TW202003612A - Phenolic novolac resin, method for manufacturing same, photosensitive composition, resist material, and resist film - Google Patents

Abstract

The purpose of this invention is to provide: a phenolic novolac resin that is suitable for use as a resist material having excellent sensitivity, resolution, and heat resistance; a method for manufacturing the resin; and a photosensitive composition, resist material, and resist film including the resin. Specifically, this invention provides a phenolic novolac resin characterized by being a condensate of an aromatic compound represented by formula (1) and an aliphatic aldehyde, a method for manufacturing the resin, a photosensitive composition and resist material comprising the resin, and a resist film that is a hardened film of the same. (R1, R2, and R4 are each either a hydrogen atom, alkyl group, alkoxy group, aryl group, aralkyl group, or halogen atom. R3 and R are each either a hydrogen atom, a hydrocarbon group, or a structural moiety with one or more alkoxy groups, halogen atoms, or hydroxyl groups on a hydrocarbon group. m, n, and p are each an integer from 0 to 4.).

Description

Novolac type phenol resin, its manufacturing method, photosensitive composition, photoresist material and photoresist film

The invention relates to a novolak type phenol resin suitable for use as a photoresist material and a photoresist material using the same.

Photoresists used in the manufacture of semiconductors such as ICs and LSIs, the manufacture of display devices such as LCDs, the manufacture of original printing plates, etc. are known to use photosensitizers such as alkali-soluble resins and 1,2-naphthoquinonediazide compounds. Positive photoresist. Among the aforementioned alkali-soluble resins, there is a literature suggesting to use a mixture containing m-cresol novolak resin and p-cresol novolak resin as a positive-type photoresist composition of an alkali-soluble resin (refer to, for example, Patent Document 1)

The positive-type photoresist composition described in Patent Document 1 is a product developed to improve the visibility of sensitivity and the like. In recent years, the high integration of semiconductors is developing, and there is a tendency for the pattern to be further thinned. Gradually, more excellent sensitivity is needed. However, the positive-type photoresist composition described in Patent Document 1 has a problem that sufficient sensitivity corresponding to thinning cannot be obtained. In addition, from the viewpoint of performing various heat treatments in the manufacturing process of semiconductors and the like, higher heat resistance is also required, but the positive photoresist composition described in Patent Document 1 has a problem that it does not have sufficient heat resistance.

In addition, regarding a composition having excellent sensitivity and high heat resistance, there are literatures suggesting that after reacting p-cresol and the like with an aromatic aldehyde, then adding phenols and formaldehyde, and reacting it under an acid catalyst, the obtained Phenolic resin for photoresist (refer to, for example, Patent Document 2). Although this phenol resin for photoresist has improved heat resistance compared with the past, it has not yet reached the level required to fully cope with the high heat resistance required in recent years.

Patent Document 3 proposes a photoresist composition containing novolak resin using a mixture of m-cresol, p-cresol, xylenol/trimethylphenol mixture, formaldehyde and aromatic aldehyde.

Patent Document 4 proposes a photoresist composition containing a novolak resin using a mixture of 2,3-xylenol and cresol with formaldehyde and an aromatic aldehyde mixture containing two or more OH groups. However, the positive-type photoresist composition described in Patent Document 4 has not yet reached the level required to meet the high heat resistance required in recent years.

Phenolic resins have been produced by various methods in the past. For example, a method of reacting phenols and aldehydes in the presence of an acid catalyst in ethanol is known (refer to, for example, Patent Document 5). However, with the method described in the aforementioned Patent Document 5, a phenolic phenol resin with a high molecular weight cannot be obtained, and therefore it is difficult to obtain a photoresist composition that becomes a coating film with higher heat resistance.

Patent Literature 6 proposes a photoresist composition containing a product of a mixture of o-cresol, 2,5-dimethylphenol, 3,5-dimethylphenol and aldehydes.

Patent Document 7 proposes a photoresist composition containing a novolak resin introduced with an acid-dissociable group and an organic carboxylic acid.

On the other hand, when manufacturing a patterned structure, for example, in a wafer-level package, as the wiring density increases, an electrochemical deposition method of electronic wiring is used (see, for example, Non-Patent Document 1). For the gold bumps, copper pillars and copper wires used for rearrangement in wafer-level packaging, in order to form the final metal structure in the advanced wiring technology, the mold for the photoresist that is later plated is necessary. This photoresist layer is very thick compared to the photoresist used in the IC manufacturing of critical layers. Both the pattern size and the photoresist thickness are typically 2 μm to 100 μm. Therefore, the photoresist must be patterned with a high aspect ratio (photoresist thickness to line width).

One of the solutions is that when synthesizing novolak resins, aliphatic polyaldehydes are used as a nodule for m-cresol or p-cresol. However, it is difficult to balance the heat resistance and alkali dissolution rate of the important characteristics of thick film photoresist.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-55359

[Patent Document 2] Japanese Unexamined Patent Publication No. 2008-88197

[Patent Document 3] Japanese Patent Laid-Open No. 2002-107925

[Patent Document 4] Japanese Patent Laid-Open No. 9-73169

[Patent Document 5] Japanese Patent Laid-Open No. 8-286370

[Patent Document 6] Japanese Patent Laid-Open No. 3-294861

[Patent Document 7] Japanese Patent Laid-Open No. 9-6003

[Non-patent literature]

[Non-Patent Document 1] Gary Solomon, Electrochemically deposited solder bumps for wafer-level packaging, PACKAGING/ASSEMBLY, Solid State Technology, pages 83,84,86,88 April 2001

The object of the present invention is to provide a novolac-type phenol resin, which can be suitably used as a photoresist material having excellent sensitivity, excellent resolution, and excellent heat resistance; and a method for manufacturing the same, a photosensitive composition containing the resin, Photoresist material and photoresist film.

The present inventors have repeatedly studied and found that, by using a novolak type phenol resin containing a condensate of a phenol compound of a specific carboxylic acid and an aliphatic aldehyde, the above-mentioned problems can be solved, and the present invention has been completed.

That is, the present invention provides a novolak type phenol resin characterized by a condensation product of an aromatic compound (A) and an aliphatic aldehyde (B) represented by the following formula (1), and a method for manufacturing the same , And the photosensitive composition containing the resin, the photoresist material, and the photoresist film of the cured film thereof.

