TW201634508A - 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

Phenolic phenol resin, photosensitive composition, resist material, coating film, and resist coating film

The present invention relates to a novolac type phenol resin, a photosensitive composition containing the same, and a photosensitive composition containing the resin, which are excellent in heat resistance, flexibility, alkali developability, sensitivity, and resolution. The resist material obtained and the coating film (resist coating film) using the resist material.

As a resist used for manufacturing semiconductors such as ICs and LSIs, manufacturing of display devices such as LCDs, and printing of original printing plates, it is known to use an alkali-soluble resin and 1,2-diazepine naphthoquinone (1,2- Naphthoquinone diazide) Positive photoresist of sensitizers such as compounds. Specifically, for example, a positive-type photoresist composition using a mixture of a m-cresol novolac resin and a p-cresol novolac resin as the alkali-soluble resin has been proposed (for example, see Patent Document 1).

In recent years, there has been a tendency for higher semiconductor integration and a thinner pattern, and a more excellent sensitivity is required. The positive-type resist composition described in Patent Document 1 has been developed for the purpose of improving developability such as sensitivity, but there is a problem in that it is not possible to obtain sufficient sensitivity for thinning. Further, since various heat treatments are performed in the production steps of semiconductors and the like, higher heat resistance is required. However, the positive-type photoresist composition described in Patent Document 1 has a problem that heat resistance is insufficient.

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

Moreover, in recent years, in the field of semiconductors, higher integration has been promoted. One of the package forms of the highly integrated semiconductor component is a wafer level package. In the wafer level package, an electron chemical deposition method of an electronic wiring described in Non-Patent Document 1 is used as the wiring density is increased. In the wafer level package, in order to form the final metal structure, gold bumps, copper pillars, and copper wires must be re-wiring, but in order to perform the rewiring, a mold for the resist to be electroplated later is required (mold ). This resist (resist layer) is very thick compared to the resist used in the formation of critical layers when manufacturing an IC. Typically, the size of the pattern and the thickness of the resist are as thick as 2 μm to 100 μm, so the photoresist must be patterned with a high aspect ratio (resist thickness relative to the line size). Further, in order to pattern the photoresist with a high aspect ratio, it is necessary to obtain a resist composition of a coating film which is excellent in flexibility even when the film thickness is increased.

In order to obtain a resist coating film which is excellent in flexibility even in a thick film, for example, a resist containing a phenol resin using an aliphatic polyaldehyde as a bridging agent for m-cresol or p-cresol is known. Composition (for example, refer to Patent Document 3).

[Patent Document 1] Japanese Patent Laid-Open No. Hei 2-055359

[Patent Document 2] International Publication No. 2012/141165

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2012-234019

[Non-Patent Document 1] Solomon, "Electrochemically Deposited Solder Bumps for Wafer-Level Packaging, Packaging/Assembly", Solid State Technology, April 2001, p.84~88

However, it is difficult to achieve the heat resistance and the alkali dissolution rate while using the resist coating film obtained by using the resist composition described in Patent Document 3.

An object of the present invention is to provide a novolac type phenol resin which is suitable for use in a coating film which is excellent in flexibility and alkali resistance, alkali developability, sensitivity and resolution even when it is a thick film. A photosensitive composition of the resin, a resist material obtained by using the photosensitive composition, and a coating film (resist coating film) using the resist material.

In order to solve the above problems, the present inventors have conducted intensive studies and found that a phenolic trinuclear compound is used instead of m-cresol or p-cresol, and a monoaldehyde or a polyaldehyde is used as a bridging agent together. The present invention has been completed by obtaining a novolac type phenol resin which is excellent not only in the case of a thick film but also in heat resistance and alkali dissolution rate.

That is, the present invention relates to a novolac type phenol resin characterized in that the novolac type phenol resin is selected from the group consisting of the compound represented by the following formula (1) and the following formula in the presence of an acid catalyst. (2) One or more kinds of phenolic trinuclear compound (A), monoaldehyde (B) and polyaldehyde (C) in the group of compounds shown are reacted to obtain:

In the formula (1), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 8 carbon atoms which may have a substituent; when a plurality of R ¹ are present, the same may be the same Alternatively, when there are a plurality of R ² , the same may be the same or different. When there are multiple R ³ , the same may be the same or different; p and q are each an integer of 1 to 4, respectively. r is an integer from 0 to 4, and s is 1 or 2; wherein the sum of r and s is 5 or less];

In the formula (2), R ¹ , R ² , R ³ , p and q are the same as the above formula (1), and t represents an integer of 0 to 5].

Moreover, the present invention relates to a photosensitive composition, a resist material, a coating film, and a resist coating film, characterized in that the photosensitive composition is characterized by containing the above-described novolac type phenol resin and a photosensitive agent, and the resist material is The coating film is characterized in that it is composed of the above-mentioned photosensitive composition, and the resist coating film is characterized by being composed of the above-mentioned resist material.

According to the phenolic phenol resin of the present invention and the photosensitive composition containing the resin, it is possible to obtain a coating film which is excellent in flexibility even when it is a thick film, and which is excellent in heat resistance, alkali developability, sensitivity, and resolution. Therefore, the photosensitive composition can be used for a resist material.

Fig. 1 is a GPC chart of the phenolic trinuclear compound (1) obtained in Synthesis Example 1.

Fig. 2 is a chart showing the ¹³ C-NMR spectrum of the phenolic trinuclear compound (1) obtained in Synthesis Example 1.

Fig. 3 is a GPC chart of the phenol resin (1) obtained in Synthesis Example 2.

Fig. 4 is a GPC chart of the phenol resin (2) obtained in Synthesis Example 3.

Fig. 5 is a GPC chart of the phenol resin (3) obtained in Synthesis Example 4.

Fig. 6 is a GPC chart comparing the phenol resin (4) obtained in Synthesis Example 1.

Fig. 7 is a GPC chart comparing the phenol resin (5) obtained in Synthesis Example 2.

The novolac type phenol resin of the present invention is characterized in that it is selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2) in the presence of an acid catalyst. One or more kinds of the phenolic trinuclear compound (A), the monoaldehyde (B), and the polyaldehyde (C) are obtained by a reaction. The phenolic trinuclear compound (A) which is a raw material of the novolac type phenol resin of the present invention has a phenolic property on all three benzene rings by an appropriate ratio of the compound represented by the formula (1) a trivalent compound of a hydroxyl group) is combined with a compound represented by the formula (2) (a trinuclear compound composed of two benzene rings having a phenolic hydroxyl group and a benzene ring having no phenolic hydroxyl group), and can be controlled. The amount of hydroxyl groups of the obtained novolac type phenol resin further controls the alkali solubility to a desired level.

