JP6269904B1 - Method for producing novolac resin - Google Patents

Abstract

Method for producing novolac resin having very high heat resistance and excellent long-term storage stability under various temperature conditions, novolac resin produced by the production method, and photosensitive composition containing the novolac resin Alternatively, a curable composition and a resist material using the same are provided. A method for producing a novolac resin, comprising reacting a polyhydroxybenzene compound (A) and an aldehyde compound (C) in a protic solvent (S), and a novolac resin produced by the production method.

Description

  The present invention is a method for producing a novolac resin having very high heat resistance and excellent long-term storage stability under various temperature conditions, a novolac resin produced by the production method, and a photosensitive composition containing the same The present invention relates to an object or a curable composition and a resist material using these.

  Phenolic hydroxyl group-containing resins such as novolak resins are used in adhesives, molding materials, paints, photoresist materials, epoxy resin raw materials, epoxy resin curing agents, etc., as well as heat resistance and moisture resistance in cured products As a curable composition mainly composed of a phenolic hydroxyl group-containing resin itself, or as a curing agent such as an epoxy resin, it is widely used in the electrical and electronic fields such as semiconductor sealing materials and insulating materials for printed wiring boards. It is used.

  Among these, in the field of photoresists, a wide variety of resist pattern formation methods that have been subdivided according to applications and functions have been developed one after another, and as a result, the required performance for resist resin materials has become more sophisticated and diversified. Yes. For example, in addition to high developability to form fine patterns accurately and with high production efficiency on highly integrated semiconductors, it is necessary to have properties such as cured products that are flexible and resistant to cracking when forming thick films. When used as a resist underlayer film, dry etching resistance and heat resistance are required, and when used as a resist permanent film, toughness such as substrate followability is required in addition to heat resistance. Furthermore, from the viewpoint of quality and reliability, long-term storage stability in various environments around the world is one of the important performances.

  As a resist resin material excellent in developability and heat resistance, for example, a novolak resin composed of alkylphenol such as cresol and xylenol and dihydroxybenzene is known (see Patent Documents 1 and 2 below). These novolak resins are excellent in terms of alkali solubility and photosensitivity, and are excellent in terms of obtaining resist patterns with high resolution, but they have low heat resistance and long-term storage stability under relatively high temperature conditions. Since the properties were not sufficient, development of a resin material having these performances was required.

JP 11-258808 A JP 2000-137324 A

  Therefore, the problem to be solved by the present invention is not only excellent in developability and photosensitivity, but also has a very high heat resistance and a method for producing a novolac resin that is excellent in long-term storage stability under various temperature conditions, An object of the present invention is to provide a novolac resin produced by the production method, a photosensitive composition or a curable composition containing the novolac resin, and a resist material using these.

  As a result of intensive studies to solve the above problems, the present inventors have produced a novolac resin using polyhydroxybenzene as an essential reaction raw material in a protic solvent. The inventors have found that a novolac resin excellent in long-term storage stability under various temperature conditions can be obtained, and the present invention has been completed.

  That is, the present invention relates to a method for producing a novolac resin, comprising reacting a polyhydroxybenzene compound (A) and an aldehyde compound (B) in a protic solvent (S).

  The present invention further relates to a method for producing a photosensitive composition comprising a novolac resin produced by the above production method and a photosensitive agent.

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

  The present invention further relates to a method for producing a curable composition comprising a novolac resin produced by the above production method and a curing agent.

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

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

  The present invention further relates to a novolac resin produced by the production method.

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

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

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

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

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

  According to the present invention, a method for producing a novolac resin having very high heat resistance and excellent long-term storage stability under various temperature conditions, a novolac resin produced by the production method, and the novolac resin A photosensitive composition or a curable composition to be contained, and a resist material using these can be provided.

  The method for producing a novolak resin of the present invention is characterized in that the polyhydroxybenzene compound (A) and the aldehyde compound (B) are reacted 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 the benzene ring, and the substitution position of the phenolic hydroxyl group and the presence or absence of other substituents are not particularly limited. Moreover, a polyhydroxybenzene compound (A) may be used individually by 1 type, and may be used in combination of 2 or more types. Specific examples of the polyhydroxybenzene compound (A) include, for example, the following structural formula (2)

［ｍは２又は３である。式中Ｒ^２は脂肪族炭化水素基、アルコキシ基、アリール基の何れかであり、ｎは０、１又は２である。］
で表される分子構造を有する化合物等が挙げられる。

[M is 2 or 3. In the formula, R ² is any of an aliphatic hydrocarbon group, an alkoxy group, and an aryl group, and n is 0, 1, or 2. ]
The compound etc. which have the molecular structure represented by these are mentioned.

R ² in the structural formula (2) is an aliphatic hydrocarbon group, an alkoxy group, or an aryl group. The aliphatic hydrocarbon group may be linear or branched, and may have an unsaturated bond in the structure. Specific examples include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, and nonyl group alkyl group. And a cycloalkyl group such as a cyclohexyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and a t-butoxy group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, and a structural site in which an alkyl group, an alkoxy group, a halogen atom, or the like is substituted on the aromatic nucleus. Especially, since it becomes a novolak-type resin excellent in heat resistance, R ² is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably n is 0.

