WO2016103850A1 - Novolac type phenolic resin, photosensitive composition, resist material, coating film, and resist coating film - Google Patents

Abstract

Provided are: a novolac type phenolic resin which is suitable for the achievement of a coating film that has excellent flexibility even if formed thick, while exhibiting excellent heat resistance, alkali developability, sensitivity and resolution; and the like. The present invention specifically provides a novolac type phenolic resin which is obtained by reacting (A) one or more phenolic trinuclear compounds selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (2), (B) a monoaldehyde and (C) a polyaldehyde in the presence of an acid catalyst. (In the formulae, each of R¹, R² and R³ independently represents an optionally substituted alkyl group having 1-8 carbon atoms; R⁴ represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group; each of p and q independently represents an integer of 1-4; r represents an integer of 0-4; and s represents 1 or 2. In this connection, the sum of r and s is 5 or less.)

Description

Novolac type phenolic resin, photosensitive composition, resist material, coating film, and resist coating film

The present invention uses a novolak-type phenol resin suitable for obtaining a resist coating film excellent in heat resistance, flexibility, alkali developability, sensitivity, and resolution, a photosensitive composition containing the resin, and the photosensitive composition. And a coating film (resist coating film) using the resist material.

A positive photoresist using a photosensitive agent such as an alkali-soluble resin and a 1,2-naphthoquinonediazide compound as a resist used in the manufacture of semiconductors such as IC and LSI, the manufacture of display devices such as LCDs, and the manufacture of printing original plates It has been known. Specifically, for example, a positive photoresist composition using a mixture of m-cresol novolak resin and p-cresol novolak resin as the alkali-soluble resin has been proposed (see, for example, Patent Document 1). .

In recent years, higher integration of semiconductors has been increasing, and there is a tendency for patterns to become finer, and higher sensitivity has been demanded. Although the positive photoresist composition described in Patent Document 1 has been developed for the purpose of improving developability such as sensitivity, there is a problem that sufficient sensitivity corresponding to thinning cannot be obtained. Furthermore, since various heat treatments are performed in the manufacturing process of semiconductors and the like, higher heat resistance is also required. However, the positive photoresist composition described in Patent Document 1 does not have sufficient heat resistance. There was a problem.

In order to solve this problem, a positive photoresist composition containing a novolac-type phenol resin obtained by condensing a phenolic trinuclear compound and formaldehyde has been proposed (see, for example, Patent Document 2). .

In recent years, higher integration has been advanced in the semiconductor field. One package format for highly integrated semiconductor components is wafer level packaging. In wafer level packaging, as the wiring density increases, for example, the electrochemical deposition method of electronic wiring described in Non-Patent Document 1 is used. In wafer level packaging, gold bumps, copper posts, and copper wires need to be redistributed to form the final metal structure, but to do this, a resist type that is later electroplated (Mold) is required. This resist (resist layer) is much thicker than the resist used in the formation of critical layers in IC manufacturing. The size of the figure and the resist thickness are typically as thick as 2 μm to 100 μm. Therefore, it is necessary to pattern the photoresist with a high aspect ratio (resist thickness with respect to line size). And in order to pattern into a photoresist with a high aspect ratio, the resist composition from which the coating film which is excellent in a softness | flexibility is obtained even if it thickens is required.

In order to obtain a resist coating film having excellent flexibility even with a thick film, for example, a resist composition containing a novolak resin using an aliphatic polyaldehyde as a nodule of metacresol or paracresol is known (for example, Patent Documents). 3).

Japanese Patent Laid-Open No. 2-05359 International Publication No. 2012/141165 JP 2012-234019 A

However, it has been difficult for the resist coating film obtained using the resist composition described in Patent Document 3 to achieve both heat resistance and alkali dissolution rate.

The problem to be solved by the present invention is a novolac type phenolic resin suitable for obtaining a coating film excellent in flexibility even in the case of a thick film and having excellent heat resistance, alkali developability, sensitivity, and resolution, It is providing the photosensitive composition containing resin, the resist material obtained using the said photosensitive composition, and the coating film (resist coating film) using the said resist material.

As a result of intensive studies to solve the above problems, the present inventors use a phenolic trinuclear compound instead of metacresol or paracresol, and further use both monoaldehydes and polyaldehydes as nodules. As a result, it was found that a novolac type phenol resin having excellent flexibility in the case of a thick film and having good heat resistance and alkali dissolution rate can be obtained, and the present invention has been completed.

That is, the present invention has the following general formula (1)

[In Formula (1), R ¹ , R ² , and R ³ each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent. When a plurality of R ¹ are present, they may be the same or different. When a plurality of R ² are present, they may be the same or different. When a plurality of R ³ are present, May be the same or different. p and q are each independently an integer of 1 to 4, r is an integer of 0 to 4, and s is 1 or 2. However, the sum of r and s is 5 or less. ]
And a compound represented by the following general formula (2)

[In Formula (2), R ¹ , R ² , R ³ , p, and q are the same as those in Formula (1), and t represents an integer of 0 to 5. ]
Obtained by reacting one or more phenolic trinuclear compounds (A), monoaldehydes (B), and polyaldehydes (C) selected from the group consisting of compounds represented by It is related with the novolak-type phenol resin characterized by the above-mentioned.

The present invention also comprises a photosensitive composition comprising the novolak-type phenolic resin and a photosensitive agent, a resist material comprising the photosensitive composition, and the photosensitive composition. And a resist coating film comprising the resist material.

The novolac type phenolic resin and the photosensitive composition containing the resin according to the present invention provide a coating film that is excellent in flexibility even in the case of a thick film, and excellent in heat resistance, alkali developability, sensitivity, and resolution. Can do. For this reason, the said photosensitive composition can be used for a resist material.

2 is a GPC chart of a phenol trinuclear compound (1) obtained in Synthesis Example 1. 3 is a ¹³ C-NMR spectrum chart of the phenolic trinuclear compound (1) obtained in Synthesis Example 1. FIG. 6 is a GPC chart of a novolac resin (1) obtained in Synthesis Example 2. 6 is a GPC chart of a novolac resin (2) obtained in Synthesis Example 3. 6 is a GPC chart of a novolac resin (3) obtained in Synthesis Example 4. 3 is a GPC chart of a novolak resin (4) obtained in Comparative Synthesis Example 1. 6 is a GPC chart of a novolak resin (5) obtained in Comparative Synthesis Example 2.

The novolak-type phenol resin according to the present invention is one or more phenolic trinuclear compounds selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). It is characterized by being obtained by reacting (A), a monoaldehyde (B) and a polyaldehyde (C) in the presence of an acid catalyst. As a phenol type trinuclear compound (A) used as a raw material of the novolak type phenol resin according to the present invention, a compound represented by the general formula (1) (a trinuclear compound having a phenolic hydroxyl group in all three benzene rings) ) And a compound represented by the general formula (2) (a trinuclear compound composed of two benzene rings having a phenolic hydroxyl group and a benzene ring not having a phenolic hydroxyl group) in an appropriate ratio, The amount of hydroxyl groups of the resulting novolak-type phenol resin can be controlled, and as a result, the alkali solubility can be easily controlled to a desired level.