In the general formulae (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. Wherein, the sum of r and S is 5 or less. In the formula (2), t is an integer of 0 to 5.

In the general formulae (1) and (2), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 8 carbon atoms which may have a substituent. In the case where a plurality of R ¹ are present, the same may be the same or different. When there are a plurality of R ² , the same may be the same or different. When there are multiple R ³ , the same may be the same. It can also be different.

The alkyl group may be linear or branched, and may also have a cyclic structure, preferably a linear group. In the present invention, the alkyl group as 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 further preferably a linear chain. The alkyl group having 1 to 3 carbon atoms.

The hydrogen atom in the alkyl group of R ¹ , R ² or R ^{3 in} the general formulae (1) and (2) may be substituted with a substituent. The number of hydrogen atoms which may be substituted is not particularly limited, and is preferably 1 to 3, more preferably 1 or 2. Further, when one alkyl group has a plurality of substituents, the substituents may be the same 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, a halogen atom, and the like. In the substituent of the alkyl group, as a carbon Examples of the alkoxy group having 1 to 6 atomic atoms include a methoxy group, an ethoxy group, a propoxy group, a n-butoxy group, a third butoxy group, a pentyloxy group, an isoamyloxy group, and a hexyloxy group. Oxyl, cyclohexyloxy and the like. Further, examples of the aryl group which may have a substituent include a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

Specifically, examples of the alkyl group of R ¹ , R ² and R ^{3 in} the general formulae (1) and (2) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group. Base, tert-butyl, pentyl, isopentyl, hexyl, cyclohexyl, hydroxyethyl, hydroxypropyl, fluoromethyl, methoxyethyl, ethoxyethyl, methoxypropyl, benzene Methyl, hydroxyphenylmethyl, dihydroxyphenylmethyl, tolylmethyl, xylylmethyl, naphthylmethyl, hydroxynaphthylmethyl, dihydroxynaphthylmethyl, phenylethyl , hydroxyphenylethyl, dihydroxyphenylethyl, tolylethyl, xylylethyl, naphthylethyl, hydroxynaphthylethyl, dihydroxynaphthylethyl, preferably methyl, ethyl The group is a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group or a hexyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

R ¹ and R ² in the general formulae (1) and (2) are preferably an alkyl group having the same number of carbon atoms. Further, R ¹ and R ^{2 are} preferably each in the respective benzene rings to which R ¹ and R ² are bonded, and are bonded at the same position as observed from a carbon atom bonded to a phenolic hydroxyl group of the benzene ring. The carbon atom. The benzene ring bonded to R ¹ and the benzene ring bonded to R ² are respectively bonded with a phenolic hydroxyl group. Preferably, the position of the phenolic hydroxyl group is also the same in each benzene ring. Further, p and q are also preferably the same number. As p and q, it is preferably 2.

r in the general formulae (1) and (2) is an integer of 0 to 4. Wherein r is preferably 0.

The compound represented by the above formula (1) is, for example, a compound represented by any one of the following formulae (1-1) to (1-18). In the general formulae (1-1) to (1-18), R ¹ , R ² and R ³ are the same as the above formula (1), r 1 represents an integer of 0 to 4, and r 2 represents an integer of 0 to 3. As the compound represented by the formulae (1-1) to (1-18), a compound wherein R ¹ and R ² are each a methyl group or an ethyl group and r1 and r2 are 0, more preferably R ¹ and R are preferable. ² is a compound in which methyl groups and r1 and r2 are 0.

In the aspect of obtaining the novolac type phenol resin which can obtain a coating film having heat resistance and high resolution, the compound represented by the above formula (1) is preferably a compound of the formula (1-1) or (1-2). a compound represented by (1-7), (1-8), (1-13) or (1-14), more preferably a formula (1-1), (1-7) or (1- The compound shown in 13) is more preferably a compound represented by the formula (1-1).

The compound represented by the above formula (2) is, for example, a compound represented by any one of the following formulae (2-1) to (2-6). In the general formulae (2-1) to (2-6), R ¹ , R ² , R ³ and t are the same as the above formula (2). As the compound represented by the formulae (2-1) to (2-6), a compound wherein R ¹ and R ² are each a methyl group or an ethyl group and t is 0, more preferably R ¹ and R ² are preferable. A compound which is methyl and t is 0.

The compound represented by the above formula (2) is preferably a compound of the formula (2-1) or (2-2) in terms of obtaining a novolac type phenol resin having a coating film having heat resistance and high resolution. The compound shown is more preferably a compound represented by the formula (2-1).

The compound represented by the above formula (1) is obtained, for example, by substituting an alkyl group under the condition that the reactivity of the carbon atom on the aromatic hydrocarbon group of the alkyl-substituted phenol (d1) is poor. The phenol (d1) is condensed with a hydroxyl group-containing aromatic aldehyde (d2). Specifically, for example, the compound represented by the above 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 above formula (2) is obtained, for example, by substituting an alkyl group under the condition that the difference in the reactivity energy of the carbon atom on the aromatic hydrocarbon group of the alkyl-substituted phenol (d1) can be utilized. The phenol (d1) is condensed with an aromatic aldehyde (hydroxyl-free aromatic aldehyde) (d'2) having no hydroxyl group. Specifically, for example, the compound represented by the above formula (1) can be subjected to polycondensation of an alkyl-substituted phenol (d1) and a hydroxyl-free aromatic aldehyde (d'2) in the presence of an acid catalyst. obtain.

The above alkyl-substituted phenol (d1) is bonded to a hydrogen atom on the benzene ring of phenol A compound in which a part or all of it is substituted with an alkyl group. The alkyl group may, for example, be an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group. Examples of the alkyl-substituted phenol (d1) include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, and p-third. Monoalkylphenol such as phenol, o-cyclohexyl phenol, m-cyclohexyl phenol, p-cyclohexyl phenol; 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4 a dialkylphenol such as xylenol or 2,6-xylenol; a trialkylphenol such as 2,3,5-trimethylphenol or 2,3,6-trimethylphenol; and the like. Further, in the alkyl-substituted phenol, in terms of excellent balance between heat resistance and alkali solubility, it is preferred that the number of substitutions of the alkyl group on the benzene ring of phenol is two, and as a specific example, Preferred is 2,5-xylenol or 2,6-xylenol. These alkyl-substituted phenols (d1) may be used alone or in combination of two or more. It is preferred to use only one.