  M in the structural formula (2) 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, those in which the hydroxyl substitution position is any of the 1,2-position, the 1,3-position, and the 1,4-position. When m is 3, for example, those in which the hydroxyl substitution position is any of 1,2,3-position, 1,2,4-position, and 1,3,5-position. Among them, since a novolak resin excellent in heat resistance and long-term storage stability can be obtained, a dihydroxybenzene compound in which m is 2 is preferable, and a resorcinol type compound having a hydroxyl group in the 1,3-position is particularly preferable. preferable.

  In the production method of the present invention, a phenolic hydroxyl group-containing compound (C) other than the compound (A) may be used in combination with the polyhydroxybenzene compound (A). Examples of the other phenolic hydroxyl group-containing compound (C) include hydroxybenzene compounds, (poly) hydroxynaphthalene compounds, (poly) hydroxyanthracene compounds, biphenol compounds, and bisphenol compounds. Examples of the hydroxybenzene compound include: phenols; alkylphenols such as cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, butylphenol, t-butylphenol, pentylphenol, octylphenol, nonylphenol, cumylphenol; fluorophenol, chlorophenol, Halogenated phenols such as bromophenol and iodophenol; arylphenols such as phenylphenol; phenols having a functional group such as aminophenol, nitrophenol, dinitrophenol, and trinitrophenol. Examples of the (poly) hydroxynaphthalene compound include naphthol, dihydroxynaphthalene, compounds in which an alkyl group, an alkoxy group, a halogen atom, or the like is substituted on the aromatic nucleus. Examples of the (poly) hydroxyanthracene compound include anthracenol and compounds in which an alkyl group, an alkoxy group, a halogen atom, or the like is substituted on the aromatic nucleus. Examples of the biphenol compound include compounds in which an alkyl group, an alkoxy group, a halogen atom, or the like is substituted on biphenol and its aromatic nucleus. Examples of the bisphenol compound include bisphenol A, bisphenol F, bisphenol B, bisphenol S, and compounds in which an alkyl group, an alkoxy group, a halogen atom, or the like is substituted on these aromatic nuclei. These may be used alone or in combination of two or more.

  When the other phenolic hydroxyl group-containing compound (C) is used, a novolac resin having excellent heat resistance and long-term storage stability can be obtained. Therefore, the polyhydroxybenzene compound (A) and the other phenolic hydroxyl group are obtained. It is preferable that the ratio of the said polyhydroxybenzene compound (A) with respect to the total mass with a containing compound (C) is the range of 1-30 mass%, and it is more preferable that it is the range of 1-20 mass%.

  Among the other phenolic hydroxyl group-containing compounds (C), it is preferable to use a hydroxybenzene compound or a hydroxynaphthalene compound because a novolak resin excellent in heat resistance and long-term storage stability can be obtained. At this time, the ratio of the hydroxybenzene compound or hydroxynaphthalene compound to the total mass of the polyhydroxybenzene compound (A) and the other phenolic hydroxyl group-containing compound (C) is preferably in the range of 50 to 99% by mass, A range of 80 to 99% by mass is more preferable. Furthermore, with respect to the total mass of the polyhydroxybenzene compound (A) and the other phenolic hydroxyl group-containing compound (C), the total of the polyhydroxybenzene compound (A) and the hydroxybenzene compound or hydroxynaphthalene compound is 50 mass. % Is preferably used, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.

  The aldehyde compound (B) is not particularly limited as long as it can form a novolak-type resin by causing a condensation reaction with a phenol hydroxyl group-containing compound such as the polyhydroxybenzene compound (A). For example, formaldehyde, trioxane, acetaldehyde, propion Aldehyde, tetraoxymethylene, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, crotonaldehyde, acrolein, etc. Is mentioned. These may be used alone or in combination of two or more. Among them, it is preferable to use formaldehyde because of excellent reactivity. Formaldehyde may be used either as formalin in an aqueous solution or as paraformaldehyde in a solid state. Moreover, when using together formaldehyde and another aldehyde compound, it is preferable to use another aldehyde compound in the ratio of 0.05-1 mol with respect to 1 mol of formaldehyde.

  Examples of the protic solvent (S) include water, 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, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin, 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 Alcoholic solvents such as Le like. These solvents may be used alone or in combination of two or more kinds. The amount of the protic solvent (S) used is preferably in the range of 50% by mass to 300 parts by mass with respect 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 performed in the protic solvent (S), the reaction order, the reaction ratio of each component, and the like are particularly limited. It is not a thing and it can adjust suitably according to desired resin design. Specific examples of the reaction order include methods such as the following methods 1 to 3.

(Method 1) The polyhydroxybenzene compound (A) and other phenolic hydroxyl group-containing compound (C) used as needed are used together and reacted with the aldehyde compound (B) to form a novolak type. A method for producing a resin.
(Method 2) One or more kinds of the polyhydroxybenzene compound (A) and other phenolic hydroxyl group-containing compound (C) used as necessary are reacted with the aldehyde compound (B) to produce one kind of novolak type resin intermediate. A method for producing a block type novolak resin by reacting one or more kinds of the obtained various novolak type resin intermediates with an aldehyde compound (B) after the production of the plurality of types.
(Method 3) A novolak resin obtained by reacting one or more of the polyhydroxybenzene compound (A) and other phenolic hydroxyl group-containing compound (C) used as necessary with the aldehyde compound (B). A novolak-type resin intermediate obtained by producing an intermediate, one or more of the polyhydroxybenzene compound (A) and other phenolic hydroxyl group-containing compound (C) used as necessary, and the aldehyde A method for producing a novolac resin by reacting the compound (B).