(In the formula, R ₁ , R ₂ , and R ₄ are each independently, and represent any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom, and R ₃ and R are each independently, and represent a hydrogen atom. , A hydrocarbon group, any one of the structural parts having one or more alkoxy groups, halogen atoms, and hydroxyl groups on the hydrocarbon group, m, n, and p are each independent and represent an integer of 0 or 1 to 4.)

According to the present invention, a photosensitive composition having excellent sensitivity, excellent resolution, and excellent heat resistance can be provided, and a novolak type phenol resin as a photoresist can be suitably used. The photoresist material containing the resin has high contrast characteristics (the ADR (Alkali Dissolution Rate) difference before and after the addition of the photosensitizer is large), and is different from the use of general photoresist novolak resins (m, p-cresol, Compared to the case of formalin copolymerization), the heat resistance is drastically improved.

FIG. 1 is a GPC chart of the precursor compound (1) in Examples.

2 is a ¹ H-NMR chart of the precursor compound (1) in Examples.

FIG. 3 is a GPC chart of the precursor compound (2) in the examples.

4 is a ¹³ C-NMR chart of the precursor compound (2) in Examples.

Fig. 5 is a GPC chart of the novolak type phenol resin (A) in the examples.

6 is a GPC chart of the novolak type phenol resin (B) in the examples.

7 is a GPC chart of the novolak type phenol resin (C) in the examples.

8 is a GPC chart of the novolak type phenol resin (D) in the examples.

9 is a GPC chart of the novolak type phenol resin (E) in the comparative example.

10 is a GPC chart of the novolak type phenol resin (F) in the comparative example.

The following is a detailed description of one embodiment of the present invention. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not hinder the effects of the present invention.

The novolak type phenol resin of the present invention is characterized in that it is a condensate of an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B).

(In the formula, R ₁ , R ₂ , and R ₄ are each independently, and represent any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom, and R ₃ and R are each independently, and represent a hydrogen atom. , A hydrocarbon group, any one of the structural parts having one or more alkoxy groups, halogen atoms, and hydroxyl groups on the hydrocarbon group, m, n, and p are each independent and represent an integer of 0 or 1 to 4.)

The novolak type phenol resin of the present invention typically has a triarylmethane structure. By having this triarylmethane structure, the aromatic ring can be contained at a high density, so the novolak type phenol resin of the present invention has very high heat resistance. In addition, in the triarylmethane structure of the aforementioned formula (1), two hydroxyl groups and carboxyl groups are substituted on aromatic rings different from each other without forming a strong hydrogen bond. It is considered that the novolak type phenol resin of the present invention can maintain good proton dissociation properties and can exhibit excellent alkali developability.

In the aforementioned formula (1), the alkyl group of R ₁ , R ₂ , and R ₄ is preferably an alkyl group having 1 to 9 carbon atoms, specifically, methyl, ethyl, propyl, iso Propyl, butyl, tertiary butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, etc. alkyl groups having 1 to 9 carbon atoms and cycloalkyl groups having 3 to 9 carbon atoms.

In the aforementioned formula (1), the alkoxy groups of R ₁ , R ₂ and R ₄ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and cyclohexyloxy Base etc.

In the aforementioned formula (1), the aryl groups of R ₁ , R ₂ and R ₄ include phenyl, tolyl, xylyl, naphthyl and anthracenyl.

In the aforementioned formula (1), the aralkyl groups of R ₁ , R ₂ and R ₄ include benzyl, phenethyl, phenylpropyl, naphthylmethyl and the like.

In the aforementioned formula (1), the halogen atoms of R ₁ , R ₂ and R ₄ include fluorine atom, chlorine atom, bromine atom, iodine atom and the like.

In the aforementioned formula (1), the hydrocarbon group of R ₃ and R may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and particularly preferably the aforementioned alkyl group and aryl group.

In the aforementioned formula (1), "structural sites having one or more alkoxy groups, halogen atoms, and hydroxyl groups" for R ₃ and R include halogenated alkyl groups, halogenated aryl groups, and 2-methoxyethoxy groups , Alkoxyalkoxy such as 2-ethoxyethoxy and the like, alkylalkoxy substituted with hydroxy.

In the aforementioned formula (1), m, n, and p are independent of each other and are integers of 0 or 1 to 4, and when m and n are substituents other than hydrogen atoms, it is preferably an integer of 2 or 3, respectively. At this time, in the case where m and n are 2, respectively, the two R ₁ and the two R ₂ are independent, preferably an alkyl group having 1 to 3 carbon atoms. In addition, two R ₁ and two R ₂ are preferably bonded to the 2,5-position of the phenolic hydroxyl group.

In the aforementioned formula (1), p is preferably an integer of 0, 1, or 2.

As the aromatic compound (A) represented by the aforementioned formula (1), a compound of the same structure may be used alone, or a plurality of compounds having different molecular structures may be used.

The aforementioned aromatic compound (A) can be obtained by, for example, a phenol (a1) which may have a substituent and an aromatic aldehyde (a2) having a carboxyl group or its ester derivative and/or an aromatic having a carboxyl group or its ester derivative The ketone (a3) is obtained by polycondensation. At this time, the aromatic ring of the aromatic aldehyde (a2) and the aromatic ketone (a3) may have a substituent.

The aforementioned phenol (a1) which may have a substituent is a compound in which a part or all of the hydrogen atoms bonded to the aromatic ring of the phenol are substituted with any of an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom, Only one type may be used or two or more types may be used in combination.

Examples of the aforementioned alkyl group include alkyl groups having 1 to 9 carbon atoms, and methyl group is particularly preferred. Examples of the alkyl-substituted phenol (a1) include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol and p-third butyl Monoalkylphenols such as phenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, etc.; 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2, Dialkylphenols such as 4-xylenol and 2,6-xylenol; trialkylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol. Among these alkyl-substituted phenols, from the viewpoint of excellent balance between heat resistance and alkali solubility, the number of alkyl substitutions on the aromatic ring of the phenol is preferably 2, and specific examples include 2,5- Xylenol, 2,6-xylenol, etc.

Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and cyclohexyloxy groups. The compound having an alkoxy group as a substituent includes, for example, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m-ethoxyphenol, p-ethoxyphenol, o Propoxyphenol, m-propoxyphenol, p-propoxyphenol, 2-methylpropoxyphenol, o-butoxyphenol, m-butoxyphenol, p-butoxyphenol, third butoxyphenol , O-amyloxyphenol, m-amyloxyphenol, p-amyloxyphenol, o-hexyloxyphenol, m-hexyloxyphenol, p-hexyloxyphenol, o-cyclohexyloxyphenol, m-cyclohexyloxyphenol , Monoalkoxyphenol such as p-cyclohexyloxyphenol, 2,5-dimethoxyphenol, 3,5-dimethoxyphenol, 3,4-dimethoxyphenol, 2,4-dimethoxyphenol Dimethoxyphenol such as methoxyphenol 2,6-dimethoxyphenol, and trimethoxyphenol such as 3,4,5-trimethoxyphenol and 2,4,6-trimethoxyphenol.

