TW201806995A - Method for producing novolac type resin - Google Patents

Abstract

The purpose of the present invention is to provide the following: a method for producing a novolac type resin which exhibits extremely high heat resistance and excellent long-term storage stability under a variety of temperature conditions; a novolac type resin produced using this production method; a photosensitive composition or curable composition containing this novolac type resin; and a resist material using same. Provided are the following: a method for producing a novolac type resin, which is characterized by reacting a polyhydroxybenzene compound (A) and an aldehyde compound (C) in a protic solvent (S); and a novolac type resin produced using this production method.

Description

Method for producing novolac resin

The present invention relates to a method for producing a novolak-type resin having very high heat resistance and excellent long-term storage stability under various temperature conditions, a novolak-type resin produced by the above-mentioned production method, a photosensitive composition containing the same, or A curable composition and the use of such a resist material.

Phenolic hydroxyl-containing resins such as novolac resins are used in adhesives, molding materials, coatings, photoresist materials, epoxy resin raw materials, epoxy resin hardeners, etc. In addition, due to the heat resistance or humidity resistance of the cured product It is also widely used as a hardening composition containing a phenolic hydroxyl group-containing resin as a main agent or as a hardener such as epoxy resin, and is widely used in electrical and electronic materials such as semiconductor sealing materials and insulating materials for printed wiring boards. field.

Among them, in the photoresist field, various resist pattern forming methods that have been subdivided according to applications or functions are gradually being developed, and as a result, the performance required for the resin materials for resists is also highly advanced and diversified. For example, it is needless to say that the high developability for forming fine patterns on highly integrated semiconductors with high production efficiency is accurate. Needless to say, in the case of forming a thick film, the hardened material must be soft and difficult to crack In the case of use in a resist base film, dry etching resistance or heat resistance is required, and in the case of use in a permanent resist film, in addition to resistance In addition to thermal properties, toughness such as substrate followability is also required. Furthermore, from the viewpoint of quality and reliability, long-term storage stability in various environments around the world is also one of the important performances.

As a resin material for a resist excellent in developability or heat resistance, for example, novolak-type resins composed of alkylphenols such as cresol or xylenol and dihydroxybenzene are known (see Patent Documents 1 and 2 below). Although these novolac resins are excellent resin materials in terms of high alkali solubility and high sensitivity to obtain high resolution resist patterns, they have low heat resistance and relatively high temperature conditions. The long-term storage stability is also insufficient, so it is required to develop a resin material that has these properties.

[Prior technical literature] [Patent Literature]

[Patent Document 1]

Japanese Patent Laid-Open No. 11-258808

[Patent Document 2]

JP 2000-137324

Therefore, the problem to be solved by the present invention is to provide a method for producing a novolak resin that is excellent in not only developability or sensitivity, but also has very high heat resistance and excellent long-term storage stability under various temperature conditions. The novolak-type resin produced contains a photosensitive composition or a curable composition of the above-mentioned novolak-type resin, and these resist materials are used.

The present inventors have made intensive studies in order to solve the above-mentioned problems, and as a result, they have found that by producing a novolak resin having polyhydroxybenzene as an essential reaction raw material in a protic solvent, a very high heat resistance can be obtained. The novolac-type resin which is also excellent in long-term storage stability under various temperature conditions has completed the present invention.

That is, this invention relates to the manufacturing method of a novolak-type resin which makes a polyhydroxybenzene compound (A) and an aldehyde compound (B) react in a protic solvent (S).

The present invention further relates to a method for producing a photosensitive composition in which a novolac resin and a photosensitizer produced by the above-mentioned production method are blended.

The present invention further relates to a method for producing a resist film using the photosensitive composition produced by the above-mentioned production method.

The present invention further relates to a method for producing a curable composition by blending a novolac resin and a hardener produced by the above-mentioned production method.

The present invention further relates to a method for producing a cured product using a curable composition produced by the above-mentioned production method.

The present invention further relates to a method for producing a resist film using a curable composition produced by the above-mentioned production method.

The present invention further relates to a novolac resin manufactured by the above-mentioned manufacturing method.

The present invention further relates to a photosensitive composition containing a novolac resin and a photosensitizer produced by the above-mentioned production method.

The present invention further relates to a resist material using the photosensitive composition. material.

The present invention further relates to a curable composition containing a novolac resin and a curing agent produced by the above-mentioned production method.

The present invention further relates to a cured product of the above-mentioned curable composition.

The present invention further relates to a resist material using the curable composition.

According to the present invention, it is possible to provide a method for producing a novolak-type resin having very high heat resistance and excellent long-term storage stability under various temperature conditions, a novolak-type resin produced by the production method, and the above-mentioned novolak-type resin A photosensitive composition or a curable composition, and a resist material using these.

The method for producing a novolak resin of the present invention is characterized in that it reacts a polyhydroxybenzene compound (A) and an aldehyde compound (B) in a protic solvent (S).

The polyhydroxybenzene compound (A) may be any compound as long as it has a plurality of phenolic hydroxyl groups on a benzene ring, and the substitution position of the phenolic hydroxyl group or the presence or absence of other substituents is not particularly limited. Moreover, a polyhydroxybenzene compound (A) may be used individually by 1 type, and may use 2 or more types together. Specific examples of the polyhydroxybenzene compound (A) include the following structures: A compound having a molecular structure represented by formula (2), and the like.

[m is 2 or 3, wherein R ² is any of aliphatic hydrocarbon group, alkoxy group, and aryl group, and n is 0, 1 or 2]

R ² in the structural formula (2) is any one of an aliphatic hydrocarbon group, an alkoxy group, and an aryl group. The aliphatic hydrocarbon group may be a linear type, a branched type, or an unsaturated bond in the structure. Specific examples include alkyl or cyclohexyl such as methyl, ethyl, propyl, isopropyl, butyl, third butyl, pentyl, hexyl, heptyl, octyl, nonyl alkyl, etc. Isocycloalkyl, etc. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a third butoxy group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, and a structural site in which an aromatic nucleus is substituted with an alkyl group, an alkoxy group, or a halogen atom. Among them, in terms of being a novolac resin having excellent heat resistance, R ^{2 is} preferably an alkyl group having 1 to 6 carbon atoms, and more preferably n is 0.