In the general formulas (1) and (2), p and q are each independently an integer of 1 to 4, r is an integer of 0 to 4, and s is 1 or 2. However, the sum of r and s is 5 or less. In the general formula (2), t is an integer of 0 to 5.

In general formulas (1) and (2), R ¹ , R ² , and R ³ each independently represents an alkyl group having 1 to 8 carbon atoms that may have a substituent. When a plurality of R ¹ are present, they may be the same or different. When a plurality of R ² are present, they may be the same or different. When a plurality of R ³ are present, May be the same or different.

The alkyl group may be linear, branched, or a group having a cyclic structure, but is preferably a linear group. In the present invention, the alkyl group of R ¹ , R ² , or R ³ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and linear carbon More preferred is an alkyl group having 1 to 3 atoms.

The hydrogen atom in the alkyl group of R ¹ , R ² , or R ^{3 in} the general formulas (1) and (2) may be substituted with a substituent. The number of hydrogen atoms that can be substituted is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2. When one alkyl group has a plurality of substituents, each substituent may be the same as or different from each other.

Examples of the substituent include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aryl group which may have a substituent, and a halogen atom. Among the substituents of the alkyl group, examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an n-butyloxy group, a t-butyloxy group, a pentyloxy group, and an isoamyloxy group. Hexyloxy group, cyclohexyloxy group and the like. In addition, examples of the aryl group which may have a substituent include a phenyl group, a naphthyl group, an indenyl group, and a biphenyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

Specific examples of the alkyl group represented by R ¹ , R ² , and R ^{3 in} the general formulas (1) and (2) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , T-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, hydroxyethyl group, hydroxypropyl group, fluoromethyl group, methoxyethyl group, ethoxyethyl group, methoxypropyl group, phenylmethyl group, hydroxyphenyl Methyl group, dihydroxyphenylmethyl group, tolylmethyl group, xylylmethyl group, naphthylmethyl group, hydroxynaphthylmethyl group, dihydroxynaphthylmethyl group, phenylethyl group, hydroxyphenylethyl group, dihydroxyphenylethyl group, tolylethyl group, xylylethyl group, naphthylethyl group Group, hydro And naphthylethyl group and dihydroxynaphthylethyl group. Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl group and hexyl group are preferable. Group or ethyl group is more preferable, and methyl group is still more preferable.

R ¹ and R ^{2 in} general formulas (1) and (2) are preferably alkyl groups having the same number of carbon atoms. Further, each of R ¹ and R ² are, in the benzene ring of each R ¹ and R ² are bonded, attached to the carbon atom in the same position when viewed from the carbon atom to which phenolic hydroxyl group such as benzene ring has is attached It is preferable. A phenolic hydroxyl group is bonded to each of the benzene ring to which R ¹ is bonded and the benzene ring to which R ² is bonded. The position at which this phenolic hydroxyl group is bonded is also the same in each benzene ring. preferable. Furthermore, p and q are preferably the same number. As p and q, 2 is preferable.

R in the general formulas (1) and (2) is an integer of 0 to 4. Among these, r is preferably 0.

Examples of the compound represented by the general formula (1) include compounds represented by any one of the following general formulas (1-1) to (1-18). In the general formulas (1-1) to (1-18), R ¹ , R ² , and R ³ are the same as those in the general formula (1), r1 represents an integer of 0 to 4, and r2 is 0 Represents an integer of ~ 3. The general formula (1-1) to the compound represented by the formula (1-18), Compound ^{R 1} and ^{R 2} are both methyl or ethyl group, and r1 and r2 is 0 Preferably, ^{R 1} R ² and R ² are both methyl groups, and r1 and r2 are 0.

As the compound represented by the general formula (1), since a novolac type phenol resin capable of obtaining a coating film having heat resistance and high resolution is obtained, the general formulas (1-1), (1-2), Compounds represented by (1-7), (1-8), (1-13), or (1-14) are preferred, and are represented by the general formulas (1-1), (1-7), or (1- The compound represented by 13) is more preferred, and the compound represented by formula (1-1) is more preferred.

Examples of the compound represented by the general formula (2) include compounds represented by any one of the following general formulas (2-1) to (2-6). In the general formulas (2-1) to (2-6), R ¹ , R ² , R ³ , and t are the same as those in the general formula (2). The general formula (2-1) to the compound represented by the formula (2-6), compound ^{R 1} and ^{R 2} are both methyl or ethyl group, and t is 0 are preferred, ^{R 1} and R ^A compound in which both ² are methyl groups and t is 0 is more preferable.

As the compound represented by the general formula (2), a novolac type phenol resin capable of obtaining a coating film having heat resistance and high resolution can be obtained. Therefore, the compound represented by the general formula (2-1) or (2-2) The compound represented by Formula (2-1) is more preferable.

The compound represented by the general formula (1) includes, for example, an alkyl-substituted phenol (d1) and a hydroxyl group-containing aromatic aldehyde (d2), and a carbon atom on the aromatic hydrocarbon group of the alkyl-substituted phenol (d1). It can be obtained by carrying out the condensation under conditions where the difference in reaction activity energy can be utilized. Specifically, for example, the compound represented by the general formula (1) is obtained by polycondensing an alkyl-substituted phenol (d1) and a hydroxyl group-containing aromatic aldehyde (d2) in the presence of an acid catalyst. .

The compound represented by the general formula (2) is, for example, alkyl-substituted phenol (d1) and an aromatic aldehyde having no hydroxyl group (hydroxyl-free aromatic aldehyde) (d′ 2). It can be obtained by performing condensation under conditions that can utilize the difference in the reaction activity energy of carbon atoms on the aromatic hydrocarbon group of phenol (d1). Specifically, for example, the compound represented by the general formula (1) is obtained by polycondensing an alkyl-substituted phenol (d1) and a hydroxyl group-free aromatic aldehyde (d′ 2) in the presence of an acid catalyst. Is obtained.

The alkyl-substituted phenol (d1) is a compound in which part or all of the hydrogen atoms bonded to the phenol benzene ring are substituted with an alkyl group. Examples of the alkyl group include alkyl groups having 1 to 8 carbon atoms, and a methyl group is particularly preferable. Examples of the alkyl-substituted phenol (d1) include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, pt-butylphenol, o Monoalkylphenols such as cyclohexylphenol, m-cyclohexylphenol and p-cyclohexylphenol; dialkyl such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4-xylenol, 2,6-xylenol Examples include alkylphenols; trialkylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol. Among these alkyl-substituted phenols, those having a substitution number of alkyl groups on the benzene ring of phenol of 2 are preferable because of excellent balance between heat resistance and alkali solubility. Specific examples include 2,5- Xylenol and 2,6-xylenol are preferred. These alkyl-substituted phenols (d1) can be used alone or in combination of two or more, but preferably only one is used.

The hydroxyl group-containing aromatic aldehyde (d2) is a compound having at least one aldehyde group and at least one hydroxyl group in the aromatic ring. Examples of the hydroxyl group-containing aromatic aldehyde (d2) include hydroxybenzaldehydes such as salicylaldehyde, m-hydroxybenzaldehyde and p-hydroxybenzaldehyde; dihydroxybenzaldehydes such as 2,4-dihydroxybenzaldehyde and 3,4-dihydroxybenzaldehyde; vanillin And vanillin compounds such as ortho vanillin, isovanillin and ethyl vanillin; Among these hydroxyl group-containing aromatic aldehydes (d2), p-hydroxybenzaldehyde (4-hydroxybenzaldehyde) and 2,4-dihydroxybenzaldehyde are available because they are easily available industrially and have a good balance between heat resistance and alkali solubility. 3,4-dihydroxybenzaldehyde is preferred, and p-hydroxybenzaldehyde is more preferred.