Examples of the aryl group include phenyl, hydroxyphenyl, dihydroxyphenyl, hydroxyalkoxyphenyl, alkoxyphenyl, tolyl, xylyl, naphthyl, hydroxynaphthyl, and dihydroxynaphthyl. . Examples of the compound having an aryl group as a substituent include o-phenol, m-phenol, p-phenol, 2,6-diphenol, methoxyphenol, and cresol.

Examples of the aralkyl group include phenylmethyl, hydroxyphenylmethyl, dihydroxyphenylmethyl, tolylmethyl, xylylmethyl, naphthylmethyl, hydroxynaphthylmethyl, and dihydroxynaphthylmethyl , Phenethyl, hydroxyphenethyl, dihydroxyphenethyl, tolylethyl, ethyl, naphthylethyl, hydroxynaphthylethyl, dihydroxynaphthylethyl, etc. Examples of the phenol compound having an aralkyl group include phenylmethylphenol, hydroxyphenylmethylphenol, dihydroxyphenylmethylphenol, phenethylphenol, and hydroxyphenethylphenol.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom. Examples of the compound having the halogen atom as a substituent include monohalogenated phenols such as fluorophenol, chlorophenol, bromophenol, and iodophenol, difluorophenol, dichlorophenol, dibromophenol, and diiodophenol. , Trifluorophenol, trichlorophenol, tribromophenol, triiodophenol and other trihalogenated phenols.

The aforementioned aromatic aldehyde (a2) is a compound having at least one carboxyl group or its ester derivative and an aldehyde group in the aromatic ring, and may further have an alkyl group, an alkoxy group, a halogen atom, or the like as a substituent on the aromatic ring. Examples of the aforementioned aromatic aldehyde (a2) include 4-methyl benzoic acid, 2-methyl benzoic acid, 3-methyl benzoic acid, methyl 4-methyl benzoate, and 4-methyl benzoic acid. Ethyl benzoate, propyl 4-formyl benzoate, isopropyl 4-methyl benzoate, butyl 4-methyl benzoate, isobutyl 4-methyl benzoate, 4- The ester derivatives represented by such as third butyl methylbenzoate, cyclohexyl 4-methylacetylbenzoate, and third octyl 4-methylbenzoyl ester are not limited thereto. In addition, among these aromatic aldehydes (a2), the easiness of obtaining industrially, the heat resistance of the cured product obtained by using the obtained novolak type phenol resin photoresist and the alkali dissolution as the photoresist From the viewpoint of excellent balance of properties, 4-methyl benzoic acid is preferred. These aromatic aldehydes (a2) may be used alone or in combination of two or more.

The aforementioned aromatic ketone (a3) is a compound having at least one carboxyl group or its ester derivative and a carbonyl group in the aromatic ring, and may further have an alkyl group, an alkoxy group, a halogen atom, or the like as a substituent on the aromatic ring. Examples of the above-mentioned aromatic ketone (a3) include 2-acetoyl benzoic acid, 3-ethenyl benzoic acid, 4-ethenyl benzoic acid, and methyl 2-ethenyl benzoate, 2-ethenyl benzoate Ethyl benzoate, propyl 2-ethyl benzoate, isopropyl 2-ethyl benzoate, butyl 2-ethyl benzoate, isobutyl 2-acetyl benzoate, 2- The ester derivatives represented by tert-butyl acetobenzoate, cyclohexyl 2-acetobenzoate, tert-octyl 2-acetobenzoate and the like are not limited thereto. In addition, among these aromatic ketones (a3), the ease of industrial acquisition, the heat resistance of a cured product obtained from a photoresist using a novolac type phenol resin, and the balance as a photoresist are excellent In the future, 2-acetoyl benzoic acid or 4-acetoyl benzoic acid is preferred. These aromatic ketones (a3) may be used alone or in combination of two or more.

烷、乙醛、丙醛、四氧亞甲基(tetraoxy methylene)、聚甲醛、氯醛、六亞甲基四胺、乙二醛、正丁醛、己醛、烯丙醛、巴豆醛、丙烯醛等。這些醛化合物(B)可只使用一種或併用兩種以上。另外，前述脂肪族醛(B)以使用甲醛為佳，亦可併用甲醛與其他的脂肪族醛。在併用甲醛與其他的脂肪族醛的情況，其他脂肪族醛的使用量，相對於甲醛1莫耳，以設定在0.05~1莫耳的範圍為佳。 Examples of the aforementioned aliphatic aldehyde (B) include formaldehyde, paraformaldehyde (parafornaldehyde), 1,3,5-trialdehyde

Alkanes, acetaldehyde, propionaldehyde, tetraoxymethylene, polyoxymethylene, chloroaldehyde, hexamethylenetetramine, glyoxal, n-butyraldehyde, hexanal, allylaldehyde, crotonaldehyde, propylene Aldehyde and so on. These aldehyde compounds (B) may be used alone or in combination of two or more. In addition, it is preferable to use formaldehyde for the aforementioned aliphatic aldehyde (B), and formaldehyde and other aliphatic aldehydes may be used in combination. In the case of using formaldehyde in combination with other aliphatic aldehydes, the use amount of other aliphatic aldehydes is preferably set in the range of 0.05 to 1 mol relative to 1 mol of formaldehyde.

The method for producing the novolak type phenol resin (C) of the present invention includes the following three steps.

(step 1)

The phenol compound (a1) and the aromatic aldehyde (a2) and/or the aromatic ketone (a3) are heated in the range of 60 to 140°C in the presence of an acid catalyst, if necessary, using a solvent to perform polycondensation To obtain the aforementioned aromatic compound (A).

(Step 2)

The aforementioned aromatic compound (A) obtained in Step 1 is separated from the reaction solution.

(Step 3)

The aromatic compound (A) and the aliphatic aldehyde (B) separated in step 2 are heated in the range of 60 to 140°C in the presence of an acid catalyst and, if necessary, a solvent to perform polycondensation to obtain Invented novolak type phenol resin (C).