In the structural formula (2), m is 2 or 3. The substitution position of the hydroxyl group in the structural formula (2) is not particularly limited. When m is 2, for example, the substitution position of the hydroxyl group may be any of 1,2-, 1,3-, and 1,4-positions. In the case where m is 3, for example, the substitution position of the hydroxyl group may be any of 1, 2, 3-, 1, 2, 4-, and 1, 3, 5-positions. Among these, in terms of obtaining a novolac resin having excellent heat resistance and long-term storage stability, a dihydroxybenzene compound having m of 2 is preferred, and resorcinol having a hydroxyl group at 1,3-position is particularly preferred. Compound.

In the production method of the present invention, a compound (C) containing a phenolic hydroxyl group other than the compound (A) may be used together with the polyhydroxybenzene compound (A). Examples of the other phenolic hydroxyl-containing compound (C) include a hydroxybenzene compound, a (poly) hydroxynaphthalene compound, a (poly) hydroxyanthracene compound, a biphenol compound, and a bisphenol compound. Examples of the hydroxybenzene compound include phenol; cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, butylphenol, third butylphenol, pentylphenol, octylphenol, Alkyl phenols such as nonylphenol, cumylphenol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol, iodophenol; arylphenols such as phenylphenol; aminophenol, nitrophenol, dinitrophenol, triphenylphenol Functional phenols such as nitrophenol. Examples of the (poly) hydroxynaphthalene compound include naphthol, dihydroxynaphthalene, and a compound substituted with an alkyl group, an alkoxy group, a halogen atom, or the like on the aromatic core. Examples of the (poly) hydroxyanthracene compound include anthracenol and compounds having an aromatic core substituted with an alkyl group, an alkoxy group, a halogen atom, or the like. Examples of the biphenol compound include biphenol and compounds having an aromatic core substituted with an alkyl group, an alkoxy group, a halogen atom, or the like. Examples of the bisphenol compound include bisphenol A, bisphenol F, bisphenol B, and bisphenol S, and compounds in which an aromatic core is substituted with an alkyl group, an alkoxy group, a halogen atom, or the like. These can be used individually or in combination of 2 or more types.

When the other phenolic hydroxyl-containing compound (C) is used, the polyhydroxybenzene compound (A) is more than the above in terms of obtaining a novolak-type resin excellent in heat resistance and long-term storage stability. The ratio of the total mass of the hydroxybenzene compound (A) and other phenolic hydroxyl-containing compound (C) is preferably in the range of 1 to 30% by mass, and more preferably in the range of 1 to 20% by mass.

Among the above-mentioned other phenolic hydroxyl-containing compounds (C), it is preferable to use a hydroxy group in terms of obtaining a novolac resin having excellent heat resistance and long-term storage stability. Benzene compound or hydroxynaphthalene compound. At this time, the ratio of the total mass of the hydroxybenzene compound or the hydroxynaphthalene compound to the above-mentioned polyhydroxybenzene compound (A) and other phenolic hydroxyl-containing compound (C) is preferably in the range of 50 to 99% by mass, and more preferably The range is 80 to 99% by mass. Furthermore, it is preferable to use the above-mentioned polyhydroxybenzene compound (A) and hydroxybenzene compound in a total amount of 50% by mass or more with respect to the total mass of the polyhydroxybenzene compound (A) and other phenolic hydroxyl-containing compound (C). Or a hydroxynaphthalene compound, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

The aldehyde compound (B) may be any one that can form a novolac resin by causing a condensation reaction with a phenolic hydroxyl-containing compound such as the polyhydroxybenzene compound (A), and examples thereof include formaldehyde, Alkane, acetaldehyde, propionaldehyde, tetraformaldehyde, polyformaldehyde, trichloroacetaldehyde, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, hexanal, allylaldehyde, benzaldehyde, phenylacetaldehyde, O-Tolualdehyde, Salicylaldehyde, Crotonaldehyde, Acrolein, etc. These can be used individually or in combination of 2 or more types. Among these, formaldehyde is preferably used in terms of excellent reactivity. Formaldehyde can be used in the form of an aqueous solution, i.e., formalin, or in a solid state, i.e., in the form of paraformaldehyde, which can be either. In the case where formaldehyde is used in combination with other aldehyde compounds, it is preferable to use other aldehyde compounds at a ratio of 0.05 to 1 mole relative to 1 mole of formaldehyde.

Examples of the protic solvent (S) include water or methanol, ethanol, propanol, ethyl lactate, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,5 -Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,3-propanediol, diethylene glycol, polyethylene Glycol, glycerol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether And other alcoholic solvents. These solvents can be used individually or in the form of a mixture of two or more solvents. Above proton The amount of the solvent (S) to be used is preferably in a range of 50% to 300% by mass relative to the total mass of the reaction raw materials.

In the present invention, as long as the reaction between the polyhydroxybenzene compound (A) and the aldehyde compound (B) is carried out in a protic solvent (S), the reaction order or the reaction ratio of each component is not particularly limited, and may be determined according to the requirements. The required resin design is appropriately adjusted. As an example of a specific reaction sequence, the method of the following methods 1-3 is mentioned, for example.

(Method 1) The above polyhydroxybenzene compound (A) and other phenolic hydroxyl group-containing compound (C) are used as a whole, and they are reacted with the aldehyde compound (B) to produce a novolac resin. method.

(Method 2) After reacting the above-mentioned polyhydroxybenzene compound (A) and one or more other phenolic hydroxyl group-containing compounds (C) as necessary with the aldehyde compound (B) to produce one or more novolac resin intermediates A method of reacting one or more of the various novolak-type resin intermediates obtained with the aldehyde compound (B) to produce a capped novolak-type resin.

(Method 3) The polyhydroxybenzene compound (A) and one or more other phenolic hydroxyl group-containing compounds (C) used as needed are reacted with the aldehyde compound (B) to produce a novolak-type resin intermediate. The obtained novolak-type resin intermediate, the above-mentioned polyhydroxybenzene compound (A), and one or more other phenolic hydroxyl-containing compounds (C) used as necessary react with the above-mentioned aldehyde compound (B) to produce a novolak-type resin method.