The hydroxyl group-free aromatic aldehyde (d′ 2) is a compound having at least one aldehyde group in the aromatic ring and not having a phenolic hydroxyl group. Examples of the hydroxyl group-free aromatic aldehyde (d′ 2) include benzaldehyde; alkylbenzaldehyde such as methylbenzaldehyde, ethylbenzaldehyde, dimethylbenzaldehyde, and diethylbenzaldehyde; alkoxybenzaldehyde such as methoxybenzaldehyde and ethoxybenzaldehyde; Among these hydroxyl group-free aromatic aldehydes (d′ 2), benzaldehyde is preferable.

The compound represented by the general formula (1) or (2) includes, for example, the alkyl-substituted phenol (d1), the hydroxyl group-containing aromatic aldehyde (d2) or the hydroxyl group-free aromatic aldehyde (d′ 2), Can be obtained by polycondensation in the presence of an acid catalyst. For example, by polycondensation of 2,5-xylenol and 4-hydroxybenzaldehyde in the presence of an acid catalyst, R ¹ and R ^{2 in the} general formula (1-1) are both methyl groups, and r A compound is obtained in which is 0. By polycondensation of 2,6-xylenol and 4-hydroxybenzaldehyde in the presence of an acid catalyst, in the general formula (1-2), R ¹ and R ² are both methyl groups, and r is 0 Is obtained.

Examples of the acid catalyst include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, manganese acetate and the like. These acid catalysts can be used alone or in combination of two or more. Of these acid catalysts, sulfuric acid and paratoluenesulfonic acid are preferred because of their excellent activity. The acid catalyst may be added before the reaction or may be added during the reaction.

The polycondensation of the alkyl-substituted phenol (d1) and the hydroxyl group-containing aromatic aldehyde (d2) or the hydroxyl group-free aromatic aldehyde (d′ 2) may be performed in the presence of an organic solvent, if necessary. . Examples of the organic solvent include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin and other polyols; 2-ethoxyethanol, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene Glycol ethers such as glycol ethyl methyl ether and ethylene glycol monophenyl ether; Cyclic ethers such as 1,3-dioxane and 1,4-dioxane; Glycol esters such as ethylene glycol acetate; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone Is mentioned. These organic solvents can be used alone or in combination of two or more. Among these organic solvents, 2-ethoxyethanol is preferable because the resulting compound has excellent solubility.

The reaction temperature for polycondensing the alkyl-substituted phenol (d1) with the hydroxyl group-containing aromatic aldehyde (d2) or the hydroxyl group-free aromatic aldehyde (d′ 2) is, for example, 60 to 140 ° C. The reaction time is, for example, 0.5 to 100 hours.

Charge ratio [(d1) / (d2)] of the alkyl-substituted phenol (d1) and the hydroxyl group-containing aromatic aldehyde (d2) and the alkyl-substituted phenol (d1) and the hydroxyl group-free aromatic aldehyde (d′ 2) ), The charge ratio [(d1) / (d′ 2)] is excellent in the removal of unreacted alkyl-substituted phenol (d1), the yield of the product and the purity of the reaction product. The ratio is preferably in the range of 1 / 0.2 to 1 / 0.5, more preferably in the range of 1 / 0.25 to 1 / 0.45.

In the reaction solution of the polycondensation of the alkyl-substituted phenol (d1) and the hydroxyl group-containing aromatic aldehyde (d2) or the hydroxyl group-free aromatic aldehyde (d′ 2), the general formula (1 ) Or (2) and the unreacted substance may remain. Moreover, an unfavorable condensate other than the compound represented by the general formula (1) or (2) may be generated. Therefore, before being used as a raw material for the novolak-type phenol resin according to the present invention (phenolic trinuclear compound (A)), it is represented by the general formula (1) or (2) from the reaction solution after the polycondensation reaction. It is preferable to purify the compound. The purity of the compound represented by the general formula (1) or (2) used as the phenol trinuclear compound (A) is preferably 85% or more, more preferably 90% or more, still more preferably 94% or more, 98% or more is particularly preferable. The purity of the compound represented by the general formula (1) or (2) can be determined from the area ratio in the GPC chart.

As a method for purifying the compound represented by the general formula (1) or (2) to increase the purity, for example, the reaction solution after the polycondensation reaction is converted to the compound represented by the general formula (1) or (2). Is filtered into the poor solvent (S1), which is insoluble or hardly soluble, and the resulting precipitate is dissolved in the compound represented by the general formula (1) or (2) In addition, there is a method in which the precipitate generated by dissolving in the solvent (S2) that is also mixed with the poor solvent (S1) and throwing again into the poor solvent (S1) is filtered. Examples of the poor solvent (S1) used in this case include water; monoalcohols such as methanol, ethanol, and propanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohyxane; toluene, xylene And aromatic hydrocarbons. Among these poor solvents (S1), water and methanol are preferable because the acid catalyst can be efficiently removed at the same time. On the other hand, examples of the solvent (S2) include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5- Polyols such as pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin; 2-ethoxyethanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether Glycol ethers such as ethylene glycol ethyl methyl ether and ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane and 1,4-dioxane; glycol esters such as ethylene glycol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like Examples include ketones. When water is used as the poor solvent (S1), acetone is preferable as the (S2). The poor solvent (S1) and the solvent (S2) can be used alone or in combination of two or more.

As a raw material of the novolak-type phenol resin according to the present invention, one or more compounds represented by the general formula (1) may be used as the phenolic trinuclear compound (A). Two or more kinds of compounds represented by the general formula (2) may be used, and one kind or two or more kinds of compounds represented by the general formula (1) and one kind or two or more kinds of the general formula (2). You may use the compound represented by these. Of the phenolic trinuclear compound (A), by adjusting the ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2), the resulting novolak-type phenol resin has a hydroxyl group. The amount can be adjusted. For example, as the ratio of the compound represented by the general formula (1) in the phenol trinuclear compound (A) is larger, a novolac type phenol resin having a higher hydroxyl solubility and higher alkali solubility is obtained. On the contrary, as the ratio of the compound represented by the general formula (2) in the phenol trinuclear compound (A) is larger, a novolak type phenol resin having a lower hydroxyl group and lower alkali solubility is obtained.

As monoaldehyde (B) used as a raw material of the novolak-type phenol resin which concerns on this invention, the compound represented by following General formula (3) can be used, for example. In General Formula (3), R ⁴ represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent. Note that the monoaldehydes (B) used as a raw material may be a single compound or a combination of two or more compounds.

