymerizable unsaturated compound derived from (c4) an unsubstituted alkyl ester group having 1 to 8 carbon atoms (hereinafter, also referred to as abbreviated as follows). It is a structural unit of the "polymerizable compound (c4)"); and further preferably has a polymerizable unsaturated compound derived from (c5) having two or more unsaturated bonds in one molecule (hereinafter, also simply referred to as "polymerizability" The structural unit of the compound (c5)"); particularly preferably, the polymerizable compound (c1), the polymerizable compound (c2), the polymerizable compound (c3), the polymerizable compound (c4), and the polymerizable compound (c5) are contained. The composition is formed.

The group -C _α H _2α - in the above formula (1) is a methylene group or an alkylmethylene group or a linear or branched alkylene group. When the group -C _α H _2α - is not bilaterally symmetric, its connection direction is not limited. The number of carbon atoms α of the group -C _α H _2α - is preferably from 2 to 4. Specific examples of the group -C _α H _2α - may, for example, be 1,2-extended ethyl, 1,2-extended propyl, 1,3-extended propyl, 1,4-tert-butyl, and the like; Among them, a 1,2-extended ethyl group or a 1,3-propanyl group is preferred, and a 1,2-extended ethyl group is particularly preferred.

The group -C _β F _2β+1 in the above formula (1) is a linear or branched fluoroalkyl group. The group -C _β F _{2β+1 has} a carbon number β of from 1 to 20, preferably from 1 to 12, more preferably from 1 to 8, and particularly preferably from 2 to 8. The group -C _β F _{2β+1 is} preferably a linear fluoroalkyl group.

The polymerizable compound (c1) in the present invention is preferably a compound represented by the above formula (5). Specific examples of the compound (c1) include compounds represented by the following formulas (c1-1) and (c1-8).

CH ₂ =CHCOOC ₂ H ₄ C ₈ F ₁₇ (c1-1)

CH ₂ =C(CH ₃ )COOC ₂ H ₄ C ₈ F ₁₇ (c1-2)

CH ₂ =CHCOOC ₂ H ₄ C ₆ F ₁₃ (c1-3)

CH ₂ =C(CH ₃ )COOC ₂ H ₄ C ₆ F ₁₃ (c1-4)

CH ₂ =CHCOOC ₂ H ₄ C ₄ F ₉ (c1-5)

CH ₂ =C(CH ₃ )COOC ₂ H ₄ C ₄ F ₉ (c1-6)

CH ₂ =CHCOOC ₂ H ₄ C ₂ F ₅ (c1-7)

CH ₂ =C(CH ₃ )COOC ₂ H ₄ C ₂ F ₅ (c1-8)

The group -C _γ H _2γ - in the above formula (2) is a linear or branched alkylene group. When the group -C _γ H _2γ - is not bilaterally symmetric, its connection direction is not limited. Specific examples of the group -C _γ H ₂ γ- include, for example, a 1,2-extended ethyl group and a 1,2-extended propyl group, preferably a 1,2-extended ethyl group.

The compound (c2) is used as a mixture of compounds having different values of the number of repeating units a in the above formula (2). The average value of a is 1 to 30, preferably 2 to 20, and particularly preferably 4 to 12. In the compound (c2), when γ is 2, (meth)acrylic acid and ethylene oxide are reacted and synthesized, and when γ is 3, (meth)acrylic acid and propylene oxide are reacted and synthesized. At this time, the number of moles of the introduced ethylene oxide or propylene oxide differs depending on the value of a with respect to 1 mol of (meth)acrylic acid. The a value is a polystyrene-equivalent number average molecular weight which can be determined by gel permeation chromatography for the compound (c2), and is added from ethylene oxide or propylene oxide introduced with respect to 1 mol of (meth)acrylic acid. The number of ears was calculated by calculating the value of the number average molecular weight obtained above.

A commercial product is suitably used as the compound (c2). As an example of such a product, NK-ESTER M-40G, NK-ESTER M-90G, AM-90G manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; Blenmer PME manufactured by Nippon Oil Co., Ltd. -200, PME-400, PME-550, etc.

In the above compound (c3), when a plurality of R ⁵ and R ⁶ are respectively present in the above formula (3), each R ⁵ may be the same or different, and each of R ⁶ may be the same or different. Further, in the above formula (4), when a plurality of R ¹⁰ and R ¹¹ are respectively present, each R ¹⁰ may be the same or different, and each of R ¹¹ may be the same or different. Further, as the compound (c3), preferably, in the above formula (3), R ⁴ , R ⁵ and R ⁶ are each an alkyl group having 1 to 20 carbon atoms or a phenyl group, and R ⁷ and R ⁸ are respectively A polymerizable unsaturated compound having a group represented by the above formula (4).

As the compound (c3), a compound represented by the following formula (c3-1) can be preferably used.

In the formula (c3-1), R ^Si is a group represented by the above formula (4), R ¹⁵ is a hydrogen atom or a methyl group, and d is an integer of 1 to 3.

Specific examples of the compound (c3-1) include compounds represented by the following formulas (c3-1-1), (c3-1-2), and (c3-1-3).

In the formula (c3-1-1), Me is a methyl group, and r, s and t are each an integer of 0 to 3.

In the formula (c3-1-2), Me and r, s and t are defined in the same manner as in the above formula (c3-1-1).

In the formula (c3-1-3), Me and r, s and t are the same as defined in the above formula (c3-1-1), and Ph is a phenyl group.

The compound (c4) may, for example, be an alkyl (meth)acrylate having an unsubstituted alkyl ester group having 1 to 8 carbon atoms. Specific examples of the compound (c4) include n-butyl methacrylate, methyl methacrylate, and 2-ethylhexyl acrylate.

Examples of the compound (c5) include a terminal methacrylated compound such as 1,4-butanediol, polyethylene glycol having a polymerization degree of 1 to 20, and polypropylene glycol having a polymerization degree of 1 to 20. . A commercial product is suitably used as the compound (c5). Examples of such products include NK-ESTER 1G, NK-ESTER 2G, NK-ESTER 3G, NK-ESTER 4G, NK-ESTER 9G, NK-ESTER 14G, etc., manufactured by Shin-Nakamura Chemical Industry Co., Ltd. .