Examples of the acid catalyst used in the above steps 1 and 3 include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used alone or in combination of two or more. Among these acid catalysts, from the viewpoint of excellent activity, sulfuric acid and p-toluenesulfonic acid are preferred in step 1, and sulfuric acid, oxalic acid, and zinc acetate are preferred in step 3. In addition, the acid catalyst can be added before the reaction or during the reaction.

烷、1,4-二

烷等的環狀醚；乙二醇醋酸酯等的二醇酯；丙酮、甲基乙基酮、甲基異丁基酮等的酮；甲苯、二甲苯等的芳香族烴等。這些溶劑可只使用一種或併用兩種以上。另外，這些溶劑之中，從所得到的化合物的溶解性優異的觀點看來，以2-乙氧基乙醇為佳。 In the above steps 1 and 3, the solvents used as necessary include monohydric alcohols such as methanol, ethanol, propanol, etc.; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butane Glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, di Polyols such as ethylene glycol, polyethylene glycol, and glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Glycol ethers such as ethylene glycol monoamyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, and ethylene glycol monophenyl ether; 1,3-bis

Alkane, 1,4-di

Cyclic ethers such as alkanes; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more. Among these solvents, 2-ethoxyethanol is preferred from the viewpoint of excellent solubility of the obtained compound.

The feed ratio of the phenol compound (a1) to the aromatic aldehyde (a2) and/or the aromatic ketone (a3) in step 1 [(a1)/[(a2)+(a3)]], never From the viewpoint of the excellent removability of the phenol compound (a1) reacted, the yield of the product, and the purity of the reaction product, the molar ratio is preferably in the range of 1/0.2 to 1/0.5, and is in the range of 1 The range of /0.25 to 1/0.45 is preferable.

The feed ratio [(A)/(B)] of the aforementioned aromatic compound (A) to the aforementioned aliphatic aldehyde (B) in step 3 can be suitably used as a method for suppressing excessive molecular weight (colloidization) From the viewpoint of the molecular weight of the novolak type phenol resin, the molar ratio is preferably in the range of 1/0.5 to 1/1.2, and preferably in the range of 1/0.6 to 1/0.9.

烷、1,4-二

烷等的環狀醚；乙二醇醋酸酯等的二醇酯；丙酮、甲基 乙基酮、甲基異丁基酮等的酮等。另外，在前述貧溶劑(S1)使用水的情況，前述(S2)以丙酮為佳。此外，前述貧溶劑(S1)及溶劑(S2)分別可只使用一種或併用兩種以上。 The method for separating the reaction solution of the aromatic compound (A) in step 2 includes, for example, pouring the reaction solution into a poor solvent (S1) in which the reaction product is insoluble or poorly soluble, and filtering the resulting precipitate, A method of dissolving and dissolving the reaction product in a solvent (S2) that is also mixed with a lean solvent (S1), pouring the lean solvent (S1) again, and filtering the resulting precipitate. Examples of the poor solvent (S1) used at this time include water; monohydric alcohols such as methanol, ethanol, and propanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohexane; toluene, Aromatic hydrocarbons such as xylene. Among these poor solvents (S1), water and methanol are preferred from the viewpoint that the acid catalyst can be efficiently removed at the same time. On the other hand, examples of the solvent (S2) include monohydric alcohols such as methanol, ethanol, and propanol; 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, poly Polyols such as ethylene glycol and glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentane Glycol ethers of basic ethers, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether, etc.; 1,3-bis

Alkane, 1,4-di

Cyclic ethers such as alkanes; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. In the case where water is used as the poor solvent (S1), acetone is preferred as the (S2). In addition, each of the aforementioned poor solvent (S1) and solvent (S2) may be used alone or in combination of two or more.

In addition, in the above steps 1 and 3, when the aromatic hydrocarbon such as toluene or xylene is used as a solvent, the aromatic compound (A) generated by the reaction dissolves in the solvent as long as it is heated above 80°C Direct cooling will cause the crystals of the aromatic compound (A) to precipitate. Therefore, the aromatic compound (A) can be separated by filtering it. In this case, the aforementioned poor solvent (S1) and solvent (S2) may not be used.

By the separation method in the above step 2, the aforementioned aromatic compound (A) represented by the following general formula (1) can be obtained.

(In the formula, R ₁ , R ₂ , and R ₄ are each independently, and represent any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom, and R ₃ and R are each independently, and represent a hydrogen atom. , A hydrocarbon group, any one of the structural parts having one or more alkoxy groups, halogen atoms, and hydroxyl groups on the hydrocarbon group, m, n, and p are each independent and represent an integer of 0 or 1 to 4.)

The weight-average molecular weight (Mw) of the novolak type phenol resin (C) obtained by the above production method is preferably in the range of 2,000 to 35,000, and preferably in the range of 2,000 to 25,000. This weight average molecular weight (Mw) is a value measured using gel permeation chromatography (hereinafter abbreviated as "GPC") under the following measurement conditions.

(Measurement conditions of GPC)

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

Pipe column: "Shodex KF802" (8.0mmΦ×300mm) manufactured by Showa Denko Co., Ltd.

+ "Shodex KF802" (8.0mmΦ×300mm) made by Showa Denko Co., Ltd.

+ Showa Denko Co., Ltd. "Shodex KF803" (8.0mmΦ×300mm)

+ "Shodex KF804" made by Showa Denko Co., Ltd. (8.0mmΦ×300mm)

Column temperature: 40℃

Detector: RI (Differential Refractometer)

Data processing: "GPC-8020 model II version 4.30" manufactured by Tosoh Corporation

Expand solvent: Tetrahydrofuran

Flow rate: 1.0mL/min

Sample: A sample obtained by filtering the resin solid content into a 0.5% by mass tetrahydrofuran solution with a microfilter (100 μl)

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" 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

In the photosensitive composition and photoresist of the present invention, the novolak type phenol resin (C) obtained by the above production method is a constituent component as an alkali-soluble resin, however, other alkali-soluble resins ( D).

The aforementioned other alkali-soluble resin (D) may be any resin that is soluble in an aqueous alkali solution, and among them, cresol novolak resin is preferred. The aforementioned cresol novolak resin is a novolak type phenol resin obtained by condensing phenolic compounds and aldehyde compounds as raw materials, and is a group selected from o-cresol, m-cresol and p-cresol At least one phenolic compound in the group is manufactured as an essential raw material.