Among the compounds represented by the general formula (3), formaldehyde; alkyl aldehydes such as acetaldehyde, propyl aldehyde, butyraldehyde, isobutyraldehyde, pentyl aldehyde, hexyl aldehyde; salicyl aldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde 2-hydroxy-4-methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde and the like; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy- 3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-hydroxy-3,5-dimethoxybenzalde A benzaldehyde having both a hydroxy group and an alkoxy group such as alkoxide; an alkoxybenzaldehyde such as methoxybenzaldehyde and ethoxybenzaldehyde; 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 6-hydroxy-2-naphthaldehyde Hydroxynaphthaldehydes such as halogenated benzaldehydes such as bromobenzaldehyde are preferred, formaldehyde or alkyl aldehydes are more preferred, formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, isobutyraldehyde, pentyl aldehyde, or hexyl aldehyde are more preferred, Is particularly preferred. When formaldehyde is used as the monoaldehydes (B), formaldehyde and other aldehydes may be used in combination. When formaldehyde and other aldehydes are used in combination, the amount of other aldehydes used is preferably in the range of 0.05 to 1 mole per mole of formaldehyde.

The polyaldehyde (C) used as a raw material for the novolak type phenol resin according to the present invention is not particularly limited as long as it is a compound having two or more aldehyde groups in the molecule. Specific examples of polyaldehydes (C) include aliphatic dialdehydes such as glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde and adipaldehyde; aromatic dialdehydes such as phthalaldehyde, isophthalaldehyde and terephthalaldehyde An aliphatic trialdehyde such as triformylmethane; an aromatic trialdehyde such as benzenetrialdehyde; Among them, terephthalaldehyde or glutaraldehyde is preferable as the polyaldehyde (C) because it is easily available and a higher heat-resistant novolak type phenol resin can be obtained. The polyaldehyde (C) used as a raw material may be a single compound or a combination of two or more compounds.

The novolak-type phenol resin according to the present invention is obtained, for example, by condensing a phenol trinuclear compound (A), a monoaldehyde (B), and a polyaldehyde (C) in the presence of an acid catalyst. . The charge ratio [(A) / (B)] of the phenolic trinuclear compound (A) and the monoaldehydes (B) can suppress excessive high molecular weight (gelation) and is suitable as a coating material. Since a molecular weight can be obtained, the molar ratio is preferably in the range of 1 / 0.5 to 1 / 1.2, and more preferably in the range of 1 / 0.6 to 1 / 0.9. In addition, the charging ratio (amount used) [(B) / (C)] of the monoaldehydes (B) and polyaldehydes (C) to be reacted with the phenol trinuclear compound (A) is 1 / (mass ratio). A range of 0.01 to 1 / 1.5 is preferable, and a range of 1 / 0.05 to 1 / 1.2 is more preferable.

Acid catalysts used in the reaction include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, hydrobromic acid, perchloric acid and phosphoric acid, sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid, and oxalic acid And organic acids such as succinic acid, malonic acid, monochloroacetic acid and dichloroacetic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. Among these, since it shows strong acidity and promotes the reaction of the phenolic trinuclear compound (A), monoaldehydes (B) and polyaldehydes (C) with high activity, sulfuric acid or p-toluenesulfonic acid is used. preferable. The amount of these acid catalysts used is preferably in the range of 0.1 to 25% by mass relative to the total mass of the reaction raw materials.

The condensation reaction of the phenolic trinuclear compound (A), the monoaldehydes (B) and the polyaldehydes (C) may be performed in the presence of an organic solvent as necessary. Examples of the organic solvent include the same organic solvents that can be used in the polycondensation of the alkyl-substituted phenol (d1) and the hydroxyl group-containing aromatic aldehyde (d2). The organic solvent can be used alone or in combination of two or more. Further, 2-ethoxyethanol is preferred as the organic solvent from the viewpoint of excellent solubility of the resulting novolak type phenol resin.

Examples of the novolak-type phenolic resin according to the present invention include, as repeating units, a structural unit (I-1) represented by the following general formula (I-1) and a structure represented by the following general formula (I-2). Group consisting of unit (I-2), structural unit (II-1) represented by the following general formula (II-1), and structural unit (II-2) represented by the following general formula (II-2) What has 1 or more types of structural site | parts selected more is preferable. In the general formulas (I-1), (I-2), (II-1), and (II-2), R ¹ and R ² are the same as those in the general formula (1), and R ⁴ is It is the same as the general formula (3). As the structural unit represented by the general formula (I-1), (I-2), (II-1), or (II-2), R ¹ and R ² are both the same group, and R ⁴ is preferably a hydrogen atom, R ¹ and R ² are both the same unsubstituted alkyl group having 1 to 3 carbon atoms, and R ⁴ is more preferably a hydrogen atom, and R ¹ and More preferably, both R ² are methyl groups and R ⁴ is a hydrogen atom.

The weight average molecular weight of the novolak type phenolic resin according to the present invention is preferably 1,000 to 100,000, more preferably 1,000 to 70,000, and still more preferably 1,000 to 35,000. Among them, the molecular weight of the novolac type phenol resin having the structural unit represented by the general formula (I-1) or the structural unit represented by the general formula (II-1) as a repeating unit has a novolac having more excellent heat resistance. Type phenol resin is obtained, the weight average molecular weight (Mw) is preferably 5,000 to 100,000, more preferably 5,000 to 70,000, still more preferably 5,000 to 35,000, 000 to 25,000 is particularly preferred. In addition, the molecular weight of the novolac type phenol resin having the structural unit represented by the general formula (I-2) or the structural unit represented by the general formula (II-2) as a repeating unit has a novolak having more excellent heat resistance. Since a type phenol resin is obtained, the weight average molecular weight (Mw) is preferably 1,000 to 5,000, more preferably 2,000 to 4,000.

In the present invention and the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the novolak type phenol resin are measured by gel permeation chromatography (hereinafter abbreviated as “GPC”) as follows. It is measured under conditions.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” (8.0 mm ID × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mm ID × 300 mm) manufactured by Showa Denko KK + “Shodex KF803” manufactured by Showa Denko KK (8.0 mm ID × 300 mm) + “Shodex KF804” (8.0 mm ID × 300 mm) manufactured by Showa Denko KK
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 in terms of resin solid content filtered through a microfilter,
Injection volume: 0.1 mL,
Standard sample: Monodispersed polystyrene below

(Standard sample: monodisperse polystyrene)
“A-500” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation

The novolak type phenolic resin according to the present invention can be used for various electric and electronic member applications such as adhesives, paints, photoresists, printed wiring boards and the like. In particular, the novolak type phenolic resin according to the present invention is excellent in balance among flexibility, heat resistance, and alkali solubility, and also has good substrate followability. For this reason, the novolak-type phenol resin according to the present invention is suitable as a resist material, particularly as a resist material for thick films. By using the novolak type phenol resin according to the present invention, a photosensitive composition suitable as a thick film resist having sensitivity, resolution, heat resistance, substrate followability and flexibility can be obtained.

The photosensitive composition according to the present invention is characterized by containing a photosensitive agent in addition to the novolac type phenol resin according to the present invention. Examples of the photosensitive agent include compounds having a quinonediazide group when the photosensitive composition according to the present invention is used as a positive resist material. Moreover, when using the photosensitive composition concerning this invention as a negative resist material, a photo-acid generator etc. are mentioned.

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, ortho Examples include complete ester compounds, partial ester compounds, amidated products, and partially amidated products with sulfonic acids having a quinonediazide group such as anthraquinone diazide sulfonic acid. These photosensitizers may be used alone or in combination of two or more.