When the copolymer [C] has a structural unit derived from the polymerizable compound (c1), the polymerizable compound (c2), and the polymerizable compound (c3) as described above, the total amount of each polymerizable compound relative to the polymerizable compound The use ratio is 10 to 55% by mass of the polymerizable compound (c1), 10 to 50% by mass of the polymerizable compound (c2), and 5 to 45% by mass of the polymerizable compound (c3).

When the copolymer [C] further has a structural unit derived from the polymerizable compound (c4), the ratio of use of each polymerizable compound to the total amount of these polymerizable compounds is that the polymerizable compound (c1) is 20 to 50% by mass. The polymerizable compound (c2) is 15 to 40% by mass, the polymerizable compound (c3) is 10 to 30% by mass, and the polymerizable compound is 20 to 35% by mass.

When the copolymer [C] further has a structural unit derived from the polymerizable compound (c5), the ratio of use of each polymerizable compound to the total amount of these polymerizable compounds is that the polymerizable compound (c1) is 25 to 35% by mass. The polymerizable compound (c2) is 20 to 30% by mass, the polymerizable compound (c3) is 15 to 20% by mass, the polymerizable compound (c4) is 25 to 35% by mass, and the polymerizable compound (c5) is 1 to 1%. 5 mass%. The compounds (c1) to (c5) used to form the copolymer [C] may be used singly or in combination of two or more.

The copolymer [C] has a mass average molecular weight (Mw) of 5,000 to 25,000, preferably 10,000 to 25,000, particularly preferably 15,000 to 25,000. The molecular weight distribution (Mw/Mn) of the copolymer [C] (the ratio of Mw to the number average molecular weight Mn) is preferably from 1 to 10, more preferably from 2 to 4.

The method for producing the copolymer [C] is not particularly limited, and may be a solution polymerization method, a block polymerization method, or an emulsion polymerization method by a conventional method such as a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, or an anionic polymerization method. Manufacturing by law. Among these production methods, since the radical polymerization method in the solution is simple, it is industrially preferable.

The polymerization initiator to be used in the production of the copolymer [C] may, for example, be a peroxide such as benzamidine peroxide or a dinonyl peroxide; 2,2'-azobisisobutyronitrile or a phenyl group An azo compound such as nitrogen triphenyl hexane.

The production of the copolymer [C] can be carried out in any case in the presence or absence of a solvent, but it is preferably carried out in the presence of a solvent from the viewpoint of workability. Examples of the solvent include alcohols, ketones, alkyl esters of monocarboxylic acids, ethers, propylene glycol and esters thereof, halogenated hydrocarbons, aromatic hydrocarbons, fluorinated inert liquids, and other polar solvents.

Examples of the solvent include, for example, ethanol, isopropanol, n-butanol, isobutanol, and tertiary butanol; and examples of the ketone include acetone, methyl ethyl ketone, and methyl ketone. Butyl ketone, methylamino ketone, etc.; as the alkyl ester of the above monocarboxylic acid, for example, methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, 2 -methyl oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, butyl 2-oxopropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, etc.; examples of the ether include methyl cellosolve, cellulase, butyl cellosolve, and butyl group. Carbitol, ethyl cellosolve acetate, tetrahydrofuran, two An alkane or the like; examples of the propylene glycol and the ester thereof include propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; Examples of the halogenated hydrocarbon include 1,1,1-trichloroethane and chloroform; and examples of the aromatic hydrocarbon include benzene, toluene, and xylene; and examples of the fluorinated inert liquid include For example, perfluorooctane, perfluorotri-n-butylamine, and the like; examples of the other polar solvent include dimethylformamide, dimethylhydrazine, and N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more.

When the copolymer [C] is produced, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioacetate or octyl thioacetate may be further used as needed.

The use ratio of the copolymer [C] in the positive radiation sensitive composition is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2 parts by mass, per 100 parts by mass of the component [A]. By using the [C] component in such a ratio, it is possible to form an interlayer insulating film having a high level of flatness without coating unevenness.

Other optional ingredients

The positive-type radiation-sensitive composition of the present invention may contain a [D] thermosensitive acid generator or a sensible base as needed, in addition to the above-mentioned [A] to [C] components, within a range that does not impair the desired effect. Other optional ingredients such as a generating agent, [E] dehydrating agent.

The sensible acid generator or the sensible alkali generator of the component [D] is defined as a compound which can release an acidic active material or a basic active material by heating, and the acidic active material or the basic active material functions as the component [A]. The action of the catalyst at the time of self-condensation and hardening of the siloxane polymer (preferably, the hydrolysis-condensation product of the hydrolyzable decane compound represented by the above formula (7)). By using such a compound of the [D] component, the heat resistance and solvent resistance of the obtained interlayer insulating film can be further improved. Further, the heat-sensitive acid generator or the alkali-generating agent as the component [D] preferably has a relatively low temperature (for example, 70 to 120 ° C) in the coating film forming step of the positive-type radiation-sensitive composition. The acidic active material or the basic active material is not released during baking, and the properties of the acidic active material or the basic active material are released during post-baking at a relatively high temperature (for example, 120 to 250 ° C) in the heating step after development. substance.

Examples of the heat-sensitive acid generator of the component [D] include a phosphonium salt such as a diphenylsulfonium salt, a triphenylsulfonium salt, a phosphonium salt, a benzothiazolium salt, an ammonium salt, a phosphonium salt or a tetrahydrothiophene salt. , sulfonium imine compounds, and the like.

Examples of the diphenylphosphonium salt include diphenylphosphonium tetrafluoroborate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroarsenate, and diphenylsulfonium trifluoromethanesulfonate. , diphenylphosphonium trifluoroacetate, diphenylphosphonium-p-toluenesulfonate, diphenylphosphonium butyl tris(2,6-difluorophenyl)borate, 4-methoxyphenyl- Phenylhydrazine tetrafluoroborate, bis(4-tributylphenyl)phosphonium tetrafluoroborate, bis(4-tributylphenyl)phosphonium hexafluoroarsenate, bis(4-tertiary Phenyl) fluorinated trifluoromethanesulfonate, bis(4-tributylphenyl)phosphonium trifluoroacetate, bis(4-tributylphenyl)phosphonium-p-toluenesulfonate, double 4-tertiary butylphenyl) camphorsulfonate and the like.

Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenyl camphorsulfonate, triphenylsulfonium tetrafluoroborate, and triphenylsulfonium trifluoroacetate. Triphenylphosphonium-p-toluenesulfonate, triphenylsulfonylbutyltris(2,6-difluorophenyl)borate, and the like.

Examples of the onium salt include an alkyl phosphonium salt, a benzyl phosphonium salt, a dibenzyl phosphonium salt, a substituted benzyl phosphonium salt, and the like.

As these onium salts, there may be mentioned, for example, as an alkyl phosphonium salt, for example, 4-ethenyloxyphenyldimethylsulfonium hexafluoroantimonate, 4-ethenyloxyphenyldimethylsulfonium hexafluoride. Arsenate, dimethyl-4-(benzyloxycarbonyloxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroantimony Acid salt, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroarsenate, dimethyl-3-chloro-4-ethoxycarbonylphenylphosphonium hexafluoroantimonate And as the benzyl sulfonium salt is, for example, benzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, 4-ethenyloxy Phenylbenzyl methyl hydrazine hexafluoroantimonate, benzyl-4-methoxyphenylmethyl hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethyl hydrazine Hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate And as the dibenzyl sulfonium salt is, for example, dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylphosphonium hexafluorophosphate, 4-ethenyloxybenzene Base two Benzyl hydrazine hexafluoroantimonate, dibenzyl-4-methoxyphenylphosphonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylphosphonium hexafluoroarsenate, Dibenzyl-3-methyl-4-hydroxy-5-tert-butylphenylphosphonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylphosphonium hexafluorophosphate a salt or the like; as a substituted benzyl sulfonium salt is, for example, p-chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylhydrazine hexafluoro Citrate, p-chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, 3,5-Dichlorobenzyl-4-hydroxyphenylmethylhydrazine hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroantimonate Wait.

Examples of the benzothiazolium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, and 3-benzylbenzothiazolium tetra Fluoroborate, 3-(p-methoxybenzyl)benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl 5--5-chlorobenzothiazolium hexafluoroantimonate.

Examples of the tetrahydrothiophene phosphonium salt include 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate and 1-(4-n-butoxynaphthalene). 1-yl)tetrahydrothiophene nonafluorobutanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-1,1,2,2-tetrafluoro-2 -(norbornane-2-yl)ethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-2-(5-tertiarybutoxycarbonyloxybicyclo) [2.2.1]Hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-2- (6-tertiary butoxycarbonyloxybicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4,7-dibutyl) Oxy-1-naphthyl)tetrahydrothiophene trifluoromethanesulfonate and the like.

Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy) succinimide (trade name "SI-105" (manufactured by midori-kagaku Co., Ltd.)), N-( Camphor sulfonate oxy) succinimide (trade name "SI-106" (manufactured by midori-kagaku Co., Ltd.)), N-(4-methylphenylsulfonyloxy) amber ylide (trade name) "SI-101" (manufactured by midori-kagaku Co., Ltd.), N-(2-trifluoromethylphenylsulfonyloxy) succinimide, N-(4-fluorophenylsulfonyloxy) Amber quinone imine, N-(trifluoromethylsulfonyloxy) phthalimide, N-(camphorsulfonyloxy) phthalimide, N-(2-trifluoro) Methylphenylsulfonyloxy) phthalimide, N-(2-fluorophenylsulfonyloxy) phthalimide, N-(trifluoromethylsulfonyloxy) Diphenylmaleimide (trade name "PI-105" (midori-kagaku Co., Ltd.)), N-(camphorsulfonyloxy) diphenylmaleimide, 4-(methyl Phenylsulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenyl Sulfonyloxy) Kimalyimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine (trade name "NDI-100" (manufactured by midori-kagaku Co., Ltd.)), N-(4-methylphenylsulfonyloxy)bicyclo[2.2. 1] G-5-ene-2,3-dicarboxy quinone imine (trade name "NDI-101" (manufactured by midori-kagaku Co., Ltd.)), N-(trifluoromethanesulfonyloxy)bicyclo[ 2.2.1] hept-5-ene-2,3-dicarboxy quinone imine (trade name "NDI-105" (manufactured by midori-kagaku Co., Ltd.)), N-(nonafluorobutanesulfonyloxy) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine (trade name "NDI-109" (manufactured by midori-kagaku Co., Ltd.)), N-(camphorsulfonyloxy) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine (trade name "NDI-106" (manufactured by midori-kagaku Co., Ltd.)), N-(camphorsulfonyloxy) -7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2. 1]Hept-5-ene-2,3-dicarboxy quinone imine, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium , N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(2-trifluoro Methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(2-trifluoromethylphenylsulfonyloxy)-7 -oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyarmine, N-(camphorsulfonate) Oxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxyindenine, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1 Heptane-5,6-oxo-2,3-dicarboxyindenine, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6 -oxo-2,3-dicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-di Carboxylimine, N-(trifluoromethylsulfonyloxy)naphthyldicarboxyphthalimide (trade name "NAI-105" (manufactured by midori-kagaku Co., Ltd.)), N-(camphorsulfonate) base) Dicarboxy quinone imine (trade name "NAI-106" (manufactured by midori-kagaku Co., Ltd.)), N-(4-methylphenylsulfonyloxy)naphthyldicarboxy quinone imine (trade name " NAI-101" (manufactured by midori-kagaku Co., Ltd.), N-(phenylsulfonyloxy)naphthyldicarboxy quinone imine (trade name "NAI-100" (manufactured by midori-kagaku Co., Ltd.)) , N-(2-trifluoromethylphenylsulfonyloxy)naphthyldicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)naphthyldicarboxy quinone imine, N-( Pentafluoroethylsulfonyloxy)naphthyldicarboxy quinone imine, N-(heptafluoropropylsulfonyloxy)naphthyldicarboxy quinone imine, N-(nonafluorobutoxysulfonyloxy) Naphthyl dicarboxy quinone imine (trade name "NAI-109" (manufactured by midori-kagaku Co., Ltd.)), N-(ethylsulfonyloxy)naphthyldicarboxy quinone imine, N-(propyl sulfonate)醯oxy)naphthyldicarboxy quinone imine, N-(butylsulfonyloxy)naphthyldicarboxy quinone imine (trade name "NAI-1004" (manufactured by midori-kagaku Co., Ltd.)), N- (pentylsulfonyloxy)naphthyldicarboxy quinone imine, N-(hexylsulfonyloxy)naphthyldicarboxy quinone imine, N-(heptylsulfonate) ) Acyl naphthyl-dicarboxy imide, N- (Sulfonic group-octyl) acyl naphthyl-dicarboxy imide, N- (nonyl sulfonylurea yloxy) naphthyl-dicarboxy-acyl imine.