The phenolic compound used as the raw material of the cresol novolak resin must be o-cresol, m-cresol, or p-cresol. However, other phenols or derivatives thereof may be used in combination. Examples of such phenol or its derivatives include phenol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, and 3,4-bisphenol Xylenols such as cresol, 3,5-xylenol, etc.; ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol, etc.; isopropylphenol, butylphenol, p-third butyl Butylphenol such as phenol; alkylphenols such as p-amylphenol, p-octylphenol, p-nonylphenol, p-cumylphenol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol, iodophenol; p-phenol , Aminophenol, nitrophenol, dinitrophenol, trinitrophenol and other 1-substituted phenols; 1-naphthol, 2-naphthol and other condensed polycyclic phenols; resorcinol, alkyl resorcinol Diphenol, gallophenol, catechol, alkyl catechol, hydroquinone, alkyl hydroquinone, phloroglucin, bisphenol A, bisphenol F, bisphenol S, dihydroxynaphthalene, etc. Valence phenol and so on. These other phenols or derivatives thereof may be used alone or in combination of two or more. In addition, when other phenols or their derivatives are used in combination, the use amount of the other phenols or their derivatives is set at 0.05 in total with respect to the cresols of o-cresol, m-cresol, and p-cresol. A range of ~1 mole is preferred.

烷、乙醛、丙醛、聚甲醛(polyoxymethylene)、氯醛、六亞甲基四胺、糠醛、乙二醛、正丁醛、己醛、烯丙醛、苯甲醛、巴豆醛、丙烯醛、四氧亞甲基、苯基乙醛、鄰甲苯甲醛、水楊醛等。這些醛化合物可只使用一種或併用兩種以上。另外，前述甲酚酚醛清漆樹脂的原料以使用甲醛為佳，亦可併用甲醛與其他的醛化合物。在併用甲醛與其他的醛化合物的情況，其他的醛化合物的使用量，以定在相對於甲醛1莫耳為0.05~1莫耳的範圍為佳。 In addition, examples of the aldehyde compound of the cresol novolak resin raw material include formaldehyde, paraformaldehyde, and trialdehyde.

Alkanes, acetaldehyde, propionaldehyde, polyoxymethylene, chloroaldehyde, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, hexanal, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, Tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, etc. These aldehyde compounds may be used alone or in combination of two or more. In addition, the raw material of the cresol novolak resin is preferably formaldehyde, and formaldehyde and other aldehyde compounds may be used in combination. In the case of using formaldehyde in combination with other aldehyde compounds, the amount of other aldehyde compounds used is preferably in the range of 0.05 to 1 mole relative to 1 mole of formaldehyde.

The condensation reaction of the phenol compound and the aldehyde compound is preferably carried out in the presence of an acid catalyst. Examples of the acid catalyst include oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used alone or in combination of two or more. Among these acid catalysts, oxalic acid is preferred from the viewpoint of excellent catalyst activity. In addition, the acid catalyst can be added before the reaction or during the reaction.

In addition, when manufacturing the cresol novolak resin, the molar ratio [(F)/(P)] of the phenol compound (P) and the aldehyde compound (F) is from the viewpoint of obtaining excellent sensitivity and heat resistance The range of 0.3 to 1.6 is preferred, and the range of 0.5 to 1.3 is preferred.

The more specific production method of the cresol novolak resin includes heating a phenolic compound, an aldehyde compound, and an acid catalyst to 60 to 140° C. to perform a polycondensation reaction, followed by dehydration and dehydration under pressure. Monolithic method.

In the photosensitive composition and photoresist material of the present invention, in addition to the novolak type phenol resin (C) and the alkali-soluble resin (D) optionally blended, a photosensitizer (E) is usually used, and the viscosity is adjusted in order It also contains a solvent (F).

As the aforementioned photosensitizer (E), a compound having a quinonediazide group can be used. Examples of the compound having a quinonediazide group include 2,3,4-trihydroxydiphenyl ketone, 2,4,4′-trihydroxydiphenyl ketone, and 2,4,6-trihydroxydiphenyl. Ketone, 2,3,6-trihydroxydiphenylketone, 2,3,4-trihydroxy-2'-methyldiphenylketone, 2,3,4,4'-tetrahydroxydiphenylketone , 2,2',4,4'-tetrahydroxydiphenyl ketone, 2,3',4,4',6-pentahydroxydiphenyl ketone, 2,2',3,4,4'-penta Hydroxydiphenyl ketone, 2,2',3,4,5-pentahydroxydiphenyl ketone, 2,3',4,4',5',6-hexahydroxydiphenyl ketone, 2,3, 3',4,4',5'-hexahydroxydiphenyl ketone and other polyhydroxy diphenyl ketone compounds; bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-tris Hydroxyphenyl)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-methyl Hydroxy-4-hydroxyphenyl)-2-propyl]phenyl]ethylene]bisphenol and other bis[(poly)hydroxyphenyl]alkanes; see (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-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, etc. (Hydroxyphenyl) methane or its methyl substitutes; 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-hydroxybenzene Methane, 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-hydroxyphenyl Methane, 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 other bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes or their methyl substitutes and the like and naphthoquinone -1,2-diazide-5-sulfonic acid or naphthoquinone-1,2-diazide-4-sulfonic acid, o-anthraquinonediazidesulfonic acid, etc. Complete ester compounds, partial ester compounds, amidated compounds or partially amidated compounds, etc. These photosensitizers (E) may be used alone or in combination of two or more.

In the photosensitive composition and photoresist of the present invention, the blending amount of the above-mentioned photosensitizer (E) is better than that of the above-mentioned novolac-type phenol from the viewpoint of obtaining good sensitivity and obtaining a desired pattern. The total 100 parts by mass of the resin (C) and the alkali-soluble resin (D) is preferably in the range of 3 to 50 parts by mass, and more preferably in the range of 5 to 30 parts by mass.

烷等的環式醚；2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙 氧基醋酸乙酯、氧醋酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丁基醋酸酯、3-甲基-3-甲氧基丁基醋酸酯、蟻酸乙酯、醋酸乙酯、醋酸丁酯、乙醯醋酸甲酯、乙醯醋酸乙酯等的酯等。這些溶劑(F)可只使用一種或併用兩種以上。 Examples of the solvent (F) include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether Diethylene glycol dialkyl ethers such as ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate Ethylene glycol alkyl ether acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.; acetone, methyl ethyl ketone, cyclohexanone, Ketones such as methyl amyl ketone; two

Cyclic ethers such as alkanes; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2- Methyl hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, acetyl Esters such as methyl acetate and ethyl acetate. These solvents (F) may be used alone or in combination of two or more.