In any of the above methods 1 to 3, the reaction between the polyhydroxybenzene compound (A) and the aldehyde compound (B) is performed in a protic solvent (S). The production method of the novolak-type resin is performed under the same reaction conditions. Specifically, it may be in the range of 0.5 to 1.2 mol relative to the total of 1 mol of various phenolic hydroxyl-containing compounds. The method using the above-mentioned aldehyde compound (B) in the surroundings and reacting them in the presence of an acid catalyst under a temperature condition of 50 to 200 ° C. After the reaction, if necessary, a step of distilling off unreacted raw materials or solvents, a step of purifying by water washing or reprecipitation, etc. may be performed.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. These can be used individually or in combination of 2 or more types.

Among these various manufacturing methods, the method 3 described above is preferred in terms of obtaining a novolac resin having excellent heat resistance and long-term storage stability. Among them, it is more preferable to produce a novolak-type resin intermediate by reacting another phenolic hydroxyl-containing compound (C) with the aldehyde compound (B), and to obtain the obtained novolak-type resin intermediate and the polyhydroxybenzene compound (A) and a method for reacting the aldehyde compound (B) (hereinafter abbreviated as "Method 3-1").

The method 3-1 will be described in detail. The step of reacting another phenolic hydroxyl-containing compound (C) with the aldehyde compound (B) to produce a novolak-type resin intermediate can be performed in the same manner as the above-mentioned general method for producing a novolak-type resin.

In terms of obtaining a novolak-type resin having high heat resistance and excellent developability, the weight-average molecular weight (Mw) of the obtained novolak-type resin intermediate is preferably in the range of 1,000 to 10,000, and more preferably 1,000. Range of ~ 5,000. The polydispersity index (Mw / Mn) is preferably in the range of 1.2 to 10, and more preferably in the range of 1.5 to 5.

In the present invention, the weight average molecular weight (Mw) and polydispersity index (Mw / Mn) are values measured by GPC under the following conditions.

[GPC measurement conditions]

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation

Column: "Shodex KF802" (8.0mm Φ × 300mm) manufactured by Showa Denko Corporation + "Shodex KF802" (8.0mm Φ × 300mm) manufactured by Showa Denko Corporation + "Shodex" manufactured by Showa Denko Corporation "KF803" (8.0mm Φ × 300mm) + "Shodex KF804" (8.0mm Φ × 300mm) manufactured by Showa Denko Corporation

Column temperature: 40 ℃

Detector: RI (differential refractometer)

Data processing: "GPC-8020 model II version 4.30" manufactured by Tosoh Co., Ltd.

Development solvent: tetrahydrofuran

Flow rate: 1.0mL / min

Sample: a microfiltration filter (100 μl) of a tetrahydrofuran solution with a resin solid content content of 0.5% by mass

Standard sample: the following monodisperse polystyrene

(Standard sample: monodisperse polystyrene)

"A-500" manufactured by Tosoh Corporation

"A-2500" manufactured by Tosoh Corporation

"A-5000" manufactured by Tosoh Corporation

"F-1" manufactured by Tosoh Corporation

"F-2" manufactured by Tosoh Corporation

"F-4" manufactured by Tosoh Corporation

"F-10" manufactured by Tosoh Corporation

"F-20" manufactured by Tosoh Corporation

Then, the obtained novolak-type resin intermediate and the above-mentioned polyhydroxy benzene were phenylated. The step of reacting the compound (A) and the aldehyde compound (B) can be performed in the same manner as the step of obtaining the novolak-type resin intermediate, except that the reaction is performed in a protic solvent (S), in the same manner as the above-mentioned general phenol type The manufacturing method of a novolak-type resin is performed in the same manner. As a more preferable reaction condition, the aldehyde compound (B) is preferably used in the range of 0.5 to 1.2 mols relative to 1 mol of the polyhydroxybenzene compound (A). In addition, in terms of making it easy to control the reaction rate or molecular weight, the reaction is preferably performed at a relatively low temperature condition of 100 ° C or lower.

After the reaction is completed, for example, water can be added to the reaction mixture solution to reprecipitate the product, and the water can be purified by decantation or the like to obtain a target novolac resin in the form of a protic solvent (S) solution. If necessary, the protic solvent (S) can be distilled off to make the novolac resin non-solvent. On the other hand, when it is desired to obtain a novolac resin in the form of a solvent solution other than the above-mentioned protic solvent (S), a desired solvent may be added to the protic solvent (S) of the novolac resin and used. The protic solvent (S) is removed by decantation or distillation, and the solvent is replaced.

The novolak-type resin produced by the method described in the above method 3-1 has a structural portion (I) represented by the following structural formula (1) at the molecular terminal.

[Wherein R ¹ is any of a hydrogen atom, an alkyl group, and an aryl group, m is 2 or 3, R ² is any of an aliphatic hydrocarbon group, an alkoxy group, and an aryl group, and n is 0, 1, or 2]

Novolac resins with this structural site (I) at the molecular end are significantly more reactive, such as When a hardener is blended with the hardener to form a hardenable composition, the heat resistance of the hardened product is very high.

The novolak-type resin manufactured by the manufacturing method of the present invention has a weight-average molecular weight (Mw) in the range of 5,000 to 50,000 in terms of being a novolak-type resin having high heat resistance and excellent developability. A more preferable range is 10,000 to 30,000. The polydispersity index (Mw / Mn) is preferably in the range of 2 to 15, and more preferably in the range of 2.5 to 10.

The novolak resin manufactured by the manufacturing method described in detail above has very high heat resistance, so it can be used in addition to various electrical and electronic components such as photoresist, liquid crystal alignment film, and printed wiring board. Used in adhesives or coatings. In addition, the novolak resin obtained by the production method of the present invention is excellent in alkali solubility or sensitivity, and is therefore particularly suitable for resist applications. It can also be used as a resist substrate in addition to general interlayer insulating films. Various resist members such as films and resist permanent films.

The photosensitive composition manufactured by the manufacturing method of this invention contains the said novolak-type resin and a photosensitizer as an essential component. The photosensitive composition may be used in combination with other resins (D) in addition to the novolac resin. The other resin (D) may be any resin as long as it is soluble in an alkaline developer or is dissolved in an alkaline developer in combination with an additive such as an acid generator.