Among these heat-sensitive acid generators, triphenylsulfonium salts, phosphonium salts, benzothiazolium salts and tetrahydrothiophene phosphonium salts are preferably used from the viewpoint of improving the heat resistance and solvent resistance of the obtained interlayer insulating film. Among them, triphenylsulfonium trifluoromethanesulfonate, triphenyl camphorsulfonate, 4-ethenyloxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4- are particularly preferred. Hydroxyphenylmethyl hydrazine hexafluoroantimonate, 4-ethoxycarbonylphenylbenzylmethyl hexafluoroantimonate, dibenzyl-4-hydroxyphenyl hexafluoroantimonate, 4-B Nonyloxyphenylbenzylmethylphosphonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, 1-(4 , 7-dibutoxy-1-naphthyl)tetrahydrothiophene fluorene triflate, N-(trifluoromethylsulfonyloxy)naphthyldicarboxy quinone imine.

Examples of the thermosensitive base generator as the component [D] include 2-nitrobenzylcyclohexylcarbamate and [[(2,6-dinitrobenzyl)oxy]carbonyl] ring. Hexylamine, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, triphenylmethanol, O-aminomethionyl hydroxy decylamine, O-aminomethyl decyl hydrazine, 4-(methylthiobenzimidyl)-1-methyl-1-morpholinoethane, (4-? Oleinobenzylidene)-1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, Hexaamine cobalt (III) tris(triphenylmethylborate) and the like. Among these heat-sensitive alkali generating agents of the component [D], from the viewpoint of improving the heat resistance of the obtained interlayer insulating film, 2-nitrobenzylcyclohexylcarbamate and O-amino group A are particularly preferable. Mercaptohydroxyamine.

The heat-sensitive acid generator or the heat-sensitive base generator of the component [D] may be used alone or in combination of two or more. The amount of the component [D] is preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass, per 100 parts by mass of the component [A]. When the amount of the component [D] is from 0.1 part by mass to 20 parts by mass, a positive-type radiation-sensitive composition excellent in heat resistance and solvent resistance of the formed interlayer insulating film can be obtained, and generation of the coating film formation step can be prevented. The precipitate is easy to form a coating film.

The dehydrating agent of the component [E] is defined as a substance which converts water into a substance other than water by a chemical reaction, or a material which occludes water by physical adsorption or inclusion. By optionally containing the [E] dehydrating agent in the positive-acting radiation-linear composition, moisture intruding from the external environment can be reduced. Therefore, by using the [E] dehydrating agent, the moisture in the composition can be lowered, thereby improving the storage stability of the composition. As such [E] dehydrating agent, at least one compound selected from the group consisting of a carboxylate, an acetal (including a ketal) and a carboxylic anhydride is preferably used.

Preferable examples of the carboxylic acid ester include an orthocarboxylic acid ester, a carboxylic acid methyl sulfonyl ester, and the like. Specific examples of the orthocarboxylic acid esters include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, and sodium orthoacetate. Ester, methyl orthopropionate, ethyl orthopropionate, and the like. Further, among these orthocarboxylic acid esters, orthoformates such as methyl orthoformate are particularly preferred. Specific examples of the mercaptoalkyl carboxylate include trimethylformamidine acetate, tributylcarbamyl acetate, trimethylformamidinecarboxylate, and trimethylformamidate oxalate.

Preferable examples of the acetal include a reaction product of a ketone and an alcohol, a reaction product of a ketone and a glycol, and a ketene alkyl acetal. Specific examples of the reactant of the ketone and the alcohol include dimethyl acetal, diethyl acetal, and dipropyl acetal.

Preferable examples of the carboxylic acid anhydride include acetic anhydride, acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and benzoic anhydride. Among these carboxylic anhydrides, acetic anhydride and succinic anhydride are preferred in terms of dehydration effect.

The amount of the [E] dehydrating agent to be used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, even more preferably 0.03 to 1 part by mass, per 100 parts by mass of the component [A]. By using the amount of the [E] dehydrating agent in an amount of 0.001 to 10 parts by mass, the storage stability of the positive-type radiation-linear composition can be improved.

Positive-type radiation linear composition

The positive-type radiation-sensitive composition of the present invention is obtained by mixing the above-mentioned [A] component of a decane polymer, the [B] component of a quinonediazide compound, and the [C] component of a monomer of a specific structure. And an optional component (heat-sensitive acid generator or heat-sensitive alkali generator of the [D] component, etc.) which is contained as needed. Usually, the positive-type radiation-sensitive composition is preferably prepared and used in a state of being dissolved or dispersed in a suitable [F] solvent. For example, a positive-type radiation-sensitive composition can be prepared by mixing the components [A], [B], and [C] and optional components in a predetermined ratio in a solvent.

As the [F] solvent which can be used for the preparation of the positive-type radiation-sensitive composition, a solvent which uniformly dissolves or disperses each component and does not react with each component is suitably used. Examples of such a solvent include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates. Propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones, esters, and the like.

Examples of the solvent include, for example, benzyl alcohol and diacetone alcohol as the alcohols, and tetrahydrofuran and diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, and diisoamyl groups as the ethers. a dialkyl ether such as ether or di-n-hexyl ether; and as the diethylene glycol alkyl ether, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether , diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; as ethylene glycol alkyl ether acetates such as methyl fibrin acetate, ethyl fibrin acetate , ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc.; as propylene glycol monoalkyl ethers are, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether , propylene glycol monobutyl ether, etc.; as propylene glycol monoalkyl ether acetates are, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl Ethyl acetate, etc.; as propylene glycol monoalkyl ether propionate, for example, propylene glycol monomethyl ether propionate, propylene glycol Ethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, etc.; as aromatic hydrocarbons, for example, toluene, xylene, etc.; as ketones, for example, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, etc.; as esters such as methyl acetate, ethyl acetate, propyl acetate, acetic acid Propyl ester, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate , butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropyl Butyl acrylate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate Ester, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate Butyoxyacetate Ester, ethyl butoxylate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl ester, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, and the like.