Examples of the aromatic (poly) hydroxy compound used here include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4, 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′-hexahydroxyben Polyhydroxy benzophenone compounds such phenone;

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) A tris (hydroxyphenyl) methane compound such as phenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, or a methyl-substituted product 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- Methylph Nyl) -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 Methyl-substituted products thereof.

When a compound having a quinonediazide group is used as a photosensitizer in the photosensitive composition according to the present invention, the amount of the compound becomes a composition with excellent photosensitivity, so that the novolac type phenol resin according to the present invention (according to the present invention) When the photosensitive composition contains other resin components, the ratio is 5 to 50 parts by mass with respect to 100 parts by mass of the total resin component including the novolac type phenol resin according to the present invention. The ratio is preferably 5 to 30 parts by mass.

Examples of the photoacid generator include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, and the like.

Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Specific examples of preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluorochlorosulfonate, Phenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4,7-di-n- Butoxynaphthyltetrahydrothiophenium trifluorolo Tan sulfonates.

Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, and phenyl-bis (trichloromethyl) -s-triazine. S-triazine derivatives such as 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, and the like.

Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples of preferred sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenacylsulfonyl) methane.

Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, and o-nitrobenzyl p-toluene sulfonate.

Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide.

Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.

When a photoacid generator is used as the photosensitizer in the photosensitive composition according to the present invention, the amount of the photoacid generator is a composition having excellent photosensitivity, and therefore the novolak-type phenolic resin according to the present invention In the case where the adhesive composition contains other resin components, the ratio is 5 to 50 parts by mass with respect to 100 parts by mass of the total resin component including the novolac type phenol resin according to the present invention. The proportion is preferably 5 to 30 parts by mass.

The photosensitive composition according to the present invention may contain an organic base compound for neutralizing the acid generated from the photoacid generator during exposure. The addition of the organic base compound has an effect of preventing the dimensional variation of the resist pattern due to the movement of the acid generated from the photoacid generator. Examples of the organic base compound used here include organic amine compounds selected from nitrogen-containing compounds. Specifically, pyrimidine, 2-aminopyrimidine, 4-aminopyrimidine, 5-aminopyrimidine, 2,4-diaminopyrimidine, 2,5-diaminopyrimidine, 4,5-diaminopyrimidine, 4,6-diaminopyrimidine, 2,4,5-triaminopyrimidine, 2,4,6-triaminopyrimidine, 4,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-hydroxypyrimidine, 4-hydroxy Pyrimidine, 5-hydroxypyrimidine, 2,4-dihydroxypyrimidine, 2,5-dihydroxypyrimidine, 4,5-dihydroxypyrimidine, 4,6-dihydroxypyrimidine, 2,4,5-trihydroxypyrimidine, 2,4,6 -Trihydroxypyrimidine, 4,5,6-trihydroxypyrimidine, 2 4,5,6-tetrahydroxypyrimidine, 2-amino-4-hydroxypyrimidine, 2-amino-5-hydroxypyrimidine, 2-amino-4,5-dihydroxypyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4-amino-2,5-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-5-methylpyrimidine, 2-amino-4,5-dimethylpyrimidine 2-amino-4,6-dimethylpyrimidine, 4-amino-2,5-dimethylpyrimidine, 4-amino-2,6-dimethylpyrimidine, 2-amino-4-methoxypyrimidine, 2-amino-5-methoxy Pyrimidine, 2-amino-4,5-dimethoxypyrimidine, 2-amino-4,6-dimethoxy Limidine, 4-amino-2,5-dimethoxypyrimidine, 4-amino-2,6-dimethoxypyrimidine, 2-hydroxy-4-methylpyrimidine, 2-hydroxy-5-methylpyrimidine, 2-hydroxy-4,5- Dimethylpyrimidine, 2-hydroxy-4,6-dimethylpyrimidine, 4-hydroxy-2,5-dimethylpyrimidine, 4-hydroxy-2,6-dimethylpyrimidine, 2-hydroxy-4-methoxypyrimidine, 2-hydroxy-4 -Methoxypyrimidine, 2-hydroxy-5-methoxypyrimidine, 2-hydroxy-4,5-dimethoxypyrimidine, 2-hydroxy-4,6-dimethoxypyrimidine, 4-hydroxy-2,5-dimethoxypyrimidine, 4-hydroxy- Pyrimidines such as 2,6-dimethoxypyrimidine Compound;

Pyridine compounds such as pyridine, 4-dimethylaminopyridine, 2,6-dimethylpyridine;

Amine compounds substituted with a hydroxyalkyl group having 1 to 4 carbon atoms, such as diethanolamine, triethanolamine, triisopropanolamine, tris (hydroxymethyl) aminomethane, bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane ;

Examples include aminophenol compounds such as 2-aminophenol, 3-aminophenol, and 4-aminophenol. These may be used alone or in combination of two or more. Among them, the pyrimidine compound, the pyridine compound, or the amine compound having a hydroxy group is preferable, and the amine compound having a hydroxy group is particularly preferable because of excellent dimensional stability of the resist pattern after exposure.

When the organic base compound is added, the addition amount is preferably in the range of 0.1 to 100 mol%, preferably in the range of 1 to 50 mol%, with respect to the content of the photoacid generator. Is more preferable.

The photosensitive composition according to the present invention may use other resins as the resin component in addition to the novolac type phenol resin according to the present invention. Other resins are preferably those that are soluble in an alkali developer, or those that are soluble in an alkali developer when used in combination with an additive such as an acid generator (alkali-soluble resin).

Other resins used here include, for example, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenolic compounds, modified novolaks of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds. Resins, phenol aralkyl resins (Zyloc resins), naphthol aralkyl resins, trimethylol methane resins, tetraphenylol ethane resins, biphenyl modified phenol resins, biphenyl modified naphthol resins, aminotriazine modified phenol resins, and various vinyl polymers It is done.

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

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 the other resin is used, the blending ratio of the novolac type phenol resin and the other resin according to the present invention can be arbitrarily adjusted depending on the desired application. Among them, since the effect of the novolac type phenol resin according to the present invention is sufficiently exhibited, the novolac type phenol resin according to the present invention is 60% by mass with respect to the total of the novolac type phenol resin according to the present invention and other resins. It is preferable to use more, and it is more preferable to use 80% by mass or more.

The photosensitive composition according to the present invention may contain a surfactant for the purpose of improving the 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; having a silicone structure site in the molecular structure Examples thereof include silicone surfactants. These may be used alone or in combination of two or more. The amount of these surfactants to be added is 0.001 to 2 with respect to 100 parts by mass of the resin solid content (including the novolac type phenol resin according to the present invention as the resin solid content) in the photosensitive composition according to the present invention. It is preferable to use in the range of parts by mass.

The photosensitive composition according to the present invention may further contain a filler. The filler can improve the hardness and thermal decomposition resistance of the coating film. The filler contained in the photosensitive composition according to the present invention may be an organic filler, but is preferably an inorganic filler. Examples of inorganic fillers include silica, mica, talc, clay, bentonite, montmorillonite, kaolinite, wollastonite, calcium carbonate, calcium hydroxide, magnesium carbonate, titanium oxide, alumina, aluminum hydroxide, barium sulfate, and titanium. Examples thereof include barium acid, potassium titanate, zinc oxide, and glass fiber. Among them, it is preferable to use silica because the coefficient of thermal expansion can be lowered.