In the photosensitive composition and photoresist of the present invention, the blending amount of the solvent (F) is set from the viewpoint of obtaining fluidity of the composition and obtaining a uniform coating film by a coating method such as spin coating. It is preferable that the solid content concentration in the composition is 15 to 65% by mass.

In the photosensitive composition and photoresist of the present invention, in addition to the aforementioned novolak type phenol resin (C), other alkali-soluble resins (D), photosensitizers (E), and solvents (F) that are optionally blended In addition, various additives may be blended as long as the effect of the present invention is not hindered. Examples of such additives include surfactants such as fillers, pigments, and leveling agents, adhesion enhancers, and dissolution accelerators.

The photosensitive composition and photoresist of the present invention can be obtained by mixing the novolak type phenol resin (C), other alkali-soluble resin (D), a photosensitizer (E), and a solvent (F) , In accordance with the various additives necessary to add, stir and mix in the usual way to make a uniform liquid to prepare.

In addition, when blending solid materials such as fillers and pigments into the photosensitive composition and photoresist of the present invention, it is preferable to disperse and mix them using a dispersing device such as a dissolver, homogenizer, and three-roll mill. . In addition, in order to remove coarse particles or impurities, a mesh filter, a membrane filter, or the like may be used to filter the composition.

The photosensitive composition and the photoresist material of the present invention are exposed through the photomask, and the resin composition undergoes structural changes in the exposed portion, which promotes solubility in the alkali developing solution. On the other hand, in the non-exposed area, the low solubility in the alkali developing solution is maintained. Therefore, by the difference in solubility, it can be patterned by alkali imaging and used as a photoresist.

Examples of the light source that exposes the photosensitive composition and photoresist of the present invention include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams. Among these light sources, ultraviolet light is preferred, and g-rays (wavelength 436 nm), i-rays (wavelength 365 nm), and EUV lasers (wavelength 13.5 nm) of high-pressure mercury lamps are suitable.

In addition, as the alkali developer used for the developed image after exposure, inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc.; ethylamine, positive Primary amines such as propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; dimethylethanolamine and triethanolamine Alcohol amines; Quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; alkaline aqueous solutions such as cyclic amines such as pyrrole and piperidine. In these alkaline developing solutions, alcohols, surfactants, etc. may be added as appropriate to use. The alkali concentration of the alkaline developing solution is usually in the range of 2 to 5 mass%, and generally 2.38 mass% tetramethylammonium hydroxide aqueous solution is used.

[Example]

The following examples are disclosed to further illustrate the present invention. However, the present invention is not limited to these examples.

<modulation of composition>

The synthesized novolac type phenol resin and propylene glycol monomethyl ether acetate (PGMEA) were mixed and dissolved at 20/75 (parts by mass), and subjected to precision filtration with a 0.1 μm PTFE dish filter to produce a composition. .

<Evaluation of alkali developability>

The above-prepared composition was applied on a 5-inch silicon wafer with a spin coater and the thickness was about 1 μm, and dried on a hot plate at 110° C. for 60 seconds. After immersing the obtained wafer in a developing solution (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, it was dried on a hot plate at 110°C for 60 seconds. The film thickness before and after immersion in the developing solution was measured, and the difference was divided by 60 to determine the alkali developability (ADR1(Å/s)). In addition, a photosensitive composition (P-200 manufactured by Toyo Kogyo Co., Ltd.) used as a photoresist was prepared with a novolak type phenol resin/P-200/PGMEA=20/5/75 (parts by mass) to prepare a photosensitive composition , The measurement was carried out in the same manner using this substance, and the obtained value was defined as (ADR2(Å/s)). Similarly, as the developing solution, a 15% sodium carbonate aqueous solution was used, and the values measured with and without a photosensitizer were defined as alkali developability (ADR3(Å/s)) and alkali developability (ADR4(Å/s) ).

<heat resistance evaluation>

After the above-prepared composition (non-photosensitive material) was applied on a 5-inch-diameter silicon wafer using a spin coater, it was dried at 110° C. for 60 seconds to obtain a film with a thickness of 1 μm. The film was scraped, and the glass transition point temperature (hereinafter abbreviated as "Tg") was measured. In addition, Tg is measured using a differential scanning calorimeter ("Differential Thermal Scanning Calorimeter (DSC) Q100" manufactured by TA Instruments Co., Ltd.) under a nitrogen atmosphere at a temperature range of -100 to 200°C and a heating rate of 10 ℃/min. The evaluation criteria are as follows.

○: Tg is above 150℃

×: Tg is below 150℃

<Synthesis of Precursor Compound (1)> Manufacturing Example 1

In a 2000ml four-necked flask equipped with a condenser, 293.2g (2.4mol) of 2,5-xylenol and 150g (1mol) of 4-methyl benzoic acid were dissolved in 500ml of 2-ethoxyethanol . After cooling in an ice bath while adding 10 ml of sulfuric acid, it was heated and stirred at 100° C. for 2 hours with a mantle heater to make it react. After the reaction, the resulting solution was reprecipitated with water to obtain a crude product. After re-dissolving the crude product in acetone and reprecipitating with water, the resulting product was filtered and vacuum dried to obtain 292 g of a pale peach crystal precursor compound (1). The GPC purity was 95.3%, and it was confirmed to be the target compound by ¹ H-NMR. The GPC chart of the precursor compound (1) is shown in FIG. 1, and the ¹ H-NMR chart is shown in FIG. 2.

<Synthesis of Precursor Compound (2)> Manufacturing Example 2

In a 2000 ml four-necked flask equipped with a condenser, 293.2 g (2.4 mol) of 2,5-xylenol and 122 g (1 mol) of 2-hydroxybenzaldehyde were charged and dissolved in 500 ml of 2-ethoxyethanol. After cooling in an ice bath while adding 10 ml of sulfuric acid, it was heated and stirred at 100° C. for 2 hours in a heating bag to make it react. After the reaction, the resulting solution was reprecipitated with water to obtain a crude product. After re-dissolving the crude product in acetone and reprecipitating with water, the resulting product was filtered and vacuum dried to obtain 213 g of a white crystal precursor compound (2). The GPC purity was 98.2%, and it was confirmed as the target compound by ¹³ C-NMR. The GPC chart of the precursor compound (2) is shown in FIG. 3, and the ¹³ C-NMR chart is shown in FIG. 4.