Among these solvents, ethers such as dialkyl ethers and diethylene glycol alkyl ethers are preferred from the viewpoints of excellent solubility and dispersibility, non-reactivity of each component, and ease of formation of a coating film. Classes, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters, particularly preferably diethylene glycol diethyl ether, diethylene glycol Ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, cyclohexanone, propyl acetate, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate. These solvents may be used singly or in combination.

Further, among these solvents, ethers such as dialkyl ethers such as diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, diisoamyl ether and di-n-hexyl ether are preferred. Amyl ether. By using such a solvent, when the radiation sensitive composition is coated on a large glass substrate by a slit coating method, the drying step time can be shortened, and the coating property can be further improved (uneven coating unevenness).

In addition to the above solvents, if necessary, it may be combined with benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl Acetone, isophorone, caproic acid, capric acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyl A high boiling point solvent such as lactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate or carbitol acetate is used together.

When the positive-type radiation-sensitive composition is prepared in a solution or dispersion state, it occupies a component other than the [F] solvent in the solution (that is, the total of [A], [B], and [C] components, and other optional components. The ratio of the amount can be arbitrarily set depending on the purpose of use and the desired film thickness, and is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, most preferably 15 to 35% by mass.

Formation of interlayer insulating film

Next, a method of forming an interlayer insulating film on a substrate using the positive-type radiation-sensitive composition described above will be described. This method includes the following steps described in the following order.

(1) a step of forming a coating film of the positive-type radiation-sensitive composition on a substrate,

(2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation,

(3) a step of developing the coating film irradiated with radiation in the step (2), and

(4) a step of heating the coating film developed in the step (3).

(1) Step of forming a coating film of the positive-type radiation-sensitive composition on a substrate

In the step (1), after applying the solution or dispersion of the positive-acting radiation-sensitive composition onto the substrate, it is preferred to remove the solvent by heating (pre-baking) the coated surface to form a coating film. Examples of the substrate that can be used include glass, quartz, rhodium, and resin. Specific examples of the resin include open-loop polymers of polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, polyimine, and cyclic olefin. Hydride, etc.

The coating method of the composition solution or the dispersion liquid is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method can be employed. Among these coating methods, a spin coating method or a slit die coating method is particularly preferred. The pre-baking conditions vary depending on the type of each component, the mixing ratio, etc., and are preferably carried out at 70 to 120 ° C for about 1 to 10 minutes.

(2) a step of irradiating at least a part of the coating film with radiation

In the step (2) above, at least a part of the formed coating film is exposed. In this case, when a part of the coating film is exposed, it is usually exposed by a mask having a predetermined pattern. As the radiation used for exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet rays of 365 nm is particularly preferable.

The exposure amount in this step is a value obtained by measuring the intensity at a wavelength of 365 nm of the radiation by an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.), preferably 500 to 6,000 J/m ² , more preferably 1,500 Å. 1,800J/m ² .

(3) Development step

In the step (3), the exposed coating film is developed to remove an unnecessary portion (irradiated portion of the radiation) to form a predetermined pattern. As the developing solution used in the developing step, an aqueous solution of an alkali (basic compound) is preferred. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and ammonia, and tetrabasic ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Salt and so on.

Further, in such an aqueous alkali solution, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. The concentration of the alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining appropriate developability. As the developing method, an appropriate method such as a liquid-filling method, a dipping method, a shaking dipping method, or a shower method can be used. The development time varies depending on the composition of the positive-type radiation-linear composition, and is preferably about 10 to 180 seconds. After such development treatment, for example, after 30 to 90 seconds of running water washing, for example, by air drying with compressed air or compressed nitrogen, a desired pattern can be formed.

(4) Heating step

In the step (4), a patterned film is heated by a heating means such as a hot plate or an oven to promote the self-hardening reaction of the component [A] and the hardening reaction of the component [C], whereby a cured product can be obtained. In particular, when a heat-sensitive acid generator or a heat-sensitive base generator of the component [D] is used, an acidic active material or a basic active material is generated in a heating step, which serves as a catalyst to further promote condensation of the [A] component. reaction. The heating temperature in this step is, for example, 120 to 250 °C. The heating time varies depending on the type of the heating device, for example, 5 to 30 minutes when the heating step is performed on the hot plate, and 30 to 90 minutes when the heating step is performed in the oven. A stepwise baking method or the like which performs two or more heating steps can also be used. Thus, a pattern-like film corresponding to the required interlayer insulating film can be formed on the surface of the substrate.

Interlayer insulating film

The film thickness of the interlayer insulating film thus formed is preferably from 0.1 to 8 μm, more preferably from 0.1 to 6 μm, most preferably from 0.1 to 4 μm.

The interlayer insulating film formed of the positive-type radiation-sensitive composition of the present invention can satisfy the generally required properties such as heat resistance, transparency, solvent resistance, and low dielectric properties as well as the following examples. It has a high degree of flatness without uneven coating. Therefore, the interlayer insulating film is suitable for use as a display element.

[Examples]

The present invention will be more specifically described in the following Synthesis Examples and Examples, but the present invention is not limited by the following examples.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolyzed condensate of the hydrolyzable decane compound of the component [A] obtained in each of the following synthesis examples and the copolymer of the component [C] are obtained by the following method. Determination by permeation chromatography (GPC).

Device: GPC-101 (made by Showa Denko Co., Ltd.)

Column: a combination of GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 (manufactured by Showa Denko Co., Ltd.)

Mobile phase: tetrahydrofuran

Synthesis example of hydrolysis condensate of hydrolyzable decane compound of [A] component [Synthesis Example 1]

After adding 25 parts by mass of propylene glycol monomethyl ether in a vessel equipped with a stirrer, 30 parts by mass of methyltrimethoxydecane, 23 parts by mass of phenyltrimethoxydecane, and 0.1 part by mass of aluminum tetraisopropoxide were added. Heat to a solution temperature of 60 °C. After the solution temperature reached 60 ° C, 18 parts by mass of ion-exchanged water was added and heated to 75 ° C for 3 hours. Next, 28 parts by mass of methyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. Then, the temperature of the solution was adjusted to 40 ° C, and while maintaining the temperature, the mixture was evaporated to remove the ion-exchanged water and the methanol produced by the hydrolysis condensation. As described above, the hydrolysis condensate (A-1) was obtained. The solid content concentration of the hydrolysis-condensation product (A-1) was 40.5 mass%, and the obtained hydrolysis-condensation product had a number average molecular weight (Mn) of 1,500 and a molecular weight distribution (Mw/Mn) of 2.