The photosensitive composition according to the present invention may further contain a curing agent. As the curing agent contained in the photosensitive composition according to the present invention, for example, a melamine compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, a guanamine compound, a glycoluril compound, Examples include urea compounds, resol resins, epoxy compounds, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, and oxazoline compounds.

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, hexamethylol melamine Examples thereof include compounds in which 1 to 6 methylol 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, Examples thereof include compounds in which 1 to 4 methylol groups of tetramethylolguanamine 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. Can be mentioned.

Examples of the resole resins include phenols, alkylphenols such as cresol and xylenol, bisphenols such as phenylphenol, resorcinol, biphenyl, bisphenol A and bisphenol F, phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene, and aldehyde compounds. Examples thereof include polymers obtained by reacting under alkaline catalyst conditions.

Examples of the epoxy compound include tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, 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, and tetramethylene glycol divinyl ether. Vinyl 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 tri Examples include vinyl ether.

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

Among these, a glycoluril compound, a urea compound, and a resole resin are preferable because the composition is excellent in curability and has excellent dry etching resistance and thermal decomposition resistance when used for resist underlayer film applications. Is particularly preferred.

When the photosensitive composition according to the present invention contains the curing agent, the blending amount of the curing agent is the novolak according to the present invention in order to maintain the excellent sensitivity of the novolak type phenol resin according to the present invention. It is 50 mass parts or less with respect to 100 mass parts of type phenol resins. Since the compounding amount of the curing agent of the photosensitive composition according to the present invention is a composition from which a film excellent in curability, heat decomposability, and alkali developability is obtained, the novolak type phenol resin 100 according to the present invention is obtained. The ratio is preferably 0.1 to 50 parts by mass with respect to part by mass, and further, the ratio is 0.1 to 30 parts by mass because a composition is obtained that provides a film with excellent photosensitivity. More preferably, the proportion is 0.5 to 20 parts by mass.

The photosensitive composition according to the present invention is preferably obtained by dissolving or dispersing various additives such as dyes, pigments, cross-linking agents, and dissolution accelerators in an organic solvent, if necessary. A coating film can be formed by applying a material dissolved in an organic solvent to a substrate or the like. Dyes, pigments, crosslinking agents, and dissolution accelerators can be appropriately selected from those commonly used as additives for resist materials in consideration of the intended use.

Examples of the organic solvent include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether propylene glycol monomethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol diethylene ether. Dialkylene glycol dialkyl ethers such as propyl ether and diethylene glycol dibutyl ether; alkylene glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate; Ketone compounds such as methyl, 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, Ester compounds such as 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 These may be used alone or in combination of two or more.

The photosensitive composition according to the present invention can be prepared by blending the above components and mixing them using a stirrer or the like. Moreover, when a photosensitive composition contains a filler and a pigment, it can adjust by disperse | distributing or mixing using dispersers, such as a dissolver, a homogenizer, and a 3 roll mill.

The photosensitive composition according to the present invention can be suitably used as a resist material. The photosensitive composition according to the present invention may be used as a resist material as it is dissolved / dispersed in an organic solvent, or may be removed by applying a film dissolved / dispersed in an organic solvent. A solvent may be used as a resist film. Examples of the support film used as the 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.

Photolithographic methods using the photosensitive composition according to the present invention include, for example, applying a photosensitive composition (resist material) dissolved and dispersed in an organic solvent onto an object to be subjected to silicon substrate photolithography, Pre-bake 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 is the creation of a resist pattern.If the photosensitive composition is positive, the target resist pattern is exposed through a predetermined mask, and the exposed portion is dissolved in an alkali developer. A resist pattern is formed. Since the photosensitive composition according to the present invention has high photosensitivity, it is possible to form a resist pattern with excellent resolution.

Examples of the exposure light source here include infrared light, visible light, ultraviolet light, far-ultraviolet light, X-rays, and electron beams. Examples of ultraviolet light include g-line (wavelength 436 nm) and h-line (wavelength 436 nm) of a high-pressure mercury lamp. Examples include a wavelength 405 nm) i-line (wavelength 365 nm), a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), and an EUV laser (wavelength 13.5 nm). Since the photosensitive composition according to the present invention has high photosensitivity and alkali developability, a resist pattern can be formed with high resolution when any light source is used.

The film thickness of the coating film formed from the photosensitive composition (resist material) according to the present invention can be arbitrarily adjusted depending on the desired application. Even when a thick film is formed, the effect of the novolac-type phenolic resin according to the present invention that can form a coating film excellent in flexibility without sacrificing heat resistance or alkali solubility is sufficiently expressed. The thickness of the coating film is preferably from 100 nm to 100 μm, more preferably from 500 nm to 100 μm, further preferably from 2 to 100 μm, still more preferably from 2 to 20 μm.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, “part” and “%” are based on mass unless otherwise specified.

<GPC measurement of resin>
The molecular weight distribution of the resin was measured by GPC under the following measurement conditions in the polystyrene standard method.

(GPC measurement conditions)
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” (8.0 mm ID × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mm ID × 300 mm) manufactured by Showa Denko KK + “Shodex KF803” manufactured by Showa Denko KK (8.0 mm ID × 300 mm) + “Shodex KF804” (8.0 mm ID × 300 mm) manufactured by Showa Denko KK
Detector: RI (differential refractometer),
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate 1.0 mL / min Sample: 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids with a microfilter (5 μL),
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
“A-1000” 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
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

<Measurement of ¹³ C-NMR spectrum of resin>
The ¹³ C-NMR spectrum of the resin was subjected to structural analysis by analyzing the DMSO-d ₆ solution of the sample using “JNM-LA300” manufactured by JEOL Ltd. The measurement conditions for ¹³ C-NMR spectrum are shown below.

( ^13C -NMR spectrum measurement conditions)
Measurement mode: SGNNE (1H complete decoupling method of NOE elimination)
Pulse angle: 45 ° C Pulse sample concentration: 30 wt%
Integration count: 10,000 times

[Synthesis Example 1] <Synthesis of phenol trinuclear compound>
A 2 L four-necked flask equipped with a condenser was charged with 293.2 g (2.4 mol) of 2,5-xylenol, 122 g (1 mol) of 4-hydroxybenzaldehyde, and 500 mL of 2-ethoxyethanol. 2,5-xylenol and 4-hydroxybenzaldehyde were dissolved in ethanol. Subsequently, 10 mL of sulfuric acid was added to the reaction solution in the four-necked flask while cooling in an ice bath, and then the mixture was heated with a mantle heater at 100 ° C. for 2 hours, and reacted with stirring. Water was added to the reaction solution after completion of the reaction and reprecipitation was performed to obtain a crude product. The crude product was redissolved in acetone, and further reprecipitation operation was performed with water. The product obtained by the reprecipitation operation was filtered off and vacuum dried to obtain 213 g of a white crystal precursor compound (phenolic trinuclear compound (1)). The phenol trinuclear compound (1) was subjected to GPC and ¹³ C-NMR spectrum measurement. As a result, it was confirmed that the compound was the target compound and the purity was 98.2% by mass in terms of the area ratio of GPC. The GPC chart of the phenolic trinuclear compound (1) is shown in FIG. 1, and the ¹³ C-NMR spectrum chart is shown in FIG.