Examples of the other resin (D) include phenol resin (D-1) other than the above novolac resin, p-hydroxystyrene, or (1,1,1,3,3,3-hexafluoro-2- A homopolymer or copolymer (D-2) of a hydroxy-containing styrene compound such as hydroxypropyl) styrene; the above-mentioned (D-1) is treated with an acid-decomposable group such as a third butoxycarbonyl group or a benzyloxycarbonyl group Or (D-2) hydroxyl group modified (D-3), (meth) acrylic acid homopolymer or copolymer (D-4), norbornene compound or tetracyclododecene compound, etc. Between alicyclic polymerizable monomer and maleic anhydride or maleimide Alternating polymer (D-5), etc.

Examples of the other phenol resin (D-1) include phenol novolac resin, cresol novolac resin, naphthol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, and dicyclopentadiene phenol addition molding resin. Phenol aralkyl resin (ZYLOCK resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenol ethane resin, biphenyl modified phenol resin (the Polyphenol compounds), biphenyl modified naphthol resins (multi-naphthol compounds with phenolic cores linked to phenolic cores), amine tris Modified phenol resin (using melamine, benzoguanidine Phenol resins such as polyphenol compounds linked to a phenol core) or aromatic ring-modified aromatic novolac resins (polyphenol compounds with a phenol core and an alkoxy-containing aromatic ring linked by formaldehyde).

Among the other phenol resins (D) described above, a cresol novolac resin or a co-condensation of cresol and other phenolic compounds is preferred in terms of being a photosensitive resin composition having high sensitivity and excellent heat resistance. Novolac resin. Specifically, the cresol novolac resin or co-condensed novolac resin of cresol and other phenolic compounds is at least one cresol selected from the group consisting of o-cresol, m-cresol and p-cresol. Novolak resin obtained by using an aldehyde compound as an essential raw material and using another phenolic compound in combination.

Examples of other phenolic compounds other than the cresol include phenol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, and 3,4 -Xylenol such as xylenol, 3,5-xylenol; ethylphenol such as o-ethylphenol, m-ethylphenol, p-ethylphenol; isopropylphenol, butylphenol, p-thirdbutyl Butylphenol, such as phenol; Alkylphenols, such as p-pentylphenol, p-octylphenol, p-nonylphenol, and p-cumylphenol; Halogenated phenols, such as fluorophenol, chlorophenol, bromophenol, and iodophenol; p-phenylphenol , Aminophenol, nitrophenol, dinitrophenol, trisphenol 1-substituted phenols such as nitrophenol; condensed polycyclic phenols such as 1-naphthol and 2-naphthol; resorcinol, alkylresorcinol, catechol, catechol, and alkylcatechol Polyphenols such as diphenol, hydroquinone, alkylhydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, dihydroxynaphthalene, etc. These other phenolic compounds may be used individually or in combination of 2 or more types. When these other phenolic compounds are used, the amount of the phenolic compound is preferably a ratio in the range of 0.05 to 1 mol relative to the total of 1 mol of the cresol raw material.

Examples of the aldehyde compound include formaldehyde, paraformaldehyde, and trialdehyde. Alkane, acetaldehyde, propionaldehyde, polyformaldehyde, trichloroacetaldehyde, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, hexanal, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, Formaldehyde, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, etc. can be used individually or in combination of two or more kinds. Among them, formaldehyde is preferred in terms of excellent reactivity, and formaldehyde may be used in combination with other aldehyde compounds. When the formaldehyde is used in combination with other aldehyde compounds, the amount of the other aldehyde compounds used is preferably 1 mol relative to the formaldehyde, and is preferably in the range of 0.05 to 1 mol.

Regarding the reaction ratio of the phenolic compound to the aldehyde compound during the production of the novolac resin, in terms of obtaining a photosensitive resin composition excellent in sensitivity and heat resistance, the aldehyde compound is preferably 0.3 compared to 1 mol of the phenolic compound. The range is from ~ 1.6 mol, more preferably from 0.5 to 1.3.

The reaction of the phenolic compound and the aldehyde compound can be performed in the presence of an acid catalyst at a temperature of 60 to 140 ° C, and then a method of removing water or residual monomers under reduced pressure. Examples of the acid catalyst used here include oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. They can be used individually or in combination of two or more kinds. Among them, oxalic acid is preferred in terms of excellent catalyst activity.

Among the cresol novolac resins described in detail above or co-condensed novolac resins of cresol and other phenolic compounds, m-cresol novolac resin using m-cresol alone or m-cresol and p-cresol in combination are preferred. Cresol novolac resin. In the latter, in terms of being a photosensitive resin composition having an excellent balance between sensitivity and heat resistance, the molar ratio of the reaction between m-cresol and p-cresol is better [m-cresol / p-cresol]. The range is from 10/0 to 2/8, and more preferably from 7/3 to 2/8.

When the other resin (D) is used, the blending ratio of the novolac resin and the other resin (D) can be arbitrarily adjusted according to the required application. For example, the novolak resin obtained by the production method of the present invention is excellent in heat resistance and excellent in alkali solubility or sensitivity. Therefore, a photosensitive composition containing this as a main component is most suitable for a resist application. At this time, the ratio of the above-mentioned novolac resin in the total of the resin components is preferably 60% by mass or more, and more preferably 80% by mass or more.

In addition, the high heat resistance of the novolak-type resin obtained by the production method of the present invention is an unprecedented outstanding level. Therefore, in order to further improve the sensitivity of the photosensitive composition containing other resins (D) as the main component, For heat resistance, a part of the novolac resin may be added. In this case, the blending ratio of the novolac resin and the other resin (D) is preferably in the range of 3 to 80 parts by mass relative to 100 parts by mass of the other resin (D).

Examples of the photosensitizer include compounds having a quinonediazide group. Specific examples of the compound having a quinonediazide group include, for example, an aromatic (poly) hydroxy compound and naphthoquinone-1,2-diazide-5-sulfonic acid and naphthoquinone-1,2-diazide -4-sulfonic acid, o-anthraquinonediazidesulfonic acid and the like, such as quinonediazide sulfonic acid full ester compounds, partial ester compounds, amido compounds or partial amido compounds.