The aromatic aldehyde (d2) having a hydroxyl group is a compound having at least one aldehyde group and at least one hydroxyl group on the aromatic ring. Examples of the hydroxyl group-containing aromatic aldehyde (d2) include hydroxybenzaldehyde such as salicylaldehyde, m-hydroxybenzaldehyde, and p-hydroxybenzaldehyde; 2,4-dihydroxybenzaldehyde and 3,4-dihydroxybenzaldehyde; Dihydroxybenzaldehyde; vanillin-based compounds such as vanillin, o-vanillin, isovanillin, and ethyl vanillin. Among these hydroxyl group-containing aromatic aldehydes (d2), p-hydroxybenzaldehyde (4-hydroxybenzaldehyde) is preferred in terms of ease of industrial availability, excellent balance between heat resistance and alkali solubility. , 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, more preferably p-hydroxybenzaldehyde.

The above-mentioned hydroxyl group-free aromatic aldehyde (d'2) is a compound having at least one aldehyde group on the aromatic ring and having no phenolic hydroxyl group. Examples of the aromatic group-free aromatic aldehyde (d'2) include benzaldehyde; alkylbenzaldehyde such as methylbenzaldehyde, ethylbenzaldehyde, dimethylbenzaldehyde, and diethylbenzaldehyde; An alkoxy benzaldehyde such as oxybenzaldehyde or ethoxybenzaldehyde. Among these non-hydroxyl-containing aromatic aldehydes (d'2), benzaldehyde is preferred.

The compound represented by the above formula (1) or (2) is obtained, for example, by subjecting the above alkyl-substituted phenol (d1) to the above-mentioned aromatic aldehyde having a hydroxyl group (d2) in the presence of an acid catalyst. Or a polyhydroxyl-free aromatic aldehyde (d'2) for polycondensation. For example, R ¹ and R ² in the above formula (1-1) are all methyl groups by polycondensing 2,5-xylenol with 4-hydroxybenzaldehyde in the presence of an acid catalyst. A compound in which r is 0. By polycondensing 2,6-xylenol with 4-hydroxybenzaldehyde in the presence of an acid catalyst, R ¹ and R ² in the above formula (1-2) are all methyl and r is Compound of 0.

Examples of the acid catalyst 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. Further, among these acid catalysts, sulfuric acid and p-toluenesulfonic acid are preferred in terms of excellent activity. The acid catalyst can be added before the reaction or added in the middle of the reaction.

The polycondensation of the above alkyl-substituted phenol (d1) with the above-mentioned aromatic aldehyde (d2) having a hydroxyl group or the aromatic aldehyde (d'2) having no hydroxyl group can also be carried out in the presence of an organic solvent. Examples of the organic solvent include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, Polyethylene 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, B Glycol ether such as diol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether; Alkane, 1,4-two a cyclic ether such as an alkane; a glycol ester such as ethylene glycol acetate; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone. These organic solvents may be used alone or in combination of two or more. Further, in these organic solvents, 2-ethoxyethanol is preferred because the solubility of the obtained compound is excellent.

The reaction temperature at which the alkyl-substituted phenol (d1) and the aromatic aldehyde (d2) having a hydroxyl group or the aromatic aldehyde (d'2) having no hydroxyl group are polycondensed is, for example, 60 to 140 °C. Further, the reaction time is, for example, 0.5 to 100 hours.

The addition ratio [(d1)/(d2)] of the above alkyl-substituted phenol (d1) to the above-mentioned aromatic aldehyde (d2) containing a hydroxyl group, and the above-mentioned alkyl-substituted phenol (d1) and the above-mentioned aromatic aldehyde having no hydroxyl group The addition ratio of (d'2) [(d1)/(d'2)] is excellent in the removability of the unreacted alkyl-substituted phenol (d1), the yield of the product, and the purity of the reaction product. In other words, the molar 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.

There is a possibility that a polycondensate remains in a reaction solution of polycondensation of the above alkyl-substituted phenol (d1) with the above-mentioned aromatic aldehyde (d2) having a hydroxyl group or aromatic aldehyde (d'2) having no hydroxyl group. The compound and the unreacted product are represented by the above formula (1) or (2). Further, there is a possibility that a condensate other than the compound represented by the above formula (1) or (2) is formed. Therefore, it is preferred to use the reaction solution after the polycondensation reaction in advance to refine the above-described general formula (1) or (2) before use as a raw material (phenolic trinuclear compound (A)) of the novolac type phenol resin of the present invention. Compound. The purity of the compound represented by the above formula (1) or (2) used as the phenolic trinuclear compound (A) is preferably 85% or more, more preferably 90% or more, still more preferably 94% or more. Particularly good is 98% or more. The purity of the compound represented by the formula (1) or (2) can be determined from the area ratio in the GPC chart.

The method of purifying the compound represented by the formula (1) or (2) to improve the purity is, for example, a method in which the reaction solution after the polycondensation reaction is introduced into the formula (1) or (2). A poor solvent (S1) in which the compound is insoluble or poorly soluble is obtained to obtain a precipitate, and the obtained precipitate is separated by filtration, and then the obtained precipitate is dissolved until the compound represented by the formula (1) or (2) is dissolved and also The solvent (S2) mixed in the poor solvent (S1) is again introduced into the poor solvent (S1) to cause a precipitate, and the resulting precipitate is separated by filtration. Examples of the poor solvent (S1) used at this time include water; monoalcohols such as methanol, ethanol, and propanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohexane; toluene and xylene. An aromatic hydrocarbon. In the case of the poor solvent (S1), it is preferred to remove the acid catalyst at the same time, and water or methanol is preferred. On the other hand, examples of the solvent (S2) include monools such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol 1,3-propanediol, and 1,4-butanediol; 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,3-propanediol, 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 monopentyl ether, Glycol ether such as ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether; Alkane, 1-4-two a cyclic ether such as an alkane; a glycol ester such as ethylene glycol acetate; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone. Further, when water is used as the poor solvent (S1), the above (S2) is preferably acetone. In addition, the poor solvent (S1) and the solvent (S2) may be used alone or in combination of two or more.