  In any of the above methods 1 to 3, production of a general phenol novolac resin except that the reaction of the polyhydroxybenzene compound (A) and the aldehyde compound (B) is performed in a protic solvent (S). The reaction can be performed under the same reaction conditions as in the method. Specifically, the aldehyde compound (B) is used in a range of 0.5 to 1.2 mol with respect to a total of 1 mol of various phenolic hydroxyl group-containing compounds, and the temperature is 50 to 200 ° C. in the presence of an acid catalyst. The method of making it react on conditions is mentioned. After completion of the reaction, a step of distilling off unreacted raw materials and solvents, a step of purification by washing with water, reprecipitation, or the like may be performed as necessary.

  Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Is mentioned. These may be used alone or in combination of two or more.

  Among these various production methods, the above-mentioned method 3 is preferable because a novolac resin excellent in heat resistance and long-term storage stability can be obtained. Among them, a novolak-type resin intermediate is produced by reacting the other phenolic hydroxyl group-containing compound (C) with the aldehyde compound (B), and the resulting novolak-type resin intermediate and the polyhydroxybenzene compound ( A method of reacting A) with the aldehyde compound (B) (hereinafter abbreviated as “Method 3-1”) is more preferable.

  The method 3-1 will be described in detail. The process for producing the novolak-type resin intermediate by reacting the other phenolic hydroxyl group-containing compound (C) with the aldehyde compound (B) is carried out in the same manner as in the general method for producing a phenol novolak-type resin described above. be able to.

  The obtained novolak type resin intermediate has a high heat resistance and a novolak type resin having excellent developability, so that the weight average molecular weight (Mw) is preferably in the range of 1,000 to 10,000. More preferably, it is in the range of 5,000 to 5,000. The polydispersity (Mw / Mn) is preferably in the range of 1.2 to 10, more preferably in the range of 1.5 to 5.

In the present invention, the weight average molecular weight (Mw) and the polydispersity (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” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK
+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ × 300 mm) + Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ × 300 mm)
Column temperature: 40 ° C
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.30” manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample: Filtered 0.5% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)
Standard sample: Monodispersed polystyrene below (Standard sample: Monodispersed 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

  Next, the step of reacting the obtained novolak-type resin intermediate, the polyhydroxybenzene compound (A), and the aldehyde compound (B), except that the reaction is performed in a protic solvent (S), It can carry out similarly to the manufacturing method of the general phenol novolak type resin mentioned above similarly to the process of obtaining a novolak type resin intermediate. As more preferable reaction conditions, it is preferable to use the aldehyde compound (B) in a range of 0.5 to 1.2 mol with respect to 1 mol of the polyhydroxybenzene compound (A). In addition, since the reaction rate and molecular weight can be easily controlled, the reaction is preferably carried out under a relatively low temperature condition of 100 ° C. or lower.

  After completion of the reaction, for example, water is added to the reaction mixture solution to reprecipitate the product, and the product is purified by removing water by decantation or the like, and the target novolak resin is purified with a protic solvent (S) solution. Can be obtained as If necessary, the protic solvent (S) may be further distilled off and the novolac resin may be used without solvent. On the other hand, when it is desired to obtain the novolak type resin as a solvent solution other than the protic solvent (S), a desired solvent is added to the protic solvent (S) of the novolak type resin, and the proton is then decanted or distilled. The solvent (S) can be removed and solvent replacement can be performed.

  The novolak-type resin produced by the method such as Method 3-1 has the following structural formula (1) at the molecular end.

［式中Ｒ^１は水素原子、アルキル基、アリール基の何れかである。ｍは２又は３である。Ｒ^２は脂肪族炭化水素基、アルコキシ基、アリール基の何れかであり、ｎは０、１又は２である。］
で表される構造部位（Ｉ）を有するものとなる。該構造部位（Ｉ）を分子末端に有するノボラック型樹脂は反応性が著しく高く、例えば、硬化剤と配合して硬化性組成物とした場合の硬化物における耐熱性が非常に高いものとなる。

[Wherein R ¹ is any one of a hydrogen atom, an alkyl group, and an aryl group. m is 2 or 3. R ² is an aliphatic hydrocarbon group, an alkoxy group or an aryl group, and n is 0, 1 or 2. ]
It has a structural site (I) represented by The novolak type resin having the structural site (I) at the molecular end is extremely high in reactivity, and for example, the heat resistance in the cured product when it is blended with a curing agent to form a curable composition is very high.

  Since the novolak resin produced by the production method of the present invention is a novolak resin having high heat resistance and excellent developability, its weight average molecular weight (Mw) is in the range of 5,000 to 50,000. It is preferable that it is in the range of 10,000 to 30,000. The polydispersity (Mw / Mn) is preferably in the range of 2 to 15, and more preferably in the range of 2.5 to 10.