Example 1 (Production Example 3: Synthesis of novolak type phenol resin resin (A-1))

A 300 ml four-necked flask equipped with a condenser was charged with 18.8 g (0.05 mol) of the precursor compound (1) and 1.6 g (0.05 mol) of 92% paraformaldehyde, and dissolved in 15 ml of 2-ethoxyethanol. 15ml of acetic acid. After cooling in an ice bath while adding 10 ml of sulfuric acid, the temperature was raised to 80°C in an oil bath, and heating and stirring were continued for 4 hours to react. After the reaction, the resulting solution was reprecipitated with water to obtain a crude product. After re-dissolving the crude product in acetone and reprecipitation with water, the resulting product was filtered and vacuum dried to obtain 16.9 g of novolak resin (A) as a red powder. The GPC results of the novolak resin (A) were number average molecular weight (Mn) = 3331, weight average molecular weight (Mw) = 6738, and polydispersity (Mw/Mn) = 2.02. The GPC chart of the novolak type phenol resin (A) is shown in FIG. 5.

Example 2 (Production Example 4: Synthesis of novolac type phenol resin (A-2), Mole ratio of precursor compound (1) to precursor compound (2) 25:75)

A 300 ml four-necked flask equipped with a condenser was charged with 4.5 g (0.012 mol) of the precursor compound (1), 13.2 g (0.038 mol) of the precursor compound (2), and 1.6 g (0.05 mol) of 92% paraformaldehyde To dissolve in 15 ml of 2-ethoxyethanol and 15 ml of acetic acid. After cooling in an ice bath while adding 10 ml of sulfuric acid, the temperature was raised to 80°C in an oil bath, and heating and stirring were continued for 4 hours to react. After the reaction, the resulting solution was reprecipitated with water to obtain a crude product. After the crude product was re-dissolved in acetone and further reprecipitated with water, the obtained product was filtered and vacuum dried to obtain 17.3 g of novolak-type phenol resin (A-2) as a pale red powder. The GPC results of the novolac type phenol resin (A-2) were number average molecular weight (Mn) = 2089, weight average molecular weight (Mw) = 7289, and polydispersity (Mw/Mn) = 3.49. The GPC chart of the novolak type phenol resin (A-2) is shown in Fig. 6.

Example 3 (Production Example 5: Synthesis of novolac-type phenol resin (A-3), molar ratio of precursor compound (1) to precursor compound (2) 50:50)

Except for using 9.4 g (0.025 mol) of the precursor compound (1) and 8.7 g (0.025 mol) of the precursor compound (2), in the same manner as in Example 2 (Production Example 4), a novolak-type phenol was obtained as a pale red powder 16.8 g of resin (A-3). The GPC results of the novolac type phenol resin (A-3) were number average molecular weight (Mn) = 2253, weight average molecular weight (Mw) = 7259, and polydispersity (Mw/Mn) = 3.22. The GPC chart of the novolak type phenol resin (A-3) is shown in FIG. 7.

Example 4 (Production Example 6: Synthesis of novolak type phenol resin (A-4), Mole ratio of precursor compound (1) and precursor compound (2) 75:25)

Except for using 14.3 g (0.038 mol) of the precursor compound (1) and 4.2 g (0.012 mol) of the precursor compound (2), in the same manner as in Example 2 (Production Example 4), a novolak-type phenol was obtained as a pale red powder 18.1 g of resin (A-4). The GPC results of the novolac type phenol resin (A-4) were number average molecular weight (Mn)=2438, weight average molecular weight (Mw)=5613, and polydispersity (Mw/Mn)=2.30. The GPC chart of the novolak type phenol resin (A-4) is shown in FIG. 8.

Comparative example 1 (composite comparative example 1)

A 2-L four-necked flask equipped with a stirrer and thermometer was charged with 552 g (4 mol) of 2-hydroxybenzoic acid, 498 g (3 mol) of 1,4-bis(methoxymethyl)benzene, 2.5 g of p-toluenesulfonic acid, and 500 g of toluene The temperature was raised to 120°C to carry out the de-methanol reaction. The temperature was raised and distilled under reduced pressure, and distillation under reduced pressure was carried out at 230°C for 6 hours to obtain 882 g of novolak type phenol resin (A'-1) as a pale yellow solid. The GPC results of the novolac-type phenol resin (A'-1) were number average molecular weight (Mn)=1016, weight average molecular weight (Mw)=2782, and polydispersity (Mw/Mn)=2.74. The GPC chart of the novolak type phenol resin (A'-1) is shown in FIG. 9.

Comparative example 2 (composite comparative example 2)

In a 2L four-necked flask equipped with a stirrer and a thermometer, m-cresol 648g (6mol), p-cresol 432g (4mol), oxalic acid 2.5g (0.2mol), and 42% formaldehyde 492g were heated to 100°C to react . Dehydration under normal pressure and distillation to 200°C and distillation under reduced pressure at 230°C for 6 hours yielded 736 g of novolak-type phenol resin (A'-2) as a pale yellow solid. The GPC results of 736 g of novolac type phenol resin (A′-2) were number average molecular weight (Mn)=1450, weight average molecular weight (Mw)=10316, and polydispersity (Mw/Mn)=7.116. The GPC chart of novolac type phenol resin (A'-2) (736 g) is shown in FIG. 10.

Table 1 shows the results of each measurement and evaluation of the compositions prepared using the novolak-type phenol resins of Examples 1 to 4 and Comparative Examples 1 and 2, respectively.

From the evaluation results disclosed in Table 1, it can be seen that the composition prepared from the novolak type phenol resin (A-1) obtained in Example 1 is set to 2.38% tetramethylammonium hydroxide aqueous solution in the developing solution In the case of, the composition without blending the sensitizer of the corresponding exposed part has a very fast alkali dissolution rate of 15,000 Å/sec, and has excellent sensitivity (ADR1). In addition, it can also be seen that the composition in which the photosensitizer corresponding to the unexposed portion is dissolved has a very low alkali dissolution rate of 80 Å/sec, and the pattern remains without problems after alkali development (ADR2).

In addition, it can also be seen that when the developing solution is set to a 15% sodium carbonate aqueous solution, the composition without the sensitizer of the corresponding exposed portion has a very fast alkali dissolution rate of 820Å/sec, and has excellent sensitivity ( ADR3). In addition, it can be seen that the alkali dissolution rate of the composition blended with the sensitizer corresponding to the unexposed portion is very low, which is less than 1Å/sec, and the pattern remains without problems after alkali development (ADR4). In addition, it can be seen that the Tg of the cured product is also very high, at 213°C, and is also excellent in heat resistance.