In the phenolic trinuclear compound (A), one or two or more compounds represented by the formula (1) may be used as the raw material of the phenolic phenol resin of the present invention, and one type or two or more types may be used. In the compound represented by the formula (2), one or two or more compounds represented by the formula (1) and one or two or more compounds represented by the formula (2) may be used. By adjusting the phenolic system The ratio of the compound represented by the formula (1) to the compound represented by the formula (2) in the trinuclear compound (A) can adjust the hydroxyl group content of the obtained novolac type phenol resin. For example, the larger the ratio of the compound represented by the formula (1) in the phenolic trinuclear compound (A), the more the hydroxyl group is, and the novolac type phenol resin having high alkali solubility is obtained. On the other hand, the lower the ratio of the compound represented by the formula (2) in the phenolic trinuclear compound (A), the smaller the hydroxyl group, and the novolac type phenol resin having low alkali solubility.

As the monoaldehyde (B) used as a raw material of the novolac type phenol resin of the present invention, for example, a compound represented by the following formula (3) can be used. In the formula (3), R ⁴ represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. Further, the monoaldehyde (B) used as a raw material may be one type of compound, or two or more types of compounds may be used in combination.

R ⁴ -CHO (3)

Among the compounds represented by the above formula (3), preferred are formaldehyde; alkyl aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, and hexanal; salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde and other hydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde , 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-hydroxy-3,5-dimethoxybenzene Benzaldehyde having a hydroxyl group and an alkoxy group such as formaldehyde; alkoxy benzaldehyde such as methoxybenzaldehyde or ethoxybenzaldehyde; 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, a hydroxynaphthalene formaldehyde such as 6-hydroxy-2-naphthaldehyde or a halogenated benzaldehyde such as bromobenzaldehyde, more preferably formaldehyde or an alkyl aldehyde, further preferably formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, Valeraldehyde or hexanal, particularly preferably formaldehyde. When formaldehyde is used as the monoaldehyde (B), formaldehyde can also be used. Other aldehydes are used in combination. When formaldehyde is used in combination with other aldehydes, the amount of other aldehydes used is preferably in the range of 0.05 to 1 mol per mol of formaldehyde.

The polyaldehyde (C) used as a raw material of the novolac type phenol resin of 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 the polyaldehyde (C) include aliphatic dialdehydes such as glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, and adipaldehyde; o-phthalaldehyde and isophthalaldehyde; An aromatic dialdehyde such as terephthalaldehyde; an aliphatic trialdehyde such as trimethylmethane; an aromatic trialdehyde such as benzenetrialdehyde; and the like. Among them, as the polyaldehyde (C), it is easy to obtain, and in terms of a novolac type phenol resin which can obtain higher heat resistance, terephthalaldehyde or glutaraldehyde is preferable. The polyaldehyde (C) used as a raw material may be one type of compound, or two or more types of compounds may be used in combination.

The novolac type phenol resin of the present invention is obtained, for example, by condensing a phenolic trinuclear compound (A), a monoaldehyde (B), and a polyaldehyde (C) in the presence of an acid catalyst. The addition ratio [(A)/(B)] of the phenolic trinuclear compound (A) to the monoaldehyde (B) suppresses excessive polymerization (gelation) and obtains a material as a coating film. In terms of the appropriate molecular weight, it is preferably in the range of from 1/0.5 to 1/1.2 in terms of molar ratio, more preferably in the range of from 1/0.6 to 1/0.9. Further, the addition ratio (usage amount) [(B)/(C)] of the monoaldehyde (B) and the polyaldehyde (C) which are reacted with the phenolic trinuclear compound (A) is preferably in terms of mass ratio It is in the range of 1/0.01 to 1/1.5, more preferably in the range of 1/0.05 to 1/1.2.

Examples of the acid catalyst used for 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, oxalic acid, and butyl. An organic acid such as diacid, malonic acid, monochloroacetic acid or dichloroacetic acid, or a Lewis acid such as boron trifluoride, anhydrous aluminum chloride or zinc chloride. Among them, it shows strong acidity and The high activity-promoting reaction of the phenolic trinuclear compound (A), the monoaldehyde (B) and the polyaldehyde (C) is preferably sulfuric acid or p-toluenesulfonic acid. The amount of the acid catalyst to be used is preferably in the range of 0.1 to 25% by mass based on the total mass of the reaction raw material.

The condensation reaction of the phenolic trinuclear compound (A), the monoaldehyde (B), and the polyaldehyde (C) can also be carried out in the presence of an organic solvent as needed. The organic solvent may be the same as the organic solvent which can be used in the polycondensation of the above-mentioned alkyl-substituted phenol (d1) and the above-mentioned aromatic aldehyde (d2) having a hydroxyl group. These organic solvents may be used alone or in combination of two or more. Further, in view of excellent solubility of the obtained novolac type phenol resin, 2-ethoxyethanol is preferable as the organic solvent.

The phenolic phenol resin of the present invention preferably has a structural unit selected from the structural unit (I-1) represented by the following general formula (I-1) and the following general formula (I-2). (I-2), a structural unit (II-1) represented by the following general formula (II-1), and a structural unit (II-2) represented by the following general formula (II-2) One or more structural parts are used as a repeating unit. In the general formulae (I-1), (I-2), (II-1) and (II-2), R ¹ and R ² are the same as the above formula (1), and R ⁴ and the above formula (3) )the same. As a structural unit represented by the formula (I-1), (I-2), (II-1) or (II-2), it is preferred that both R ¹ and R ² are the same group and R ⁴ is hydrogen. More preferably, both of R ¹ and R ² are unsubstituted alkyl having 1 to 3 carbon atoms and R ⁴ is a hydrogen atom, and further preferably R ¹ and R ² are both methyl and R. ⁴ is a hydrogen atom.

The weight average molecular weight of the novolac type phenol resin of the present invention is preferably from 1,000 to 100,000, more preferably from 1,000 to 70,000, still more preferably from 1,000 to 35,000. When the molecular weight of the novolac type phenol resin having the structural unit represented by the above formula (I-1) or the structural unit represented by the above formula (II-1) as a repeating unit is obtained, a phenol type which is more excellent in heat resistance can be obtained. The phenol resin is preferably 5,000 to 100,000, more preferably 5,000 to 70,000, still more preferably 5,000 to 35,000, particularly preferably 5,000 to 25,000, in terms of weight average molecular weight (Mw). Further, the molecular weight of the novolac type phenol resin having the structural unit of the above formula (I-2) or the structural unit represented by the above formula (II-2) as a repeating unit can obtain a novolac type phenol resin which is more excellent in heat resistance. In terms of the weight average molecular weight (Mw), it is preferably from 1,000 to 5,000, more preferably from 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 novolac type phenol resin are determined by gel permeation chromatography (hereinafter, abbreviated as "GPC") under the following measurement conditions. Measured.