  The novolak type resin produced by the production method described in detail above has a very high heat resistance, so that it can be used for various types of electric and electronic members such as photoresists, liquid crystal alignment films, and printed wiring boards. It can also be suitably used for adhesives and paints. In addition, the novolac resin obtained by the production method of the present invention is excellent in alkali solubility and photosensitivity, and is particularly suitable for resist applications. In addition to a general interlayer insulating film, a resist underlayer film, a resist permanent film It can be used for various resist members such as a film.

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

  Examples of the other resin (D) include other phenolic resins (D-1) other than the novolak type resin, p-hydroxystyrene and p- (1,1,1,3,3,3-hexafluoro- Homopolymer or copolymer (D-2) of a hydroxy group-containing styrene compound such as 2-hydroxypropyl) styrene, the hydroxyl group of (D-1) or (D-2) is replaced with a t-butoxycarbonyl group or benzyloxy Modified with an acid-decomposable group such as carbonyl group (D-3), homopolymer or copolymer (D-4) of (meth) acrylic acid, alicyclic such as norbornene compound and tetracyclododecene compound Examples thereof include an alternating polymer (D-5) of a polymerizable monomer and maleic anhydride or maleimide.

  Examples of the other phenol resin (D-1) include phenol novolak resin, cresol novolak resin, naphthol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zylock resin). ), Naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl modified phenolic resin (polyhydric phenol compound with phenol nucleus linked by bismethylene group), biphenyl modified naphthol resin (phenol nucleus linked by bismethylene group) Polyhydric naphthol compounds), aminotriazine-modified phenolic resins (polyhydric phenol compounds with phenolic nuclei linked by melamine, benzoguanamine, etc.) and alkoxy groups Aromatic ring-modified novolac resins (polyvalent phenolic compounds phenol nucleus and an alkoxy group-containing aromatic ring are connected by formaldehyde) and phenol resins.

  Among the other phenol resins (D), a cresol novolak resin or a co-condensed novolak resin of cresol and another phenolic compound is preferable because it is a photosensitive resin composition having high sensitivity and excellent heat resistance. The cresol novolac resin or the co-condensed novolak resin of cresol and other phenolic compound specifically includes at least one cresol selected from the group consisting of o-cresol, m-cresol and p-cresol and an aldehyde compound. It is a novolak resin obtained as an essential raw material and appropriately used in combination with other phenolic compounds.

  Other phenolic compounds other than the cresol include, for example, phenol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol Xylenol such as o-ethylphenol, m-ethylphenol, p-ethylphenol, etc .; butylphenol such as isopropylphenol, butylphenol, pt-butylphenol; p-pentylphenol, p-octylphenol, p-nonylphenol, alkylphenols such as p-cumylphenol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol and iodophenol; p-phenylphenol, aminophenol, nitrophenol, di 1-substituted phenols such as trophenol and trinitrophenol; condensed polycyclic phenols such as 1-naphthol and 2-naphthol; resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol A, bisphenol And polyhydric phenols such as F, bisphenol S, and dihydroxynaphthalene. These other phenolic compounds may be used alone or in combination of two or more. When these other phenolic compounds are used, the amount used is preferably such that the other phenolic compound is in the range of 0.05 to 1 mol with respect to a total of 1 mol of the cresol raw material.

  Examples of the aldehyde compound include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, and croton. Examples include aldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, and the like. These may be used alone or in combination of two or more. Among these, formaldehyde is preferable because of its excellent reactivity, and formaldehyde and other aldehyde compounds may be used in combination. When formaldehyde and another aldehyde compound are used in combination, the amount of the other aldehyde compound used is preferably in the range of 0.05 to 1 mol with respect to 1 mol of formaldehyde.

  The reaction ratio between the phenolic compound and the aldehyde compound in producing the novolak resin is such that a photosensitive resin composition having excellent sensitivity and heat resistance is obtained, so that the aldehyde compound is 0.3 to 1 mol per mol of the phenolic compound. The range is preferably 1.6 mol, and more preferably 0.5 to 1.3.

  The reaction between the phenolic compound and the aldehyde compound is carried out under a temperature condition of 60 to 140 ° C. in the presence of an acid catalyst, and then water and residual monomers are removed under a reduced pressure condition. Examples of the acid catalyst used here include oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, manganese acetate, etc., each of which may be used alone or in combination of two or more. May be. Of these, oxalic acid is preferred because of its excellent catalytic activity.

  Among the cresol novolak resins detailed above or co-condensed novolak resins of cresol and other phenolic compounds, cresol novolak resins using metacresol alone or cresol novolak resins using metacresol and paracresol in combination It is preferable that In the latter case, the reaction molar ratio of metacresol to paracresol [metacresol / paracresol] is a photosensitive resin composition having an excellent balance between sensitivity and heat resistance. The range is preferable, and the range of 7/3 to 2/8 is more preferable.