Examples of the aromatic (poly) hydroxy compound used herein include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, and 2,4,6-trione. Hydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxydione Benzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3', 4,4 ', 6-pentahydroxybenzophenone, 2,2', 3,4,4 '-Pentahydroxybenzophenone, 2,2', 3,4,5-pentahydroxybenzophenone, 2,3 ', 4,4', 5 ', 6-hexahydroxybenzophenone, 2 Polyhydroxybenzophenone compounds such as, 3,3 ', 4,4', 5'-hexahydroxybenzophenone; bis (2,4-dihydroxyphenyl) methane, bis (2,3,4- Trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4' -Dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, 4,4 '-{1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylene} bisphenol, 3,3'-dimethyl- {1- [4- [2- (3- ( Bis [(poly) hydroxyphenyl] alkane compounds such as methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylene} bisphenol; tris (4-hydroxyphenyl) methane, bis (4 -Hydroxy-3,5-dimethylbenzene ) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl)- 2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3, Tris (hydroxyphenyl) methane compounds such as 4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane or their methyl substitutions; Bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4 -Hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy- 2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2- Hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3 -Methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl) 4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2 -Hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy- A bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methane compound such as 4-methylphenyl) -4-hydroxyphenylmethane or a methyl substituent thereof. These photosensitizers can be used individually or in combination of 2 or more types.

The blending amount of the photosensitizer in the above-mentioned photosensitive composition is preferably 100 parts by mass with respect to a total of 100 parts by mass of the resin solid component of the photosensitive composition in terms of being a photosensitive composition having excellent sensitivity. The ratio is 5 to 50 parts by mass.

The photosensitive composition may contain a surfactant to improve film-forming properties or adhesion of a pattern when used in a resist application, and to reduce development defects. Examples of the surfactant used herein include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl Polyoxyethylene alkyl allyl ether compounds such as phenol ether, polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymer, sorbitan monolaurate, sorbitan monopalmitate, sorbitan Sorbitan fatty acid ester compounds such as aldonic monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate; polyoxyethylene sorbitan monolaurate Polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, and other polyoxylates Non-ionic surfactants such as ethylene sorbitan fatty acid ester compounds; copolymers of fluoroaliphatic polymerizable monomers and [poly (oxyalkylene)] (meth) acrylates have molecular structures such as Fluorine surfactant with fluorine atom; polysiloxane junction in molecular structure Polysiloxane-based surfactants at structural sites. These can be used individually or in combination of 2 or more types.

The blending amount of these surfactants is preferably used in the range of 0.001 to 2 parts by mass based on 100 parts by mass of the total resin solid component in the photosensitive composition.

When the photosensitive composition is used for photoresist, in addition to the novolac resin and photosensitizer, other resins (D) or surfactants, dyes, fillers, and cross-linking may be added as needed. Various additives such as agents and dissolution accelerators are dissolved in an organic solvent to prepare a composition for a resist. This may be used as a positive resist solution as it is, or a composition obtained by coating and desolvating the composition for a resist may be used as a positive resist film. Examples of the supporting film used as the resist film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. They may be single-layer films or multilayer laminated films. In addition, the surface of the support film may be a corona treated or a release agent coated.

The organic solvent used in the photosensitive composition is not particularly limited, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether. Ethylene glycol monoalkyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and other dialkylene glycol dioxane Ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and other alkylene glycol alkyl ether acetates; acetone, methyl ethyl ketone, Ketone compounds such as cyclohexanone and methylpentyl ketone; Cyclic ethers such as alkanes; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl ethoxylate, 2- Methyl hydroxy-3-methylbutanoate, butyl 3-methoxyacetate, butyl 3-methyl-3-methoxyacetate, ethyl formate, ethyl acetate, butyl acetate, acetamidine acetate Ester compounds such as esters, ethyl acetoacetate, and ethyl lactate can be used alone or in combination of two or more kinds.

The said photosensitive composition can be manufactured by mixing each said component and mixing using a stirrer etc. When the photosensitive composition contains a filler or a pigment, it can be produced by dispersing or mixing using a dispersing device such as a dispersion stirrer, a homogenizer, and a three-roll mill.

The photolithography method using the above-mentioned photosensitive composition is, for example, applying a photosensitive composition to an object subjected to a silicon substrate photolithography method, and performing pre-baking at a temperature of 60 to 150 ° C. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, and doctor blade coating. Next, although the resist pattern is produced, because the above-mentioned photosensitive composition is a positive type, the target resist pattern is exposed through a specific mask, and the exposed portion is dissolved with an alkaline developing solution. Thereby, a resist pattern is formed. Since the above-mentioned photosensitive composition has high alkali solubility in the exposed portion and alkali resistance in the non-exposed portion, it can form a resist pattern with excellent resolution.

The curable composition obtained by the production method of the present invention contains the novolak-type resin and the hardener obtained as described above by the production method of the present invention as essential components. The curable composition may contain other resin (E) in addition to the novolac resin. Examples of other resins (E) used herein include addition polymerization resins of alicyclic diene compounds such as various novolac resins, dicyclopentadiene, and phenol compounds, compounds containing phenolic hydroxyl groups, and alkoxy groups. Modified novolac resin, phenol aralkyl resin (ZYLOCK resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenol ethane resin, biphenyl modified phenol resin, Biphenyl modified naphthol resin, amino tris Modified phenol resin and various vinyl polymers.

More specifically, the above-mentioned various novolak resins include alkanols such as phenol, cresol, and xylenol, bisphenols such as phenylphenol, resorcinol, biphenyl, bisphenol A, and bisphenol F, A polymer obtained by reacting phenolic hydroxyl-containing compounds such as naphthol and dihydroxynaphthalene with aldehyde compounds under acid catalyst conditions.

Examples of the aforementioned various vinyl polymers include polyhydroxystyrene, polystyrene, polyethylene naphthalene, polyethylene anthracene, polyvinylcarbazole, polyindene, polyfluorene, polynorbornene, polycyclodecene, and polytetracycline. Homopolymer or copolymers of vinyl compounds such as dodecene, polynortricyclene, poly (meth) acrylate, and the like.

When these other resins are used, the blending ratio of the above-mentioned novolac resin and other resins (E) can be arbitrarily set according to the application, and the aspect of exhibiting the effect of excellent heat resistance exhibited by the present invention is more significantly exhibited. In terms of 100 mass parts of the novolac resin, the other resin (E) is preferably a ratio of 0.5 to 100 mass parts.

Examples of the hardener used in the present invention include a melamine compound, a guanamine compound, a glycoluril compound, and a urea compound substituted with at least one group selected from the group consisting of methylol, alkoxymethyl, and methyloxymethyl. , Soluble phenolic resin, epoxy compound, isocyanate compound, azide compound, compound containing double bond such as alkenyl ether group, acid anhydride, Oxazoline compounds, etc.

Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, a methoxymethylated compound of 1 to 6 methylol groups of hexamethylolmelamine, hexamethoxyethylmelamine, Hexyloxymethyl melamine, 1-6 methylolated compounds of hydroxymethyl in hexamethylol melamine, etc.

Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethoxymethylbenzoguanidine. 1 to 4 methylol methoxymethylated compounds of tetramethylol guanamine, 1 to 4 methylol guanamine, tetramethoxy guanamine, 1 to 4 methylol guanamine Compounds in which four methylol groups are methylated with methoxyl and the like.

Examples of the glycoluril compound include 1,3,4,6-tetra (methoxymethyl) glycol, 1,3,4,6-tetra (butoxymethyl) glycol, and 1,3,4 , 6-tetrakis (hydroxymethyl) glycol urea and the like.

Examples of the urea compound include 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetra (butoxymethyl) urea, and 1,1,3,3-tetrakis (methoxymethyl) Based) urea and the like.

Examples of the soluble phenol resin include alkanols such as phenol, cresol, and xylenol, bisphenols such as phenol, resorcinol, biphenyl, bisphenol A, and bisphenol F, naphthol, and dihydroxy. A polymer obtained by reacting a phenolic hydroxyl-containing compound such as naphthalene with an aldehyde compound under basic catalyst conditions.

Examples of the epoxy compound include diglycidyloxynaphthalene, phenol novolac epoxy resin, cresol novolac epoxy resin, naphthol novolac epoxy resin, and naphthol-phenol copolycondensation Varnish-type epoxy resin, naphthol-cresol co-acetal novolac-type epoxy resin, phenol-aralkyl-type epoxy resin, naphthol-aralkyl-type epoxy resin, 1,1-bis (2,7-di Glycidyloxy-1-naphthyl) alkane, naphthyl ether type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, Polyglycidyl ether of epoxy resin, co-condensation of phenolic hydroxyl-containing compound and alkoxy-containing aromatic compound.

Examples of the isocyanate compound include toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.

Examples of the azide compound include 1,1'-biphenyl-4,4'-diazide, 4,4'-methylenediazide, 4,4'-oxydiazide, and the like.

Examples of the compound containing a double bond such as an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, and 1,4-butanediol di Vinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane tri Vinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentaethylene Ether, trimethylolpropane trivinyl ether, and the like.

Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, and biphenyltetracarboxylic acid. Aromatic anhydrides such as dianhydride, 4,4 '-(isopropylidene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride; tetrahydrophthalic acid Formic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, inner methylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, Alicyclic carboxylic anhydrides, such as trialkyltetrahydrophthalic anhydride.

Among these, a glycoluril compound, a urea compound, a soluble phenol resin is preferable, and a glycoluril compound is more preferable at the point that it becomes a curable composition excellent in curability or hardened material heat resistance.

The blending amount of the hardener in the hardenable composition is preferably 100 mass parts of the total of the novolac resin and other resins (E) in terms of being a composition having excellent hardenability. The ratio is 0.5 to 50 parts by mass.

When the above-mentioned curable composition is used for a resist base film (BARC film), in addition to the above-mentioned novolac resin and hardener, other resins (E), surfactants, or Various additives such as a dye, a filler, a cross-linking agent, and a dissolution accelerator are dissolved in an organic solvent to prepare a composition for a resist base film.

The organic solvent used for the composition for the resist base film is not particularly limited, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol. Monomethyl ether and other alkylene glycol monoalkyl ethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether Alcohol dialkyl ethers; alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; acetone, methyl ethyl Ketone compounds such as methyl ketone, cyclohexanone, methylpentyl ketone; Cyclic ethers such as alkanes; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl ethoxylate, 2- Methyl hydroxy-3-methylbutanoate, butyl 3-methoxyacetate, butyl 3-methyl-3-methoxyacetate, ethyl formate, ethyl acetate, butyl acetate, acetamidine acetate Ester compounds such as esters, ethyl acetoacetate, and ethyl lactate can be used alone or in combination of two or more kinds.

The said composition for resist base films can be manufactured by mixing each said component and mixing using a stirrer etc. When the composition for a resist base film contains a filler or a pigment, the composition can be produced by dispersing or mixing using a dispersing device such as a dispersion stirrer, a homogenizer, and a three-roll mill.

When the resist base film is produced using the composition for a resist base film, for example, the composition for a resist base film is applied to an object subjected to a photolithography method such as a silicon substrate, and After drying at a temperature of 100 to 200 ° C, the resist base film is formed by a method such as heating and hardening at a temperature of 250 to 400 ° C. Then, a conventional photolithography method is performed on the base film to form a resist pattern, and a dry etching process is performed using a halogen-based plasma gas or the like, whereby a resist pattern can be formed by a multilayer resist method.

When the above-mentioned curable composition is used for a resist permanent film, in addition to the above-mentioned novolac resin and hardener, other resins (E), surfactants, dyes, and fillers may be added as necessary. Various additives, such as crosslinking agents, dissolution accelerators, etc., are dissolved in an organic solvent to prepare a composition for a permanent resist film. The organic solvents used here may be The same as the organic solvent used for the composition for resist base films is mentioned.

The photolithography method using the above-mentioned composition for a permanent resist film is, for example, dissolving and dispersing a resin component and an additive component in an organic solvent, and applying the same to an object subjected to a photolithography method on a silicon substrate. And pre-baking at a temperature of 60 ~ 150 ° C. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, and doctor blade coating. Next, although a resist pattern is produced, when the composition for a permanent resist film is a positive type, the target resist pattern is exposed through a specific mask, and an alkaline developing solution is used. The exposed portion is dissolved, thereby forming a resist pattern.

The permanent film composed of the composition for the above-mentioned resist permanent film can be preferably used in, for example, a semiconductor device relationship, a solder resist, a packaging material, an underfill material, a circuit element, and the like, and an encapsulation bonding layer or an integrated circuit element and circuit The adhesive layer of the substrate can be preferably used for a thin film transistor protective film, a liquid crystal color filter protective film, a black matrix, a spacer, and the like in a thin display relationship represented by LCD and OELD.

[Example]

Hereinafter, the present invention will be described in more detail by giving specific examples.