[Synthesis Example 2]

In a container with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was added, followed by 22 parts by mass of methyltrimethoxydecane, 12 parts by mass of γ-glycidoxypropyltrimethoxydecane, and 20 parts by mass. A hydrolysis condensate (A-2) was obtained in the same manner as in Synthesis Example 1 except for phenyltrimethoxydecane and 0.1 part by mass of aluminum tetraisopropoxide. The solid content concentration of the hydrolysis-condensation product (A-2) was 39.8 mass%, and the obtained hydrolysis-condensation product had a number average molecular weight (Mn) of 1,600 and a molecular weight distribution (Mw/Mn) of 2.

a copolymer of a component [C] having a specific structure [Synthesis Example 3]

In a glass flask equipped with a stirring device, a condenser and a thermometer, 28.4 parts by mass of a compound represented by the above formula (c1-1) as a compound (c1) and 20.7 parts by mass of a new Nakamura Chemical Co., Ltd. as a compound (c2) were added. "NK-ESTER M-90G" manufactured by the company, 18.1 parts by mass of a compound represented by the following formula (c3-1-1-1) as a compound of (c3), and 5.9 parts by mass of a methyl group as a compound of (c4) Methyl acrylate and 23.5 parts by mass of 2-ethylhexyl acrylate, 3.4 parts by mass of a compound of (c5) 1,4-butanediol, a terminal methacrylated compound, and 414 parts by mass of isopropyl as a solvent Alcohol, after adding 0.7 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator and 4 parts by mass of lauryl mercaptan as a chain transfer agent under reflux in a nitrogen stream, at 75 ° C The copolymerization was carried out under reflux for 8 hours to obtain a solution containing the copolymer (C-1). Thereafter, the solvent was removed under heating at 70 ° C or lower using an evaporator to separate the copolymer (C-1). The obtained copolymer (C-1) had a number average molecular weight Mn of 2,800, a weight average molecular weight Mw of 5,300, and a molecular weight distribution (Mw/Mn) of 1.9.

In the formula, Me is a methyl group.

[Synthesis Example 4]

The copolymer (C-2) was obtained in the same manner as in the above Synthesis Example 3 except that the amount of the lauryl mercaptan added as the chain transfer agent was 1 part by mass. The obtained copolymer (C-2) had a number average molecular weight Mn of 4,700, a weight average molecular weight Mw of 11,000, and a molecular weight distribution (Mw/Mn) of 2.3.

[Synthesis Example 5]

The copolymer (C-3) was obtained in the same manner as in the above Synthesis Example 3 except that the lauryl mercaptan as a chain transfer agent was not used, and the temperature and time of copolymerization were 73 ° C and 10 hours, respectively. The obtained copolymer (C-3) had a number average molecular weight Mn of 5,600, a weight average molecular weight Mw of 21,000, and a molecular weight distribution (Mw/Mn) of 3.8.

[Synthesis Example 6]

In a glass flask equipped with a stirring device, a condenser, and a thermometer, 31.8 parts by mass of a compound represented by the above formula (c1-3) as a compound (c1), and 31.6 parts by mass of a new Nakamura Chemical Co., Ltd. as a compound (c2) were added. "NK-ESTER M-90G" manufactured by the company, 29.0 parts by mass of a compound represented by the following formula (c3-1-1-1) as a compound of (c3) and 414 parts by mass of isopropyl alcohol in a nitrogen stream After adding 0.7 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator and 4 parts by mass of lauryl mercaptan as a chain transfer agent under reflux, it was refluxed at 75 ° C for 8 hours. Copolymerization was carried out to obtain a solution containing the copolymer (C-4). Thereafter, the solvent was removed under heating at 70 ° C or lower using an evaporator to separate the copolymer (C-4). The obtained copolymer (C-4) had a number average molecular weight Mn of 3,000 and a weight average molecular weight Mw of 6,000. Further, the molecular weight distribution (Mw/Mn) was 2.0.

[Synthesis Example 7]

In a glass flask equipped with a stirring device, a condenser, and a thermometer, 24.2 parts by mass of a compound represented by the above formula (c1-5) as a compound (c1), and 20.7 parts by mass of a new Nakamura Chemical Co., Ltd. as a compound (c2) were added. "NK-ESTER M-90G" manufactured by the company, 21.5 parts by mass of a compound represented by the following formula (c3-1-1-1) as a compound of (c3), and 29.4 parts by mass of a methyl group as a compound of (c4) N-butyl acrylate and 414 parts by mass of isopropyl alcohol, and 0.7 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator and 4 parts by mass as a polymerization initiator were added under reflux in a nitrogen stream. After the transfer agent of lauryl mercaptan was refluxed at 75 ° C for 8 hours, copolymerization was carried out to obtain a solution containing the copolymer (C-5). Thereafter, the solvent was removed under heating at 70 ° C or lower using an evaporator to separate the copolymer (C-5). The obtained copolymer (C-5) had a number average molecular weight Mn of 2,600 and a weight average molecular weight Mw of 5,000. Further, the molecular weight distribution (Mw/Mn) was 1.9.

Preparation of positive-type radiation linear composition [Example 1]

In the solution containing the hydrolysis-condensation product (A-1) obtained in Synthesis Example 1 (corresponding to 100 parts by mass of the hydrolysis-condensation product (A-1) (solid content)), 30 parts by mass of the component (B) was mixed. 4,4'-[1-[4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]extended ethyl]biphenol (1.0 mol) and 1,2-naphthoquinone a condensate (B-1) of azide-5-sulfonyl chloride (2.0 mol), 0.50 parts by mass of a copolymer (C-1) obtained in Synthesis Example 3 as a component [C], and then adding diethyl ether as a solvent After the solid content concentration was 25% by mass, the diol ethyl methyl ether was filtered through a membrane screening procedure having a diameter of 0.2 μm to prepare a positive-acting radiation linear composition (S-1).

[Examples 2 to 7 and Comparative Examples 1 to 3]

A positive-type radiation-sensitive composition was prepared in the same manner as in Example 1 except that the types and amounts of the respective components were as described in Table 1. Further, Comparative Examples 1 and 2 used the following surfactant instead of the copolymer of the [C] component.