  When using the said other resin (D), the compounding ratio of the said novolak-type resin and other resin (D) can be arbitrarily adjusted with a desired use. For example, the novolac resin obtained by the production method of the present invention is excellent in heat resistance, and is excellent in alkali solubility and photosensitivity. is there. At this time, the ratio of the novolac resin in the total resin component is preferably 60% by mass or more, and more preferably 80% by mass or more.

  Moreover, since the high heat resistance which the novolak-type resin obtained by the manufacturing method of the present invention has is an unprecedented level, the heat resistance of the photosensitive composition containing the other resin (D) as a main component. In order to further improve the properties, a part of the novolac resin may be added and used. In this case, the blending ratio of the novolac resin and the other resin (D) is preferably 3 to 80 parts by mass of the novolac resin with respect to 100 parts by mass of the other resin (D). .

  Examples of the photosensitive agent include compounds having a quinonediazide group. Specific examples of the compound having a quinonediazide group include, for example, an aromatic (poly) hydroxy compound, naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, orthoanthra Examples thereof include complete ester compounds, partial ester compounds, amidated products, and partially amidated products with sulfonic acids having a quinonediazide group such as quinonediazidesulfonic acid.

  Examples of the aromatic (poly) hydroxy compound used here include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3, 6-trihydroxybenzophenone, 2,3,4-trihydroxy-2′-methylbenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 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, 2,3,3 ′, 4,4 ′, 5′-hexahydroxybenzo Polyhydroxy benzophenone compounds such Enon;

  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] ethylidene} bisphenol, 3,3′-dimethyl- {1- [4- [2- ( Bis [(poly) hydroxyphenyl] alkane compounds such as 3-methyl-4-hydroxyphenyl) -2-propyl] phenyl] ethylidene} bisphenol;

  Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -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-dimethyl) Phenyl) -3,4-dihydroxyphenylmethane, tris (hydroxyphenyl) methane compounds such as bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane or methyl-substituted products thereof;

  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- Methylfe ) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxy Phenylmethane, 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-4-methylphenyl) -4-hydroxyphenylmethane and the like bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methane compounds or their Chill substituents and the like. These photosensitizers may be used alone or in combination of two or more.

  Since the compounding amount of the photosensitive agent in the photosensitive composition becomes a photosensitive composition excellent in photosensitivity, the ratio of 5 to 50 parts by mass with respect to 100 parts by mass in total of the resin solid content of the photosensitive composition. It is preferable that

  The photosensitive composition may contain a surfactant for the purpose of improving film-forming property and pattern adhesion when used for resist applications, and reducing development defects. Examples of the surfactant used here include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ether compounds such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene Polyoxyethylene alkyl allyl ether compounds such as ethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid ester compounds such as polyoxyethylene sorbitan monolaurate, poly Nonionic surfactants such as polyoxyethylene sorbitan fatty acid ester compounds such as xylethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate; fluoro fat Fluorosurfactants having a fluorine atom in the molecular structure, such as a copolymer of a polymerizable monomer having a group and [poly (oxyalkylene)] (meth) acrylate; Examples thereof include silicone surfactants. These may be used alone or in combination of two or more.

  It is preferable to use these surfactants in a range of 0.001 to 2 parts by mass with respect to 100 parts by mass in total of the resin solid content in the photosensitive composition.

  When the photosensitive composition is used for photoresist applications, in addition to the novolak type resin and the photosensitive agent, other resins (D), surfactants, dyes, fillers, cross-linking agents, and dissolution agents may be used as necessary. Various additives such as an accelerator can be added and dissolved in an organic solvent to obtain a resist composition. This may be used as it is as a positive resist solution, or may be used as a positive resist film obtained by removing the solvent by applying the resist composition in a film form. Examples of the support film used as a resist film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate, and may be a single layer film or a plurality of laminated films. The surface of the support film may be a corona-treated one or a release agent.

  The organic solvent used in the photosensitive composition is not particularly limited, and examples thereof include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether. Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; alkylene glycols such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Alkyl ether acetate; ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone; cyclic ethers such as dioxane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, Ethyl ethoxy acetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate And ester compounds such as ethyl lactate. These may be used alone or in combination, or two or more of them may be used in combination.

  The said photosensitive composition can be manufactured by mix | blending said each component and mixing using a stirrer etc. Further, 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 dissolver, a homogenizer, or a three roll mill.

  In the photolithography method using the photosensitive composition, for example, the photosensitive composition is applied onto an object to be subjected to silicon substrate photolithography, and prebaked 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, doctor blade coating and the like. Next, the formation of a resist pattern, since the photosensitive composition is a positive type, by exposing the intended resist pattern through a predetermined mask, by dissolving the exposed portion with an alkaline developer, A resist pattern is formed. Since the photosensitive composition has high alkali solubility in the exposed area and alkali resistance in the non-exposed area, it is possible to form a resist pattern with excellent resolution.

  The curable composition obtained by the production method of the present invention contains the novolac resin obtained by the production method of the present invention and a curing agent as essential components. The curable composition may contain other resin (E) in addition to the novolac resin. Other resins (E) used here include, for example, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, Modified novolak resin, phenol aralkyl resin (Xylok resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl modified phenol resin, biphenyl modified naphthol resin, aminotriazine modified phenol resin, and various vinyl polymers Etc.