In addition, from the evaluation results disclosed in Table 1, it can be seen that the composition of the present invention prepared from the novolak type phenol resin (A-2) obtained in Example 2 is set to 2.38% hydroxide in the developing solution In the case of an aqueous solution of tetramethylammonium, a composition that does not incorporate a sensitizer corresponding to the exposed portion has a very fast alkali dissolution rate of 6,500Å/sec and has excellent sensitivity (ADR1). In addition, it can be seen that the alkali dissolution rate of the composition blended with the sensitizer corresponding to the unexposed portion is very low at 42Å/sec, and the pattern remains without problems after alkali development (ADR2).

It can also be seen that when the developing solution is set to a 15% sodium carbonate aqueous solution, the composition that does not incorporate the sensitizer corresponding to the exposed part has a very fast alkali dissolution rate of 410Å/sec and has excellent sensitivity (ADR3). In addition, it can be seen that the alkali dissolution rate of the composition blended with the sensitizer corresponding to the unexposed portion is very low, which is less than 1Å/sec, and the pattern remains without problems after alkali development (ADR4). In addition, it can be seen that the Tg of the cured product is also very high, at 186°C, and is also excellent in heat resistance.

Similarly, as disclosed in Table 1, in the composition prepared in Example 3 from the novolac type phenol resin (A-3), ADR1~4 were 7,200Å/sec, 53Å/sec, 480Å/sec, Less than 1Å/sec. shows excellent results. In addition, it can be seen that the Tg of the cured product is also very high, at 191°C, and is also excellent in heat resistance.

In addition, in the same manner, as disclosed in Table 1, the composition of the present invention prepared from the novolak type phenol resin (A-4) in Example 4 has ADR1 to 4 of 8,000 Å/sec and 56 Å/sec, respectively. , 540Å/sec, less than 1Å/sec, showing excellent results. In addition, it can be seen that the Tg of the cured product is also very high, at 196°C, and is also excellent in heat resistance.

On the other hand, Comparative Example 1 is an example in which a well-known phenolic novolak resin obtained by performing a condensation reaction of 2-hydroxybenzoic acid and 3,4-dihydroxybenzaldehyde as a composition of an alkali-soluble resin. It can be seen that in the composition prepared in Comparative Example 1, when the developing solution is set to 2.38% tetramethylammonium hydroxide aqueous solution, the alkali dissolution rate of the composition without the sensitizer corresponding to the exposed portion is slow, as 3,500Å/sec, insufficient sensitivity (ADR1). In addition, it can also be seen that when the developing solution is set to a 15% sodium carbonate aqueous solution, the alkali dissolution rate of the composition without the sensitizer corresponding to the exposed portion is slow, less than 1Å/sec, and the sensitivity is insufficient (ADR3). In addition, it can be seen that the Tg of the cured product is low at 52°C, and the heat resistance is also insufficient.

In addition, Comparative Example 2 is an example of using a well-known phenolic novolak resin obtained by condensing m-cresol and p-cresol with formaldehyde as a composition of an alkali-soluble resin. It can be seen that in the composition prepared in Comparative Example 2, when the developing solution is set to 2.38% tetramethylammonium hydroxide aqueous solution, the alkali dissolution rate of the composition not blended with the photosensitive agent corresponding to the exposed portion is slow, as 110Å/sec, insufficient sensitivity (ADR1). In addition, it can also be seen that when the developing solution is set to a 15% sodium carbonate aqueous solution, the alkali dissolution rate of the composition without the sensitizer corresponding to the exposed portion is slow, less than 1Å/sec, and the sensitivity is insufficient (ADR3). In addition, it can be seen that the Tg of the cured product is low at 110°C, and the heat resistance is also insufficient.

Claims (12)

A novolac type phenol resin characterized by a condensation product of an aromatic compound (A) and an aliphatic aldehyde (B) represented by the following formula (1),

(In the formula, R ₁ , R ₂ , and R ₄ are each independently, and represent any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom, and R ₃ and R are each independently, and represent a hydrogen atom. , A hydrocarbon group, any one of the structural parts having one or more alkoxy groups, halogen atoms, and hydroxyl groups on the hydrocarbon group, m, n, and p are each independent, and represent an integer of 0 or 1 to 4). The novolak type phenol resin according to claim 1, wherein the aforementioned aliphatic aldehyde (B) is formaldehyde and/or paraformaldehyde. The novolak type phenol resin according to claim 1 or 2, wherein the aforementioned aromatic compound (A) is a phenol compound and an aromatic aldehyde having a carboxyl group or its ester derivative and/or an aromatic ketone having a carboxyl group or its ester derivative Of polycondensates. The novolak type phenol resin as claimed in claim 3, wherein the aforementioned aromatic aldehyde having a carboxyl group is methyl benzoic acid. The novolak type phenol resin according to any one of claims 1 to 4, wherein the aforementioned aromatic compound (A) is used for condensation with the aliphatic aldehyde (B) after separation and purification. A method for manufacturing a novolac type phenol resin, characterized by separating and purifying an aromatic compound (A) represented by the following formula (1), and then condensing it with an aliphatic aldehyde (B),

(In the formula, R ₁ , R ₂ , and R ₄ are each independently, and represent any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom, and R ₃ and R are each independently, and represent a hydrogen atom. , A hydrocarbon group, any one of the structural parts having one or more alkoxy groups, halogen atoms, and hydroxyl groups on the hydrocarbon group, m, n, and p are each independent, and represent an integer of 0 or 1 to 4). The method for producing a novolak type phenol resin according to claim 6, wherein the aforementioned aliphatic aldehyde (B) is formaldehyde and/or paraformaldehyde. The method for producing novolak type phenol resin according to claim 6 or 7, wherein the aforementioned aromatic compound (A) is a phenol compound and an aromatic aldehyde having a carboxyl group or its ester derivative and/or having a carboxyl group or its ester derivative Aromatic ketone polycondensation compound. The method for producing a novolak type phenol resin according to claim 8, wherein the aromatic aldehyde having a carboxyl group is methyl benzoic acid. A photosensitive composition comprising the novolak type phenol resin according to any one of claims 1 to 5 and a photosensitizer. A photoresist material containing the novolak type phenol resin according to any one of claims 1 to 5. A photoresist film formed of the photoresist material according to claim 11.

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