C-1 (Comparative Example 1): an organic terpene surfactant ("SH-193" manufactured by Toray Dow Corning Silicone Co., Ltd.)

C-2 (Comparative Example 2): fluorosurfactant ("FTERGENT 222F" manufactured by NEOS Co., Ltd.)

Physical property evaluation

Using the various positive-type radiation-sensitive compositions prepared as above, the composition and various properties as a coating film or an interlayer insulating film were evaluated as follows.

[Appearance evaluation of coating film]

The radiation-sensitive composition prepared above was applied onto a 550 × 650 mm chromium-forming glass using a slit die coater (model "TR632105-CL" manufactured by Tokyo Ohka Kogyo Co., Ltd.), and the pressure reached was set to After removing the solvent under vacuum at 100 Pa, it was further prebaked at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. The appearance of the coating film was visually observed under a sodium lamp. At this time, the unevenness of the mist generated in the entire film was referred to as "fog unevenness", and the unevenness of the proximity pin from the prebaking furnace was regarded as "unevenness of the pin", and the occurrence thereof was examined. Almost no such unevenness was found to be evaluated as "good", and a case where any of these unevenness was found in a small amount was evaluated as "slightly bad", and a case clearly seen was evaluated as "not good". The evaluation results are shown in Table 1.

[Evaluation of Radiation Sensitivity of Radiation-Linear Compositions]

Hexamethyldiaziridine (HMDS) was applied to a 550 x 650 mm chrome-forming glass and heated at 60 ° C for 1 minute (HMDS treatment). The radiation-sensitive composition prepared above was applied onto the chrome-forming glass after the HMDS treatment using a slit pattern applicator "TR632105-CL", and the pressure reached was set to 100 Pa, and the solvent was removed under vacuum, and then Prebaking was carried out at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. Next, using a MPA-600FA exposure machine manufactured by Cannon Co., Ltd., a mask having a pattern of a line-to-space ratio (10:1) of 60 μm was used, and the amount of exposure to the coating film was changed, and the radiation was irradiated. The aqueous solution of tetramethylammonium hydroxide in the concentration described in 1 was developed by a liquid-holding method at 25 °C. Here, the development time was 80 seconds when a developer having a concentration of tetramethylammonium hydroxide of 0.40% by mass was used, and when a developer of 2.38 mass% was used, it was 50 seconds. Next, it was subjected to running water washing for 1 minute by ultrapure water, and then dried to form a pattern on the substrate on which the chrome film was formed after the HMDS treatment. At this time, the amount of exposure necessary to completely dissolve the spatial pattern of the line-to-space ratio (1:1) of 6 μm was investigated. This value is shown in Table 1 as the radiation sensitivity. When the value is 700 J/m ² or less, the sensitivity is considered to be good.

[Evaluation of development margin of radiation-sensitive linear composition]

The HMDS treatment of the glass (4 inch glass wafer) forming the chromium film was performed in the same manner as in the case of the above [Evaluation of the radiation sensitivity of the radiation sensitive composition]. The radiation-sensitive composition prepared above was applied onto the chrome-forming glass after the HMDS treatment using a spin coater, and the pressure reached was set to 100 Pa, and the solvent was removed by vacuum drying, and further preliminarily performed at 90 ° C for 2 minutes. Baking was carried out to form a coating film having a film thickness of 3.0 μm. Next, using a MPA-600FA exposure machine manufactured by Cannon Co., Ltd., a reticle having a pattern of a line-to-space ratio (1:1) of 6 μm was used to evaluate the radiation sensitivity corresponding to the above [radial-sensitive composition] The exposure amount of the radiation sensitivity value studied was exposed to the above-mentioned coating film, and then developed using a tetramethylammonium hydroxide aqueous solution having a concentration shown in Table 1 at a developing time as a variable at 25 ° C by a liquid-holding method. Next, it was subjected to running water washing for 1 minute by ultrapure water, and then dried to form a pattern on the substrate on which the chrome film was formed after the HMDS treatment. At this time, the development time necessary for the baseline width of 6 μm was the optimum development time, which is shown in Table 1. Further, the time from the peeling of the line pattern of 6 μm from the time when the development was further continued from the optimum development time was measured, and this time was taken as the development margin, which is shown in Table 1. When the value is 30 seconds or longer, the development margin is considered to be good.

[Evaluation of Solvent Resistance of Interlayer Insulating Film]

The radiation-sensitive composition prepared above was applied onto a glass (4 inch glass wafer) on which a chromium film was formed using a spin coater, and the pressure reached was set to 100 Pa, and the solvent was removed under vacuum, and further at 90 ° C. Pre-bake in minutes to form a coating film. For the coating film, an MPA-600FA exposing device manufactured by Cannon Co., Ltd. was used, and the cumulative irradiation amount was 9,000 J/m ² , and then, in a cleaning oven, heating at 220 ° C for 1 hour, in the glass forming the chromium film. A cured film is formed thereon. The film thickness (T1) of the cured film obtained here was measured. Then, the glass substrate on which the chromium film was formed, which was formed into the cured film, was immersed in dimethyl sulfoxide having a temperature of 70 ° C for 20 minutes, and then the film thickness (t1) of the cured film was measured again to calculate the film thickness change caused by the immersion. Rate {|t1-T1|/T1}×100[%]. The results are shown in Table 1. When the value is 5% or less, the solvent resistance is considered to be good.

[Evaluation of heat resistance of interlayer insulating film]

In the same manner as in the case of the above [Evaluation of Solvent Resistance of Interlayer Insulating Film], a cured film is formed on the glass on which the chromium film is formed. The film thickness (T2) of the cured film obtained here was measured. Then, the glass substrate on which the chromium film was formed to form the cured film was additionally heated in a cleaning oven at 240 ° C for 1 hour, and then the film thickness (t2) of the cured film was measured again, and the film thickness change rate by additional heating was calculated {{{ |t2-T2|/T2}×100[%]. The results are shown in Table 1. When the value is 5% or less, heat resistance is considered to be good.