[Synthesis Example 2] <Synthesis of novolac type phenol resin>
In a 300 mL four-necked flask equipped with a condenser, 34.8 g (0.1 mol) of the phenolic trinuclear compound (1) obtained in Synthesis Example 1 and 8.0 g (0.04 mol) of 50% glutaraldehyde. ), 15 mL of 2-ethoxyethanol and 15 mL of acetic acid were charged, and the phenol trinuclear compound (1) and glutaraldehyde were dissolved in a mixed solvent of 2-ethoxyethanol and acetic acid. Subsequently, 10 mL of sulfuric acid was added to the reaction solution in the four-necked flask while cooling in an ice bath, and then 3.0 g (0.09 mol) of 92% paraformaldehyde was added to the reaction solution at 80 ° C. with an oil bath. The temperature was raised, heated for 10 hours, and allowed to react with stirring. Water was added to the reaction solution after completion of the reaction and reprecipitation was performed to obtain a crude product. The crude product was redissolved in acetone, and further reprecipitation operation was performed with water. The product obtained by the reprecipitation operation was filtered off and vacuum-dried to obtain 32.9 g of a novolac type phenol resin (novolac resin (1)) as a red powder. A GPC chart of the novolak resin (1) is shown in FIG. When GPC was performed on the novolak resin (1), the number average molecular weight (Mn) = 2,051, the weight average molecular weight (Mw) = 7,855, and the polydispersity (Mw / Mn) = 3.83. .

[Synthesis Example 3] <Synthesis of novolac type phenol resin>
31.3 g of a novolac type phenol resin (novolac resin (2)) as a red powder was obtained in the same manner as in Synthesis Example 2, except that the amount of 50% glutaraldehyde charged was 4.0 g (0.02 mol). . A GPC chart of the novolak resin (2) is shown in FIG. When GPC was performed on the novolak resin (2), the number average molecular weight (Mn) = 1,889, the weight average molecular weight (Mw) = 6,721, and the polydispersity (Mw / Mn) = 3.56. .

[Synthesis Example 4] <Synthesis of novolac type phenol resin>
34.1 g of red powdered novolak-type phenol resin (novolak resin (3)) was obtained in the same manner as in Synthesis Example 2, except that the amount of 50% glutaraldehyde charged was 20.0 g (0.1 mol). . A GPC chart of the novolak resin (3) is shown in FIG. When GPC was performed on the novolak resin (3), the number average molecular weight (Mn) = 1,504, the weight average molecular weight (Mw) = 5,412 and the polydispersity (Mw / Mn) = 3.60. .

[Comparative Synthesis Example 1] <Synthesis of (non-flexible) novolac type phenolic resin>
In a 300 mL four-necked flask equipped with a condenser, 17.4 g (0.05 mol) of the phenolic trinuclear compound (1) obtained in Synthesis Example 1 and 1.6 g (0.05 mol) of 92% paraformaldehyde ), 15 mL of 2-ethoxyethanol and 15 mL of acetic acid were charged, and the phenolic trinuclear compound (1) and paraformaldehyde were dissolved in a mixed solvent of 2-ethoxyethanol and acetic acid. Subsequently, 10 mL of sulfuric acid was added to the reaction solution in the four-necked flask while cooling in an ice bath, and then the temperature was raised to 80 ° C. in an oil bath, heated for 4 hours, and reacted while stirring. Water was added to the reaction solution after completion of the reaction and reprecipitation was performed to obtain a crude product. The crude product was redissolved in acetone, and further reprecipitation operation was performed with water. The product obtained by the reprecipitation operation was separated by filtration and vacuum-dried to obtain 16.8 g of a red powder novolac type phenol resin (novolak resin (4)). A GPC chart of the novolak resin (4) is shown in FIG. When GPC was performed on the novolak resin (4), the number average molecular weight (Mn) = 1,994, the weight average molecular weight (Mw) = 7,603, and the polydispersity (Mw / Mn) = 3.81. .

[Comparative Synthesis Example 2] <Synthesis of (flexibility) cresol novolac resin>
In a 300 mL four-necked flask equipped with a condenser, 13.0 g (0.12 mol) of metacresol, 8.6 g (0.08 mol) of paracresol, 16.0 g of 50% glutaraldehyde (0.08 mol) Then, 15 mL of 2-ethoxyethanol and 15 mL of acetic acid were charged, and metacresol, para-cresol, and glutaraldehyde were dissolved in a mixed solvent of 2-ethoxyethanol and acetic acid. Subsequently, 10 mL of sulfuric acid was added to the reaction solution in the four-necked flask while cooling in an ice bath, and then 3.3 g (0.1 mol) of 92% paraformaldehyde was charged and the oil bath was heated to 80 ° C. The temperature was raised, heated for 10 hours, and allowed to react with stirring. Water was added to the reaction solution after completion of the reaction and reprecipitation was performed to obtain a crude product. The crude product was redissolved in acetone, and further reprecipitation operation was performed with water. The product obtained by the reprecipitation operation was separated by filtration and vacuum-dried to obtain 20.6 g of an orange powder of cresol novolak resin (novolak resin (5)). A GPC chart of the novolak resin (5) is shown in FIG. When GPC was performed on the novolak resin (5), the number average molecular weight (Mn) = 2,150, the weight average molecular weight (Mw) = 9,571, and the polydispersity (Mw / Mn) = 4.45. .

[Examples 1 to 3, Comparative Examples 1 and 2]
For the novolak resins (1) to (5) synthesized in Synthesis Examples 2 to 4 and Comparative Synthesis Examples 1 and 2, as shown in Table 1, novolak resins and photosensitizers (“P-200” manufactured by Toyo Gosei Co., Ltd.) 1 mol of 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylidene] bisphenol and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride And PGMEA were mixed and dissolved at 28/12/60 (parts by mass), followed by filtration using a 0.2 μm membrane filter to obtain a photosensitive composition. A coating film was prepared using these compositions, and alkali developability, sensitivity, resolution, heat resistance (Tg), substrate followability, and flexibility were evaluated according to the following. The evaluation results are shown in Table 1.

<Alkali developability evaluation>
The photosensitive composition 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 to obtain a silicon wafer having a coating film. The obtained wafer was immersed in an alkali developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a 110 ° C. hot plate for 60 seconds. The film thickness of the coating film of the photosensitive composition was measured before and after immersion in the developer, and the value obtained by dividing the difference by 60 was defined as the evaluation result of alkali developability (ADR (Å / sec)). In the case of exposure, a wafer subjected to PEB (Post Exposure Bake) under conditions of 140 ° C. and 60 seconds after irradiation with 100 mJ / cm ² which is sufficiently exposed with a ghi line lamp (manufactured by USHIO INC., Multi-light). The ADR alkali developability was evaluated. The film thickness of the coating film was measured using a film thickness meter (“f-20” manufactured by Filmetrics Co., Ltd.).