[Measurement conditions for GPC]

Measuring device: "HLC-8220GPC" manufactured by Dong Chu Co., Ltd.

Pipe column: "Shodex KF802" (8.0mmI.D.×300mm) manufactured by Showa Denko Co., Ltd. + "Shodex KF802" (8.0mmI.D.×300mm) manufactured by Showa Denko Co., Ltd. + Showa Denko Co., Ltd. "Shodex KF803" (8.0mmI.D.×300mm) manufactured by Showa Denko Co., Ltd. and "Shodex KF804" (8.0mmI.D.×300mm) manufactured by Showa Denko Co., Ltd.

Column temperature: 40 ° C

Detector: RI (differential refractometer)

Data Processing: "GPC-8020 Type II Version 4.30" manufactured by Dong Chu Co., Ltd.

Developing solvent: tetrahydrofuran

Flow rate: 1.0 mL / min

Sample: a solution obtained by filtering a tetrahydrofuran solution having a resin solid content of 0.5% by mass using a microfilter

Injection volume: 0.1mL

Standard sample: monodisperse polystyrene described below

(Standard sample: monodisperse polystyrene)

"A-500" manufactured by Dong Chu Co., Ltd.

"A-2500" manufactured by Dong Chu Co., Ltd.

"A-5000" manufactured by Dong Chu Co., Ltd.

"F-1" manufactured by Dongchu Co., Ltd.

"F-2" manufactured by Dong Chu Co., Ltd.

"F-4" manufactured by Dong Chu Co., Ltd.

"F-10" manufactured by Dong Chu Co., Ltd.

"F-20" manufactured by Dong Chu Co., Ltd.

The novolac type phenol resin of the present invention can be used for applications of various electrical and electronic members such as an adhesive, a paint, a photoresist, and a printed wiring board. In particular, the novolak type phenol resin of the present invention has excellent balance of flexibility, heat resistance, and alkali solubility, and is excellent in substrate tracking. Therefore, the novolac type phenol resin of the present invention is preferable as a resist material, particularly a resist material for a thick film. By using the novolac type phenol resin of the present invention, a photosensitive composition which is suitable as a thick film resist can be obtained which has sensitivity, resolution, heat resistance, substrate followability, and flexibility.

The photosensitive composition of the present invention is characterized in that it contains a photosensitive agent in addition to the novolac type phenol resin of the present invention. As the sensitizer, for example, when the photosensitive composition of the present invention is used as a positive resist material, a compound having a quinonediazide group may be mentioned. In the case where the photosensitive composition of the present invention is used as a negative resist material, a photoacid generator or the like may be mentioned.

Specific examples of the compound having the above quinone diazide group include, for example, an aromatic (poly)hydroxy compound and naphthoquinone-1,2-diazide-5-sulfonic acid, naphthalene. a complete ester compound, a partial ester compound, a amide or a partial guanamine of a sulfonic acid having a quinonediazide group such as 醌-1,2-diazido-4-sulfonic acid or o-quinonediazidesulfonic acid Compounds, etc. These sensitizers may be used alone or in combination of two or more.

The above aromatic (poly) hydroxy compound used herein may, for example, be 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-three. Hydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxy Benzene, 2,2',4,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 2,2',3,4,4 ' - pentahydroxybenzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2, Polyhydroxybenzophenone compounds such as 3,3',4,4',5'-hexahydroxybenzophenone; bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-tri) 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]ethylidene}bisphenol, 3,3'-dimethyl-{1-[4-[2-(3- Bis[polyhydroxyphenyl]alkane compounds such as -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- Tris(hydroxyphenyl) such as dimethylphenyl)-3,4-dihydroxyphenylmethane or bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane Methane Compound or its methyl substitute; bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane , bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis ( 5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, Bis(3-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, double (5 -cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, double (3-ring Hexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4- Bis(cyclohexylhydroxyphenyl)(hydroxybenzene) such as methylphenyl)-2-hydroxyphenylmethane or bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane a methane compound or a methyl substituent thereof or the like.

In the case where a compound having a quinonediazide group is used as the sensitizer of the photosensitive composition of the present invention, the blending amount thereof is a composition excellent in light sensitivity, and is preferably relative to the present invention. When the photosensitive composition of the present invention contains a resin component, the solid content of the entire resin component of the novolac type phenol resin of the present invention is 100 parts by mass, and the ratio is 5 to 50 parts by mass. Jia is a ratio of 5 to 30 parts by mass.

Examples of the photoacid generator include an onium salt compound, a halogen-containing compound, a ruthenium compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound.

Examples of the onium salt compound include a phosphonium salt, a phosphonium salt, a phosphonium salt, a diazonium salt, and a pyridinium salt. Specific examples of the preferred onium salt include diphenylsulfonium trifluoromethanesulfonate, diphenylphosphonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, and diphenylsulfonium hexafluorophosphate. Salt, diphenylphosphonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, (4-t-butylbenzene) Diphenylphosphonium trifluoromethanesulfonate, (4-t-butylphenyl)diphenylphosphonium p-toluenesulfonate, 4,7-di-n-butoxynaphthyltetrahydrothiophene 4,7-di-n-butoxy-naphthyl tetrahydrothiophenium trifluoromethanesulfonate.

Examples of the halogen-containing compound include a hydrocarbon compound containing a halogenated alkyl group and a heterocyclic compound containing a halogenated alkyl group. Specific examples of the preferable halogen-containing compound include 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, and benzene. Base-bis(trichloromethyl)-symmetric three 4-methoxyphenyl-bis(trichloromethyl)-symmetric three Styryl-bis(trichloromethyl)-symmetric three Naphthyl-bis(trichloromethyl)-symmetric three Isometric three derivative.

Examples of the ruthenium compound include a β-ketosulphone compound, a β-sulfonyl oxime compound, and an α-diazo compound of the compound. Specific examples of the preferred hydrazine compound include 4-trityl hydrazine methyl hydrazine, 2,4,6-trimethylphenyl fluorenylmethyl hydrazine, and bis(benzhydrylmethylsulfonyl) methane.