In this example, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the polydispersity index (Mw / Mn) were measured under the measurement conditions of GPC described below.

[GPC measurement conditions]

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation

String: "Shodex KF802" (8.0mm Φ × 300mm) manufactured by Showa Denko Corporation + "Shodex KF802" (8.0mm Φ × 300mm) manufactured by Showa Denko Corporation + "Shodex KF802" manufactured by Showa Denko Corporation KF803 '' (8.0mm Φ × 300mm) + Zhao `` Shodex KF804 '' (8.0mm Φ × 300mm) manufactured by Waden Electric Co., Ltd.

Column temperature: 40 ℃

Detector: RI (differential refractometer)

Data processing: "GPC-8020 model II version 4.30" manufactured by Tosoh Co., Ltd.

Development solvent: tetrahydrofuran

Flow rate: 1.0mL / min

Sample: A filter obtained by filtering a tetrahydrofuran solution having a mass fraction of 0.5% by mass in terms of resin solid content by a micro filter

Injection volume: 0.1mL

Standard sample: the following monodisperse polystyrene

(Standard sample: monodisperse polystyrene)

"A-500" manufactured by Tosoh Corporation

"A-2500" manufactured by Tosoh Corporation

"A-5000" manufactured by Tosoh Corporation

"F-1" manufactured by Tosoh Corporation

"F-2" manufactured by Tosoh Corporation

"F-4" manufactured by Tosoh Corporation

"F-10" manufactured by Tosoh Corporation

"F-20" manufactured by Tosoh Corporation

Example 1 Production of Novolac Resin (1)

In a 2000 ml four-necked flask equipped with a condenser, 1000 parts by mass of phenol, 600 parts by mass of 41.5% formalin, and 1 part by mass of oxalic acid were added, and the temperature was raised to 99 ° C. over 2 hours while stirring. After that, while performing carbonization, stirring was continued for 3 hours. Switch to the dehydration circuit, while dehydrating, heat up to 180 ° C over 3 hours. While maintaining 180 ° C, the remaining phenol was distilled off to obtain 580 g of a pale red novolac resin intermediate (1). The number-average molecular weight (Mn) of the obtained novolak-type resin intermediate (1) was 966, the weight-average molecular weight (Mw) was 2,126, and the polydispersity index (Mw / Mn) was 2.20.

To a 2,000 ml four-necked flask equipped with a condenser tube were added 450 parts by mass of the novolac resin intermediate (1) obtained in Production Example 1, 50 parts by mass of resorcinol, and 10 parts by mass of 91.5% paraformaldehyde. And it was made to melt | dissolve in 900 mass parts of methanol. After adding 5 parts by mass of 98% sulfuric acid at room temperature, the temperature was raised to 60 ° C. over 1 hour, and stirring was continued for 20 hours. While maintaining 60 ° C, 600 parts by mass of methanol was distilled off under reduced pressure, and while stirring, 1,000 parts by mass of water was added dropwise to reprecipitate the reaction product. The separated water-soluble supernatant was removed by suction, and 300 parts by mass of methanol was added to dissolve the reaction product of the residue. 1,000 parts by mass of water was added again to reprecipitate the reaction product, and the supernatant was removed. 1,000 parts by mass of propylene glycol monoethyl ether acetate was added to dissolve the reaction product, and dehydration was performed under reduced pressure to obtain 793 parts by mass of a novolac resin (1) solution (resin portion 30% by mass). The number-average molecular weight (Mn) of the obtained novolak-type resin (1) was 3,144, the weight-average molecular weight (Mw) was 15,760, and the polydispersity index (Mw / Mn) was 5.01.

Example 2 Production of Novolac Resin (2)

In Example 1, o-cresol novolac resin ["MC-2699HH" manufactured by DIC Corporation, number average molecular weight (Mn) 1,421, weight average molecular weight (Mw) 2,295, and polydispersity index (Mw / Mn) 1.62 were used. ] 450 parts by mass was used in place of the novolak-type resin intermediate (1), and a novolak-type resin (2) solution (resin portion) was obtained in the same manner as in Example 1. 30 mass%) 785 mass parts. The number-average molecular weight (Mn) of the obtained novolak-type resin (2) was 5,633, the weight-average molecular weight (Mw) was 21,074, and the polydispersity index (Mw / Mn) was 3.74.

Example 3 Manufacture of Novolac Resin (3)

In Example 1, except that 50 parts by mass of 1,2,3-trihydroxybenzene was used instead of resorcinol, a solution of novolac resin (3) (resin part 30) was obtained in the same manner as in Example 1. Mass%) 782 parts by mass. The number-average molecular weight (Mn) of the obtained novolak-type resin (3) was 3,385, the weight-average molecular weight (Mw) was 16,543, and the polydispersity index (Mw / Mn) was 4.89.

Comparative Production Example 1 Production of Novolac Resin (1 ')

Add 900 parts by mass of o-cresol, 90 parts by mass of resorcinol, 600 parts by mass of 41.5% formalin, and 1 part by mass of oxalic acid into a 2,000 ml four-necked flask equipped with a condenser, and heat up to 2 hours while stirring After 99 ° C, carbonization was continued and stirring was continued for 3 hours. Switching to the dehydration circuit, the temperature was raised to 180 ° C over 3 hours while dehydration was performed. While maintaining 180 ° C, the remaining o-cresol was distilled off to obtain 530 g of a pale red novolac resin (1 '). The number-average molecular weight (Mn) of the obtained novolak-type resin (1 ′) was 1,032, the weight-average molecular weight (Mw) was 2,234, and the polydispersity index (Mw / Mn) was 2.16.

Evaluation of storage stability

The novolak-type resins obtained in Examples 1 to 3 and Comparative Production Example 1 were dissolved in propylene glycol monomethyl ether acetate, and a sample having a resin concentration of 15% by mass and a sample of 30% by mass were prepared. This sample was placed in a thermostatic bath set at various temperature conditions of 25 ° C, 55 ° C, and 80 ° C, and a storage test was performed for two weeks. Measure the change rate of the weight average molecular weight (Mw) before and after the storage test, and evaluate the case where the absolute value of the change rate is 10% or less, and the absolute value of the change rate exceeds ± 10% The situation was evaluated as B. The results are shown in Table 1.