[Evaluation of transparency of interlayer insulating film]

In addition to the use of a glass substrate of 550 × 650 mm ("NA35" manufactured by NH Techno Glass Co., Ltd.) instead of the glass substrate on which the chromium film is formed, in the same manner as in the case of [evaluation of solvent resistance of the interlayer insulating film], in the case of glass A cured film is formed on the substrate. Using a spectrophotometer "150-20 type double beam (manufactured by Hitachi, Ltd.)", a glass substrate having no cured film was used as a reference side, and the measurement was performed at a wavelength in the range of 400 to 800 nm. The light transmittance of the glass substrate of the cured film. The value of the lowest light transmittance at this time is shown in Table 1. When the value is 90% or more, transparency is considered to be good.

[Evaluation of film thickness uniformity (flatness) of interlayer insulating film]

In the same manner as the above [Evaluation of Transparency of Interlayer Insulating Film], a cured film was formed on a glass substrate. The film thickness of the measurement point at 20 points was measured for the cured film, and the film thickness uniformity was calculated by the following formula.

Uniformity (%) of film thickness = (maximum-minimum film thickness of cured film) × 100 / ((average value of coating film thickness of 20 points) × 2)

When the film thickness uniformity of the cured film thus calculated is 1% or less, it is considered that the film thickness uniformity is good. In addition, the measurement points of the above 20 points were determined as follows. In other words, a region (450 × 550 mm) inside the range of 5 cm is removed from each of the long side and the short side of the substrate (550 × 650 mm) as a measurement region, and a straight line in the longitudinal direction and the short side direction of the region. Each of the above is determined by 10 points (20 points in total) every 4 cm, and these are used as measurement points.

[Evaluation of Relative Dielectric Constant of Interlayer Insulating Film]

The radiation-sensitive composition prepared as described above was applied onto a SUS304 substrate having a smooth surface polished by sisal soft skin (soft skin) by a spin coating method, and the pressure reached was set to 100 Pa, and the solvent was removed under vacuum. Thereafter, the film was prebaked at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. The obtained coating film was exposed to a cumulative irradiation amount of 9,000 J/m ² using an MPA-600FA exposing device manufactured by Cannon Co., Ltd., and then the substrate was heated at 220 ° C for 1 hour in a cleaning oven. A cured film is formed on the substrate. A Pt/Pd electrode pattern was formed on the cured film by a vapor deposition method to produce a sample for dielectric constant measurement. The relative dielectric constant of the substrate having the electrode pattern was measured by a CV method using a HP16451B electrode manufactured by Yokogawa-Hewlett Packard Co., Ltd. and an HP4284A precision LCR meter at a frequency of 10 kHz. The measurement results are shown in Table 1. When the value is 3.9 or less, the relative dielectric constant (low dielectric property) is considered to be good.

As shown in the results of Table 1, it is possible to know the positive-type radiation-sensitive linear compositions of Examples 1 to 7 containing [A], [B], and [C] components and Comparative Examples 1 to 3 containing no [C] component. The positive-type radiation-sensitive composition is more excellent in coating unevenness in the appearance of the coating film and in the flatness of the interlayer insulating film. Further, it is also known that the positive-type radiation-sensitive composition of these embodiments has a high radiation sensitivity and development margin, and can also form a general requirement that sufficiently satisfies heat resistance, transparency, solvent resistance, and low dielectric property. The interlayer insulating film of the nature.

[Industrial Applicability]

The positive-type radiation-sensitive composition of the present invention has high radiation sensitivity and development margin as described above, and can be formed to have excellent heat resistance, transparency, solvent resistance, and low dielectric property. A flat hardened film. Therefore, the positive-type radiation-radiating composition is suitable for forming an interlayer insulating film for a display element.

Claims (7)

A positive-type radiation linear composition comprising: [A] a decane polymer, [B] a quinonediazide compound, and [C] comprising (c1) a compound represented by the following formula (5), ( C2) a compound represented by the following formula (6), (c3) a polymerizable unsaturated compound having a group represented by the following formula (3), and (c4) a polymerization of an alkyl group having 1 to 8 carbon atoms; a copolymer of a polyunsaturated compound and (c5) a polymerizable unsaturated compound having a polymerizable unsaturated compound having two or more unsaturated bonds in one molecule, and the [C] copolymer is a mass of 25 to 35 of the compound (c1) %, the compound (c2) is 20 to 30% by mass, the compound (c3) is 15 to 20% by mass, the compound (c4) is 25 to 35% by mass, and the compound (c5) is 1 to 5% by mass of the polymerizable unsaturated compound. Copolymer, CH ₂ =CR ¹ COOC ₂ H ₄ C _β F _2β+1 (5) In the formula (5), R ¹ is a hydrogen atom or a methyl group, β is an integer of 1-8, and CH ₂ =CR ² COO (C ₂ H ₄ O) _a R ³ (6) In the formula (6), R ² is a hydrogen atom or a methyl group, R ³ is an alkyl group having 1 to 12 carbon atoms, and the number average of the number of repeating units a is 4~12, In the formula (3), R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group having 1 to 20 carbon atoms, a phenyl group or a group represented by the following formula (4), b Is an integer from 0 to 3, In the formula (4), R ⁹ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 20 carbon atoms or a phenyl group, and c is an integer of 0 to 3. The positive-type radiation-sensitive linear composition of the first aspect of the invention, wherein the [A]methoxyl polymer is a hydrolysis condensate of the hydrolyzable decane compound represented by the following formula (7), (R ¹² ) _x - Si-(OR ¹³ ) _4-x (7) In the formula (7), R ¹² is a non-hydrolyzable organic group having 1 to 20 carbon atoms, and R ¹³ is an alkyl group having 1 to 4 carbon atoms. x is an integer from 0 to 3. A positive-type radiation-sensitive linear composition according to claim 1, which further comprises a [D] sensible acid generator or a sensible base generator. The positive-type radiation-sensitive composition of claim 1, further comprising [E] a dehydrating agent. The positive-type radiation-sensitive composition according to any one of claims 1 to 4, which is used for forming an interlayer insulating film of a display element. A method of forming an interlayer insulating film for a display element, the method comprising: (1) a step of forming a coating film of a positive-type radiation-sensitive linear composition of claim 5 on a substrate, (2) a step of irradiating at least a part of the coating film formed in the step (1) with radiation, (3) a step of developing the coating film irradiated with radiation in the step (2), and (4) heating in the step (3) The step of developing the coated film. An interlayer insulating film of a display element formed of a positive-type radiation-sensitive composition as in the fifth aspect of the patent application.