Examples of the sulfonic acid compound include alkylsulfonates, haloalkylsulfonates, arylsulfonates, and iminosulfonates. Specific examples of the preferred sulfonic acid compound include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, and o-nitrobenzyltrifluoromethanesulfonic acid. O-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl p-toluenesulfonate.

Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy) succinimide (N-(trifluoromethylsulfonyloxy) succinimide) and N-(trifluoromethylsulfonyloxy) N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenyl maleimide, N-( N-(trifluoromethylsulfonyloxy)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.

In the case where a photoacid generator is used as the sensitizer of the photosensitive composition of the present invention, the blending amount thereof is a composition excellent in light sensitivity, and it is preferably a phenolic phenol resin relative to the present invention. (In the case where the photosensitive composition of the present invention contains another resin component, 100 parts by mass of the solid component of the entire resin component of the novolac type phenol resin of the present invention) is 5 to 50 parts by mass, more preferably 5 ~30 parts by mass ratio.

The photosensitive composition of the present invention may further contain an organic base compound for neutralizing an acid generated from the photoacid generator upon exposure. The addition of the organic base compound has an effect of preventing the dimensional change of the resist pattern due to the movement of the acid generated from the photoacid generator. The organic base compound used herein may, for example, be an organic amine compound selected from nitrogen-containing compounds. Specific examples thereof include pyrimidine, 2-aminopyrimidine, 4-aminopyrimidine, 5-aminopyrimidine, 2,4-diaminopyrimidine, 2,5-diaminopyrimidine, 4,5-di Aminopyrimidine, 4,6-diaminopyrimidine, 2,4,5-triaminopyrimidine, 2,4,6-triaminopyrimidine, 4,5,6-triaminopyrimidine, 2,4, 5,6-tetraaminopyrimidine, 2-hydroxypyrimidine, 4-hydroxypyrimidine, 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-methoxypyrimidine, 2-amino-4,5-dimethoxypyrimidine, 2-amino-4,6-dimethoxy Pyrimidine, 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-2,6-dimethoxypyrimidine, etc. a pyrimidine compound; a pyridine compound such as pyridine, 4-dimethylaminopyridine or 2,6-lutidine; diethanolamine, triethanolamine, triisopropanolamine, tris(hydroxymethyl)aminomethane, bis ( An amine compound substituted with a hydroxyalkyl group having 1 or more carbon atoms and 4 or less carbon atoms such as 2-hydroxyethyl)imidotris(hydroxymethyl)methane; 2-aminophenol, 3-aminophenol, 4 An aminophenol compound such as an aminophenol or the like. 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 hydroxyl group is preferable from the viewpoint of excellent dimensional stability of the resist pattern after exposure, and particularly preferably an amine compound having a hydroxyl group.

In the case where the above organic base compound is added, the amount thereof is preferably in the range of 0.1 to 100 mol%, more preferably 1 to 50 mol%, based on the content of the photoacid generator.

In addition to the novolac type phenol resin of the present invention, the photosensitive composition of the present invention may be used in combination with other resins as a resin component. The other resin is preferably one which is soluble in an alkali developer or which is dissolved in an alkali developer (alkali-soluble resin) by use in combination with an additive such as a photoacid generator.

Examples of the other resin used herein include an addition polymerization resin of an alicyclic diene compound such as dicyclopentadiene and a phenol compound, a phenolic hydroxyl group-containing compound, and an alkoxy group-containing aromatic compound. Modified phenolic resin, phenol aralkyl resin (ZYLOCK resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylolethane resin, biphenyl modified phenol resin, biphenyl modification Naphthol resin, amine base Modification of phenol resin and various vinyl polymers.

More specifically, the above various phenol resins may be exemplified by an alkylphenol such as phenol, cresol or xylenol, phenylphenol, resorcin, biphenyl, bisphenol A or a double in the presence of an acid catalyst. A polymer obtained by reacting a phenolic hydroxyl group-containing compound such as phenol F, naphthol or dihydroxynaphthalene with an aldehyde compound.

Examples of the above various vinyl polymers include polyhydroxystyrene, polystyrene, polyvinyl naphthalene, polyvinyl anthracene, polyvinylcarbazole, polyfluorene, polyfluorene, polydecene, polyfluorene. A homopolymer of a vinyl compound such as an alkene, a polytetracyclododecene, a poly-nortricyclene or a poly(meth)acrylate or a copolymer of the same.

In the case of using the above other resin, the blending ratio of the novolac type phenol resin of the present invention to other resins can be arbitrarily adjusted depending on the intended use. In view of the effect of the phenolic phenol resin of the present invention, the phenolic phenol of the present invention is preferably 60% by mass or more based on the total of the novolak type phenol resin of the present invention and other resins. The resin is preferably used in an amount of 80% by mass or more.

The photosensitive composition of the present invention may contain a surfactant in order to improve film formability or pattern adhesion when used in a resist application, and to reduce development defects and the like. The surfactant used herein may, for example, be a polyoxyethylene alkyl ether compound such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether or polyoxyethylene oleyl ether, or polyoxyethylene octyl group. a polyoxyethylene alkyl allyl ether compound such as a phenol ether or a polyoxyethylene nonylphenol ether, a polyoxyethylene-polyoxypropylene block copolymer, a sorbitan monolaurate, a sorbitan monopalmitate, mountain Sorbitan fatty acid ester compound such as sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolauric Polyester, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate a nonionic surfactant such as an oxyethylene sorbitan fatty acid ester compound; a copolymer of a fluoroaliphatic group-containing polymerizable monomer and [poly(oxyalkylene)] (meth) acrylate; A fluorine-based surfactant having a fluorine atom in a molecular structure; a polyfluorene-based interfacial activity profile having a polyfluorene structure in a molecular structure. These may be used alone or in combination of two or more. The blending amount of the surfactant is preferably 0.001 to 2 parts by mass based on 100 parts by mass of the resin solid content (containing the novolac type phenol resin of the present invention as a resin solid content) in the photosensitive composition of the present invention. Range used.

The photosensitive composition of the present invention may further contain a filler. The hardness or thermal decomposition resistance of the coating film can be improved by the filler. The filler contained in the photosensitive composition of the present invention may be an organic filler, preferably an inorganic filler. Examples of the inorganic filler include cerium oxide, mica, talc, clay, bentonite, montmorillonite, kaolinite, ash stone, calcium carbonate, calcium hydroxide, magnesium carbonate, titanium oxide, aluminum oxide, and hydroxide. Aluminum, barium sulfate, barium titanate, potassium titanate, zinc oxide, glass fiber, and the like. Among them, cerium oxide is preferably used since the coefficient of thermal expansion can be lowered.