Examples 4 to 6 and Comparative Example 1

The novolak-type resins obtained in Examples 1 to 3 and Comparative Production Example 1 were manufactured and evaluated based on the following points. The results are shown in Table 2.

Manufacture of hardening composition

53 parts by mass of novolac resin solution (16 parts by mass of resin part), hardener ("1,3,4,6-tetrakis (methoxymethyl) glycol urea" manufactured by Tokyo Chemical Industry Co., Ltd.) 4 Part by mass was dissolved in 143 parts by mass of propylene glycol monomethyl ether acetate, and this was filtered through a 0.2 μm membrane filter to obtain a curable composition.

Evaluation of heat resistance

Using a spin coater, the previously obtained curable composition was applied to a 5 inch silicon wafer so as to have a thickness of about 1 μm, and dried on a heating plate at 110 ° C. for 60 seconds, and then at 230 ° C. Heat treatment was performed for 300 seconds to obtain a cured coating film. The hardened coating film obtained from the wafer was cut, and the differential mass thermogravimetric simultaneous measuring device (TG / DTA) was used to measure the mass reduction amount when the temperature was raised under the following conditions, and the temperature (Td1) when the mass reduction was obtained was determined. .

Measuring machine: "TG / DTA 6200" manufactured by Seiko Instruments Inc.

Measurement range: room temperature to 400 ° C

Heating rate: 10 ℃ / min

Examples 7 to 9 and Comparative Example 2

The novolac-type resins obtained in Examples 1 to 3 and Comparative Production Example 1 were manufactured and evaluated based on the following points. The results are shown in Table 3.

Production of photosensitive composition

24 parts by mass of the above-mentioned novolac resin was dissolved in 60 parts by mass of propylene glycol monomethyl ether acetate, and 16 parts by mass of a photosensitizer was added to the solution to dissolve it. This was filtered through a 0.2-μm membrane filter to obtain a photosensitive composition.

As the photosensitizer, "P-200" (4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylene) manufactured by Toyo Kogyo Co., Ltd. was used. Group] condensate of bisphenol 1 mol and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride 2 mol).

Evaluation of alkaline developability [ADR (nm / s)]

The previously obtained photosensitive composition was coated on a 5 inch silicon wafer with a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110 ° C. for 60 seconds. Two wafers were prepared, and one of them was set as an "unexposed sample". Another piece of a "sample exposed by the" ghi ray lamp and using (Shelter Electric Corp. of manufacture "Multi Light") irradiated with 100mJ / cm ghi ray of ^2, then at 140 deg.] C, subjected to heat treatment at 60 seconds .

After immersing both the "unexposed sample" and the "exposed sample" in an alkaline developing solution (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, they were dried on a hot plate at 110 ° C. 60 seconds. The film thickness before and after immersion of the developer in each sample was measured, and the value obtained by dividing the difference by 60 was defined as alkaline developability [ADR (nm / s)].

Evaluation of sensitivity

The previously obtained photosensitive composition was coated on a 5 inch silicon wafer with a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110 ° C. for 60 seconds. After setting the line and the gap to 1: 1 and the line width to 1 to 10 μm, a mask corresponding to the resist pattern set at intervals of 1 μm was tightly adhered to the wafer, and then a ghi ray lamp (Oxotail Motor Co., Ltd.) was used. "Multi Light" manufactured by Co., Ltd.) was irradiated with ghi rays, and heat-treated at 140 ° C for 60 seconds. Then, after immersing in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, it was dried on a hot plate at 110 ° C for 60 seconds.

For making ghi ray exposure amount from 30mJ / cm ² when the case may be incremented 5mJ / cm ² of the line width 3μm faithful reproduction of an exposure amount (exposure amount Eop) was evaluated.

Evaluation of resolution

The previously obtained photosensitive composition was coated on a 5 inch silicon wafer with a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110 ° C. for 60 seconds. Ghi ray irradiating same procedure 200mJ / cm ^2, alkaline developing operation of the mask is placed onto the wafer obtained, the evaluation of the case of using the alkali-developable previously. Use a laser microscope ("VK-X200" manufactured by Keyence Corporation) to confirm the pattern state. The line width of L / S = 1/1 is 5 μm, and the resolvable is evaluated as A, and L / S = 1 The line width of / 1 was 5 μm and the analysis was evaluated as B.

Claims (15)

A method for producing a novolac resin, in which a polyhydroxybenzene compound (A) and an aldehyde compound (B) are reacted in a protic solvent (S). For example, the manufacturing method of the scope of application for patent No. 1 is to produce a novolac resin intermediate by reacting a phenolic hydroxyl-containing compound (C) other than the above-mentioned compound (A) with the aldehyde compound (B). The obtained novolak-type resin intermediate, the polyhydroxybenzene compound (A) and the aldehyde compound (B) are reacted in a protic solvent (S). For example, the manufacturing method according to the first patent application range, wherein the protic solvent (S) is an alcohol solvent. For example, the manufacturing method of claim 1 in the patent scope, wherein the obtained novolak-type resin has a structural portion (I) represented by the following structural formula (1) at a molecular terminal, [Wherein R ¹ is any of a hydrogen atom, an alkyl group, and an aryl group, m is 2 or 3, R ² is any of an aliphatic hydrocarbon group, an alkoxy group, and an aryl group, and n is 0, 1, or 2]. A method for producing a photosensitive composition, comprising blending a novolac resin and a photosensitizer manufactured by the manufacturing method according to any one of claims 1 to 4. A method for manufacturing a resist material, which uses a photosensitive composition manufactured by a manufacturing method according to claim 5 of a patent application. A method for manufacturing a hardenable composition, the blending and utilization of which are the scope of patent applications No. 1 to 4 Novolac-type resin and hardener manufactured by any one of the manufacturing methods. A method for producing a hardened product, which uses a hardenable composition produced by a production method according to claim 7 of a patent application. A method for producing a resist material using a hardenable composition produced by a production method according to claim 7 of a patent application. A novolac resin is manufactured by a manufacturing method according to any one of claims 1 to 4. A photosensitive composition comprising a novolac resin and a sensitizer in the tenth aspect of the patent application. A resist material using the photosensitive composition of claim 11 in the scope of patent application. A hardening composition containing a novolac resin and a hardener in the tenth aspect of the patent application. A hardened material is a hardened material of the hardenable composition of the thirteenth patent application. A resist material using a hardenable composition in the thirteenth patent application.