  More specifically, the various novolak resins include phenols, alkylphenols such as cresol and xylenol, bisphenols such as phenylphenol, resorcinol, biphenyl, bisphenol A and bisphenol F, and phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene. And a polymer obtained by reacting an aldehyde compound with an acid catalyst.

  The various vinyl polymers include polyhydroxystyrene, polystyrene, polyvinyl naphthalene, polyvinyl anthracene, polyvinyl carbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly ( A homopolymer of a vinyl compound such as (meth) acrylate or a copolymer thereof may be mentioned.

  When these other resins are used, the blending ratio of the novolac resin and the other resin (E) can be arbitrarily set according to the use, but the effect of the present invention that is excellent in heat resistance is more remarkable. Therefore, it is preferable that the other resin (E) has a ratio of 0.5 to 100 parts by mass with respect to 100 parts by mass of the novolac resin.

  The curing agent used in the present invention is, for example, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, a resole resin, an epoxy substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Compound, isocyanate compound, azide compound, compound containing double bond such as alkenyl ether group, acid anhydride, oxazoline compound and the like.

  Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, and hexamethylol melamine methylol. Examples include compounds in which 1 to 6 of the groups are acyloxymethylated.

  Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, tetramethoxyethylguanamine, tetraacyloxyguanamine, tetra Examples thereof include compounds in which 1 to 4 methylol groups of methylolguanamine are acyloxymethylated.

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

  Examples of the urea compound include 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea and 1,1,3,3-tetrakis (methoxymethyl) urea. It is done.

  The resole resin may be, for example, an alkylphenol such as phenol, cresol or xylenol, a bisphenol such as phenylphenol, resorcinol, biphenyl, bisphenol A or bisphenol F, a phenolic hydroxyl group-containing compound such as naphthol or dihydroxynaphthalene, and an aldehyde compound. Examples include polymers obtained by reacting under catalytic conditions.

  Examples of the epoxy compound include diglycidyloxynaphthalene, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane, naphthylene ether type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene- Examples include phenol addition reaction type epoxy resins, phosphorus atom-containing epoxy resins, polyglycidyl ethers of cocondensates of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, and the like. .

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

  Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, 4,4'-oxybisazide, 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-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether. , Neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether Etc.

  Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4 Aromatic acid anhydrides such as '-(isopropylidene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride And alicyclic carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, and trialkyltetrahydrophthalic anhydride.

  Among these, a glycoluril compound, a urea compound, and a resole resin are preferable, and a glycoluril compound is particularly preferable because it becomes a curable composition having excellent curability and heat resistance in a cured product.

  Since the compounding quantity of the said hardening | curing agent in the said curable composition becomes a composition excellent in sclerosis | hardenability, it is 0.5-50 with respect to a total of 100 mass parts of the said novolak-type resin and other resin (E). It is preferable that it is the ratio used as a mass part.

  When the curable composition is used for resist underlayer film (BARC film), in addition to the novolak type resin and curing agent, other resins (E), surfactants, dyes, and fillers as necessary. The composition for resist underlayer film can be obtained by adding various additives such as a crosslinking agent and a dissolution accelerator and dissolving in an organic solvent.

  The organic solvent used in the resist underlayer film composition is not particularly limited, and examples thereof include alkylene glycol monomethyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether. Alkyl ethers; Dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; alkylene groups such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Cole alkyl ether acetate; Ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone; Cyclic ethers such as dioxane; Methyl 2-hydroxypropionate, Ethyl 2-hydroxypropionate, Ethyl 2-hydroxy-2-methylpropionate , Ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, acetoacetic acid Examples thereof include ester compounds such as ethyl and ethyl lactate, which may be used alone or in combination of two or more.

  The resist underlayer film composition can be produced by blending the above components and mixing them using a stirrer or the like. When the resist underlayer film composition contains a filler or a pigment, it can be produced by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three roll mill.

  In order to create a resist underlayer film from the resist underlayer film composition, for example, the resist underlayer film composition is applied onto an object to be subjected to photolithography such as a silicon substrate, and is subjected to a temperature condition of 100 to 200 ° C. Then, a resist underlayer film is formed by a method such as heat curing under a temperature condition of 250 to 400 ° C. Next, a resist pattern is formed on this lower layer film by performing a normal photolithography operation, and a resist pattern by a multilayer resist method can be formed by performing a dry etching process with a halogen-based plasma gas or the like.

  When the curable composition is used for resist permanent film applications, in addition to the novolak-type resin and curing agent, other resins (E), surfactants and dyes, fillers, crosslinking agents, A resist permanent film composition can be obtained by adding various additives such as a dissolution accelerator and dissolving in an organic solvent. The organic solvent used here is the same as the organic solvent used in the resist underlayer film composition.

  A photolithography method using the resist permanent film composition may be, for example, dissolving and dispersing a resin component and an additive component in an organic solvent, and applying the solution on an object to be subjected to silicon substrate photolithography at 60 to 150 ° C. Pre-bake under the following temperature conditions. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating and the like. Next, when creating the resist pattern, if the resist permanent film composition is positive, the target resist pattern is exposed through a predetermined mask, and the exposed portion is dissolved with an alkali developer. Thus, a resist pattern is formed.