The photosensitive composition of the present invention may further contain a curing agent. Examples of the curing agent contained in the photosensitive composition of the present invention include a melamine compound and a guanamine compound which are substituted with at least one selected from the group consisting of a methylol group, an alkoxymethyl group and a decyloxymethyl group. , an acetylene urea compound, a urea compound, a resole resin, an epoxy compound, an isocyanate compound, an azide compound, a compound containing a double bond such as an alkenyl ether group, an acid anhydride, An oxazoline compound or the like.

Examples of the melamine compound include a compound obtained by methoxymethylation of hexamethylenemethyl melamine, hexamethoxymethyl melamine, and hexamethylol melamine with 1 to 6 methylol groups, and hexamethoxy group. A compound obtained by methylating a methoxy group of 1 to 6 methylol groups of ethyl melamine, hexamethoxymethyl melamine or hexamethylol melamine.

Examples of the above guanamine compound include tetrahydroxymethyl decylamine, tetramethoxymethyl decylamine, and tetramethoxymethyl benzoquinone. a compound obtained by methoxymethylation of 1 to 4 methylol groups of tetramethylolamine, tetramethoxyethylguanamine, tetradecyloxyguanamine, tetrahydroxymethylamine A compound obtained by methylation of 1 to 4 methylol groups with a hydroxy group.

As the acetylene urea compound, for example, 1,3,4,6-tetrakis(methoxymethyl)acetylene urea, 1,3,4,6-tetrakis(butoxymethyl)acetylene urea, 1, 3,4,6-tetrakis(hydroxymethyl)acetylene urea 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-tetrazole (A). Oxymethyl) urea and the like.

Examples of the resole phenol resin include alkylphenol such as phenol, cresol or xylenol, phenylphenol, resorcin, biphenyl, bisphenol A or bisphenol in the presence of a basic catalyst. A polymer obtained by reacting a compound containing a phenolic hydroxyl group such as bisphenol, naphthol or dihydroxynaphthalene with an aldehyde compound.

Examples of the epoxy compound include tris (2,3-epoxypropyl) isocyanurate, trimethylol methane triglycidyl ether, and trimethylolpropane tricyclic ring. Oxypropyl ether, trishydroxyethylethane triglycidyl ether, and the like.

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

Examples of the above azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, and 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-propylene glycol divinyl ether, and 1,4-butanediol divinyl ether. Ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, neopentyl Tetrahydrin trivinyl ether, neopentyl alcohol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether and the like.

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

Among these, an acetylene urea compound, a urea compound, and an acetylene urea compound and a urea compound are preferable in terms of a composition which is excellent in curability and is excellent in dry etching resistance and thermal decomposition resistance when used in a resist underlayer film application. Resole phenolic resin, particularly preferably acetylene urea compound.

In the case where the photosensitive composition of the present invention contains the above-mentioned curing agent, in order to maintain the excellent sensitivity obtained by the novolac type phenol resin of the present invention, the amount of the curing agent blended is 100 parts by mass relative to the novolac type phenol resin of the present invention. It is 50 parts by mass or less. The blending amount of the above-mentioned curing agent in the photosensitive composition of the present invention is preferably a composition of a film which is excellent in curability, thermal decomposition resistance, and alkali developability, and is preferably a phenol type relative to the present invention. Phenolic resin 100 The amount of the component is from 0.1 to 50 parts by mass, and further, it is preferably a ratio of 0.1 to 30 parts by mass, and more preferably 0.5, in terms of a composition of a film excellent in light sensitivity. ~20 parts by mass ratio.

The photosensitive composition of the present invention is preferably obtained by dissolving or dispersing various additives such as a dye, a pigment, a crosslinking agent, and a dissolution promoter in an organic solvent as needed. A coating film can be formed by applying a resultant dissolved in an organic solvent or the like to a substrate or the like. The dye, the pigment, the crosslinking agent, and the dissolution promoter can be appropriately selected from those widely used as additives for the resist material in consideration of the use or the like for use.

Examples of the organic solvent include alkylene glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether. Alkyl ether; diethylene glycol dialkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; ethylene glycol single Alkyl glycol alkyl ether acetate such as methyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, cyclohexanone, methyl pentyl Ketone compounds such as ketones; Alkane and other cyclic ether; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl oxyacetate, 2- Methyl hydroxy-3-methylbutanoate, butyl 3-methoxyacetate, butyl 3-methyl-3-methoxyacetate, ethyl formate, ethyl acetate, butyl acetate, ethyl acetate An ester compound such as an ester or ethyl acetate. These may be used alone or in combination of two or more.

The photosensitive composition of the present invention can be produced by blending the above components and mixing them using a stirrer or the like. Further, when the photosensitive composition contains a filler or a pigment, it may be prepared by dispersing or mixing using a dispersing device such as a dispersing mixer, a homogenizer or a three-roll mill.

The photosensitive composition of the present invention can be preferably used as a resist material. The photosensitive composition of the present invention can be directly used as a resist material in a state of being dissolved or dispersed in an organic solvent, or can be applied to a film in a state of being dissolved or dispersed in an organic solvent to be subjected to solvent removal. The resultant was used as a resist film. The support film used as the resist film may be a synthetic resin film such as polyethylene, polypropylene, polycarbonate, or polyethylene terephthalate, and may be a single layer film or a laminated film of a plurality of films. . Further, the surface of the support film may be a corona treatment or a release agent.

In the photolithography method using the photosensitive composition of the present invention, for example, a photosensitive composition (resist material) dissolved and dispersed in an organic solvent is applied onto a target of a photolithography method on a tantalum substrate, and is 60. Pre-baking at a temperature of ~150 °C. The coating method at this time may be any one of spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, and the like. Next, when a resist pattern is formed, when the photosensitive composition is a positive type, the target resist pattern is exposed by a specific mask, and the exposed portion is dissolved by an alkali developing solution, thereby forming a resist. Agent pattern. Since the photosensitive composition of the present invention has high light sensitivity, it is possible to form a resist pattern having excellent resolution.