<Sensitivity evaluation>
After adhering a mask corresponding to a 1 to 10 μm resist pattern with a line and space of 1: 1 on a 5 inch silicon wafer having a coating film in which a photosensitive composition is applied to a thickness of about 20 μm and dried, ghi An exposure amount (Eop exposure amount) capable of faithfully reproducing 3 μm with a line lamp was determined.

<Resolution evaluation>
A photomask was placed on a 5-inch silicon wafer having a coating film on which the photosensitive composition had been applied and dried, and the film was exposed to 200 mJ / cm ² with a ghi line lamp (manufactured by Ushio Inc., Multilight). The film after irradiation was developed and dried in the same manner as in <Alkali developability evaluation>. The pattern state of the resist pattern on the wafer after development was evaluated using a laser microscope (VK-X200) manufactured by Keyence Corporation. In the evaluation, “◯” indicates that resolution was achieved at L / S = 5 μm, and “x” indicates that resolution was not possible at L / S = 5 μm.

<Evaluation of heat resistance>
The heat resistance was evaluated by the glass transition temperature (Tg) of the coating film. Specifically, a photosensitive composition is applied onto 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 to form a silicon wafer having a coating film. Obtained. The resin content was scraped from the obtained wafer and the glass transition temperature was measured. The glass transition temperature was measured using a differential scanning calorimeter (DSC) (TA Instruments, product name: Q100) under a nitrogen atmosphere, temperature range: −100 to 200 ° C., temperature rising temperature: 10 ° C. Scanning was performed under the conditions of / min, and the measurement result was taken as the glass transition temperature.

<Substrate following evaluation>
The photosensitive composition was coated on a 5-inch silicon wafer with a spin coater to a thickness of about 50 μm and dried on a hot plate at 110 ° C. for 300 seconds. The presence or absence of cracks on the coating film surface of the obtained wafer was observed using a laser microscope (VK-X200) manufactured by Keyence Corporation. In the evaluation, “◯” indicates that no crack was observed, and “X” indicates that a crack was observed.

<Flexibility>
The photosensitive composition was coated on a polyimide film having a thickness of 50 μm with a spin coater so as to have a thickness of about 5 μm, and dried on a hot plate at 110 ° C. for 300 seconds. The obtained film-like coating film was bent at 180 degrees, and the state of the bent portion was observed using a laser microscope (VK-X200) manufactured by Keyence Corporation. In the evaluation, “◯” indicates that no crack was observed, and “X” indicates that a crack was observed.

As a result, the coating films (Examples 1 to 3) of the photosensitive composition containing the novolak resins (1) to (3), which are novolak type phenol resins according to the present invention, have an ADR of 1600 Å / sec or more after exposure. The alkali developability was good, the sensitivity and resolution were high, the glass transition temperature was sufficiently high at 160 ° C. or higher, the heat resistance was good, and the substrate followability and flexibility were excellent. On the other hand, the coating film (Comparative Example 1) of the photosensitive composition containing the novolak resin (4), which is a novolak-type phenol resin synthesized using only monoaldehydes as the nodule, has an alkali developability and sensitivity. Although the resolution and heat resistance were excellent, the substrate followability and flexibility were inferior. Moreover, the coating film (comparative example 2) of the photosensitive composition containing the novolak resin (5) which is a cresol novolak resin synthesized using polyaldehydes as a nodule is excellent in substrate followability and flexibility. However, alkali developability, sensitivity, resolution, and heat resistance were all insufficient.

Claims (14)

1. The following general formula (1)
   

   

   [In Formula (1), R ¹ , R ² , and R ³ each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent. When a plurality of R ¹ are present, they may be the same or different. When a plurality of R ² are present, they may be the same or different. When a plurality of R ³ are present, May be the same or different. p and q are each independently an integer of 1 to 4, r is an integer of 0 to 4, and s is 1 or 2. However, the sum of r and s is 5 or less. ]
   And a compound represented by the following general formula (2)
   

   

   [In Formula (2), R ¹ , R ² , R ³ , p, and q are the same as those in Formula (1), and t is an integer of 0 to 5. ]
   Obtained by reacting one or more phenolic trinuclear compounds (A), monoaldehydes (B), and polyaldehydes (C) selected from the group consisting of compounds represented by A novolac-type phenolic resin, characterized in that
2. The novolak-type phenol resin according to claim 1, wherein the polyaldehyde (C) is an aliphatic dialdehyde.
3. The novolak type phenol resin according to claim 2, wherein the aliphatic dialdehyde is glutaraldehyde or adipaldehyde.
4. The novolac type phenol resin according to any one of claims 1 to 3, wherein the monoaldehyde (B) is formaldehyde.
5. The amount of the monoaldehydes (B) and the polyaldehydes (C) to be reacted with the phenol trinuclear compound (A) is 1 / 0.01 in a mass ratio [(B) / (C)]. The novolac type phenol resin according to any one of claims 1 to 4, which is ˜1 / 1.5.
6. The phenol trinuclear compound (A) is represented by the following general formulas (1-1), (1-2), (1-7), (1-8), (1-13), (1-14) , (2-1) or (2-2)
   

   

   [Wherein, R ¹ , R ² , and R ³ each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent. A plurality of R ¹ may be the same or different from each other, a plurality of R ² may be the same or different from each other, and when a plurality of R ³ are present, they may be the same or different. May be. r1 represents an integer of 0 to 4, r2 represents an integer of 0 to 3, and t represents an integer of 0 to 5. The novolak type phenol resin according to any one of claims 1 to 5, which is at least one compound selected from the group consisting of compounds represented by formula (I):
7. As a repeating unit, the following general formula (I-1)
   

   

   [In Formula (I-1), R ¹ and R ² are the same as those in Formula (1), and R ⁴ has a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Represents an optionally substituted aryl group. ]
   A structural unit (I-1) represented by the following general formula (I-2)
   

   

   [In Formula (I-2), R ¹ and R ² are the same as in Formula (1), and R ⁴ is the same as in Formula (I-1). ]
   A structural unit (I-2) represented by the following general formula (II-1)
   

   

   [In Formula (II-1), R ¹ and R ² are the same as in Formula (1), and R ⁴ is the same as in Formula (I-1). ]
   A structural unit represented by formula (II-1) and the following general formula (II-2)
   

   

   [In Formula (II-2), R ¹ and R ² are the same as in Formula (1), and R ⁴ is the same as in Formula (I-1). ]
   The novolak type phenol resin according to any one of claims 1 to 5, which has one or more structural sites selected from the group consisting of structural units (II-2) represented by
8. The novolak type phenol resin according to claim 7, wherein both R ¹ and R ² are methyl groups.
9. The structural unit represented by the general formula (I-1) or the structural unit represented by the general formula (II-1) is a repeating unit, and the weight average molecular weight is 5,000 to 25,000. The novolak type phenol resin according to claim 7.
10. The structural unit represented by the general formula (I-2) or the structural unit represented by the general formula (II-2) is a repeating unit, and the weight average molecular weight is 1,000 to 5,000. The novolak type phenol resin according to claim 7.
11. A photosensitive composition comprising the novolac-type phenolic resin according to any one of claims 1 to 10 and a photosensitive agent.
12. A resist material comprising the photosensitive composition according to claim 11.
13. A coating film comprising the photosensitive composition according to claim 11.
14. A resist coating film comprising the resist material according to claim 12.

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