  The permanent film made of the resist permanent film composition is, for example, a solder resist, a package material, an underfill material, a package adhesive layer such as a circuit element, an integrated circuit element-circuit board adhesive layer, an LCD, or an OELD for semiconductor devices. Can be suitably used for thin film transistor protective films, liquid crystal color filter protective films, black matrices, spacers and the like.

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

In this example, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the polydispersity (Mw / Mn) are measured under the following GPC measurement conditions.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK
+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ × 300 mm) + Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ × 300 mm)
Column temperature: 40 ° C
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.30” manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample: 0.5% by mass tetrahydrofuran solution filtered with a microfilter in terms of resin solids Injection volume: 0.1 mL
Standard sample: Monodispersed polystyrene below (Standard sample: Monodispersed 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 Novolak Type Resin (1) A 2000 ml four-necked flask equipped with a cooling tube was charged with 1000 parts by mass of phenol, 600 parts by mass of 41.5% formalin, and 1 part by mass of oxalic acid, and stirred for 2 hours to 99 ° C. Then, the mixture was heated up and stirred for 3 hours while dry distillation. It switched to the dehydration circuit and heated up to 180 degreeC over 3 hours, dehydrating. The remaining phenol was distilled off while maintaining 180 ° C. to obtain 580 g of a light red novolac resin intermediate (1). The obtained novolak type resin intermediate (1) had a number average molecular weight (Mn) of 966, a weight average molecular weight (Mw) of 2,126, and a polydispersity (Mw / Mn) of 2.20.

  In a 2,000 ml four-necked flask equipped with a cooling tube, 450 parts by mass of the novolak-type resin intermediate (1) obtained in Production Example 1, 50 parts by mass of resorcinol, 10 parts by mass of 91.5% paraformaldehyde were charged, and 900 parts by mass of methanol. Was dissolved in a portion. After charging 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 1,000 parts by mass of water was added dropwise with stirring 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 residual reaction product. 1000 parts by mass of water was added again to reprecipitate the reaction product, and the supernatant was removed. The reaction product was dissolved by adding 1,000 parts by mass of propylene glycol monoethyl ether acetate and dehydrated under reduced pressure to obtain 793 parts by mass of a novolac resin (1) solution (resin content: 30% by mass). The novolak resin (1) obtained had a number average molecular weight (Mn) of 3,144, a weight average molecular weight (Mw) of 15,760, and a polydispersity (Mw / Mn) of 5.01.

Example 2 Production of Novolak Type Resin (2) In Example 1, instead of the novolak type resin intermediate (1), an orthocresol novolac resin [“MC-2699HH” manufactured by DIC Corporation, number average molecular weight (Mn) 1,421, Weight average molecular weight (Mw) 2,295, polydispersity (Mw / Mn) 1.62] In the same manner as in Example 1 except that 450 parts by mass was used, a novolac resin (2) solution (resin content: 30 mass) %) 785 parts by mass were obtained. The novolak resin (2) obtained had a number average molecular weight (Mn) of 5,633, a weight average molecular weight (Mw) of 21,074, and a polydispersity (Mw / Mn) of 3.74.

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

Comparative Production Example 1 Production of Novolac Type Resin (1 ′) In a 2,000 ml four-necked flask equipped with a cooling tube, 900 parts by mass of orthocresol, 90 parts by mass of resorcinol, 600 parts by mass of 41.5% formalin, and 1 part by mass of oxalic acid The temperature was raised to 99 ° C. over 2 hours with stirring, and stirring was continued for 3 hours while dry distillation. It switched to the dehydration circuit and heated up to 180 degreeC over 3 hours, dehydrating. The remaining ortho-cresol was distilled off while maintaining 180 ° C. to obtain 530 g of a pale red novolac resin (1 ′). The obtained novolac resin (1 ′) had a number average molecular weight (Mn) of 1,032, a weight average molecular weight (Mw) of 2,234, and a polydispersity (Mw / Mn) of 2.16.

Evaluation of Storage Stability The novolak resin obtained in Examples 1 to 3 and Comparative Production Example 1 was dissolved in propylene glycol monomethyl ether acetate to prepare a sample having a resin concentration of 15% by mass and a sample having 30% by mass. . The sample was put in a thermostat set to 25 ° C., 55 ° C., and 80 ° C. and subjected to a storage test for two weeks. The rate of change of the weight average molecular weight (Mw) before and after the storage test was measured, and the case where the absolute value of the rate of change was 10% or less was evaluated as A, and the case where the absolute value of the rate of change exceeded ± 10% was evaluated as B. The results are shown in Table 1.

Examples 4 to 6 and Comparative Example 1
About the novolak-type resin obtained in Examples 1-3 and the comparative manufacture example 1, manufacture of the curable composition was manufactured and evaluated in the following way. The results are shown in Table 2.

Production of curable composition 53 parts by mass of novolak resin solution (16 parts by mass of resin), 4 parts by mass of curing agent (“1,3,4,6-tetrakis (methoxymethyl) glycoluril” manufactured by Tokyo Chemical Industry Co., Ltd.) Part 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 The curable composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, dried on a 110 ° C. hot plate for 60 seconds, and then 230 ° C. Was heated for 300 seconds to obtain a cured coating film. The obtained cured coating film is scraped off from the wafer, and the mass decrease when the temperature is raised under the following conditions is measured using a differential thermothermal gravimetric simultaneous measurement device (TG / DTA), and the 1 mass% reduction temperature (Td1) is calculated. Asked.
Measuring instrument: “TG / DTA 6200” manufactured by Seiko Instruments Inc.
Measurement range: room temperature to 400 ° C
Temperature increase rate: 10 ° C / min

Examples 7 to 9 and Comparative Example 2
About the novolak-type resin obtained in Examples 1-3 and the comparative manufacture example 1, the photosensitive composition was manufactured and evaluated in the following way. The results are shown in Table 3.

Production of Photosensitive Composition 24 parts by mass of the novolak 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. This was filtered through a 0.2 μm membrane filter to obtain a photosensitive composition.
The photosensitizer was “P-200” (4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylidene] bisphenol 1 mol and 1, manufactured by Toyo Gosei Co., Ltd. 2-naphthoquinone-2-diazide-5-sulfonyl chloride condensate).

Evaluation of Alkali Developability [ADR (nm / s)] The photosensitive composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, and then on a hot plate at 110 ° C. Dried for 60 seconds. Two wafers were prepared, and one of the wafers was designated as “no exposure sample”. The other was used as an “exposed sample” and irradiated with 100 mJ / cm ² of ghi rays using a ghi ray lamp (“Multi Light” manufactured by Ushio Electric Co., Ltd.), and then heat-treated at 140 ° C. for 60 seconds. .
Both the “non-exposed sample” and the “exposed sample” were immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds and then dried on a hot plate at 110 ° C. for 60 seconds. The film thickness of each sample before and after immersion in the developer was measured, and the value obtained by dividing the difference by 60 was defined as alkali developability [ADR (nm / s)].

Evaluation of Photosensitivity The photosensitive composition obtained above was applied 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. A mask corresponding to a resist pattern having a line-and-space ratio of 1: 1 and a line width of 1 to 10 μm set every 1 μm is brought into close contact with the wafer, and then a ghi line lamp (“Multi Light” manufactured by USHIO INC. )) Was used for irradiation with ghi rays, and heat treatment was performed at 140 ° C. for 60 seconds. Next, the film was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a hot plate at 110 ° C. for 60 seconds.
The exposure amount (Eop exposure amount) capable of faithfully reproducing the line width of 3 μm when the ghi line exposure amount was increased from 30 mJ / cm ² to 5 mJ / cm ² was evaluated.

Evaluation of Resolution The photosensitive composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, and dried on a hot plate at 110 ° C. for 60 seconds. A photomask was placed on the obtained wafer, and an alkali development operation was performed by irradiating with 200 mJ / cm ² of ghi line in the same manner as in the previous alkali developability evaluation. The pattern state is confirmed using a laser microscope ("VK-X200" manufactured by Keyence Corporation), and A / L / S = 1 is obtained when the line width of L / S = 1/1 is resolved at 5 μm. A line width of 1 was evaluated as B when the line width was 5 μm and could not be resolved.

Claims (10)

A novolac resin intermediate obtained by reacting the phenolic hydroxyl group-containing compound (C) other than the polyhydroxybenzene compound (A) with the aldehyde compound (B), and the resulting novolak resin intermediate; A method for producing a novolac resin in which a polyhydroxybenzene compound (A) and an aldehyde compound (B) are reacted in an alcohol solvent , wherein the amount of the alcohol solvent used is 50 to 300 mass based on the total mass of the reaction raw material. method for producing a% range der of is, weight average molecular weight of the obtained novolak resin (Mw) novolak resin is in the range of 5,000 to 30,000. The method of manufacturing a weight average molecular weight of the novolak type resin intermediate (Mw) is according to claim 1, wherein in the range of 1,000 to 10,000. The production method according to claim 1, wherein the polyhydroxybenzene compound (A) is a resorcinol type compound having a hydroxyl group at the 1,3-position. The resulting novolac resin has the following structural formula (1) at the molecular end.

[Wherein R ¹ is any one of a hydrogen atom, an alkyl group, and an aryl group. m is 2 or 3. R ² is an aliphatic hydrocarbon group, an alkoxy group or an aryl group, and n is 0, 1 or 2. ]
The manufacturing method of Claim 1 which has structural-part (I) represented by these. The production method according to claim 1, wherein the polydispersity (Mw / Mn) of the novolac resin is in the range of 2-15. The manufacturing method of the photosensitive composition which mix | blends the novolak-type resin manufactured with the manufacturing method as described in any one of Claims 1-5 , and a photosensitive agent. The manufacturing method of the resist material using the photosensitive composition manufactured with the manufacturing method of Claim 6 . The manufacturing method of the curable composition which mix | blends the novolak-type resin manufactured with the manufacturing method as described in any one of Claims 1-5 , and a hardening | curing agent. The manufacturing method of the hardened | cured material using the curable composition manufactured with the manufacturing method of Claim 8 . The manufacturing method of the resist material using the curable composition manufactured with the manufacturing method of Claim 8 .