Examples of the exposure light source herein include infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray, and electron beam. Examples of the ultraviolet light include g-ray (wavelength 436 nm) and h-ray (wavelength 405 nm) of a high-pressure mercury lamp. I-ray (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), EUV laser (wavelength 13.5 nm), and the like. Since the photosensitive composition of the present invention has high light sensitivity and alkali developability, a resist pattern can be produced with high resolution when any light source is used.

Film thickness of the coating film formed by the photosensitive composition (resist material) of the present invention It can be arbitrarily adjusted according to the intended use. In the case of forming a thick film, the effect of forming a coating film which is excellent in flexibility without sacrificing heat resistance or alkali solubility, which is obtained from the novolac type phenol resin of the present invention, is also sufficiently exhibited. The film thickness is preferably from 100 nm to 100 μm, more preferably from 500 nm to 100 μm, still more preferably from 2 to 100 μm, still more preferably from 2 to 20 μm.

[Examples]

Hereinafter, the present invention will be further described by way of examples and the like, but the present invention is not limited to the examples and the like. In the following, "parts" and "%" are quality standards unless otherwise specified.

<GPC measurement of resin>

The molecular weight distribution of the resin was measured by GPC in the polystyrene standard method according to the following measurement conditions.

(GPC measurement conditions)

Measuring device: "HLC-8220 GPC" manufactured by Dong Chu Co., Ltd.

Pipe column: "Shodex KF802" (8.0mmI.D.×300mm) manufactured by Showa Denko Co., Ltd. + "Shodex KF802" (8.0mmI.D.×300mm) manufactured by Showa Denko Co., Ltd. + Showa Denko Co., Ltd. "Shodex KF803" (8.0mmI.D.×300mm) manufactured by Showa Denko Co., Ltd. and "Shodex KF804" (8.0mmI.D.×300mm) manufactured by Showa Denko Co., Ltd.

Detector: RI (differential refractometer)

Measurement conditions: column temperature 40 ° C

Developing solvent Tetrahydrofuran (THF)

Flow rate 1.0mL / min

Sample: 1.0% by mass of tetrahydrofuran in terms of resin solid content by a microfilter The solution was filtered (5 μL)

Data Processing: "GPC-8020 Type II Data Analysis Version 4.30" manufactured by Dong Chu Co., Ltd.

Standard sample: The following monodisperse polystyrene having a known molecular weight is used in accordance with the measurement guide of "GPC-8020 Type II Data Analysis Version 4.30" above.

(monodisperse polystyrene)

"A-500" manufactured by Dong Chu Co., Ltd.

"A-1000" manufactured by Dong Chu Co., Ltd.

"A-2500" manufactured by Dong Chu Co., Ltd.

"A-5000" manufactured by Dong Chu Co., Ltd.

"F-1" manufactured by Dongchu Co., Ltd.

"F-2" manufactured by Dong Chu Co., Ltd.

"F-4" manufactured by Dong Chu Co., Ltd.

"F-10" manufactured by Dong Chu Co., Ltd.

"F-20" manufactured by Dong Chu Co., Ltd.

"F-40" manufactured by Dong Chu Co., Ltd.

"F-80" manufactured by Dongchu Co., Ltd.

"F-128" manufactured by Dongchu Co., Ltd.

"F-288" manufactured by Dong Chu Co., Ltd.

"F-550" manufactured by Dong Chu Co., Ltd.

< ¹³ C-NMR Spectroscopy of Resin>

The measurement of the ¹³ C-NMR spectrum of the resin was carried out by analyzing the DMSO-d ₆ solution of the sample using "JNM-LA300" manufactured by JEOL Ltd., and analyzing the structure. Hereinafter, the measurement conditions of the ¹³ C-NMR spectrum are shown.

( ¹³ C-NMR spectral measurement conditions)

Measurement mode: SGNNE (1H complete decoupling method to eliminate NOE)

Pulse angle: 45 ° C pulse

Sample concentration: 30wt%

Cumulative number: 10,000 times

[Synthesis Example 1] <Synthesis of phenolic trinuclear compound>

2,5-xylenol 293.2 g (2.4 mol) of 4-hydroxybenzaldehyde 122 g (1 mol) and 2-ethoxyethanol 500 mL were added to a four-necked flask equipped with a cooling tube of 2 L. 2,5-xylenol and 4-hydroxybenzaldehyde were dissolved in 2-ethoxyethanol. Then, while cooling in an ice bath, 10 mL of sulfuric acid was added to the reaction solution in the four-necked flask, followed by heating at 100 ° C for 2 hours in a heating mantle, and stirring was carried out while reacting. Water was added to the reaction solution after completion of the reaction to carry out a reprecipitation operation, thereby obtaining a crude product. After the crude product was redissolved to acetone, the reprecipitation operation was carried out using water. The product obtained by the reprecipitation operation was subjected to filtration separation and vacuum drying to obtain 213 g of a precursor compound (phenolic trinuclear compound (1)) as a white crystal. GPC and ¹³ C-NMR spectrum measurement of the phenolic trinuclear compound (1) confirmed that it was a target compound, and the purity was 98.2% by mass in terms of the area ratio of GPC. The graph of GPC of the phenolic trinuclear compound (1) is shown in Fig. 1, and the graph of ¹³ C-NMR spectrum is shown in Fig. 2.

[Synthesis Example 2] <Synthesis of phenolic phenol resin>

Addition to Synthesis Example 1 was carried out in a four-necked flask having a capacity of 300 mL in which a cooling tube was attached. Phenolic trinuclear compound (1) 34.8 g (0.1 mol), 50% glutaraldehyde 8.0 g (0.04 mol), 2-ethoxyethanol 15 mL, and acetic acid 15 mL in 2-ethoxyethanol and acetic acid The phenolic trinuclear compound (1) and glutaraldehyde are dissolved in the mixed solvent. Then, while cooling in an ice bath, 10 mL of sulfuric acid was added to the reaction solution in the four-necked flask, followed by addition of 92% paraformaldehyde (3.0 g (0.09 mol)), and the temperature was raised to 80 ° C in an oil bath. After heating for 10 hours, the reaction was carried out while stirring. Water was added to the reaction solution after completion of the reaction to carry out a reprecipitation operation, thereby obtaining a crude product. After the crude product was redissolved in acetone, the reprecipitation operation was carried out using water. The product obtained by the reprecipitation operation was subjected to filtration separation, and vacuum-dried to obtain 32.9 g of a red powder of a novolac type phenol resin (phenolic resin (1)). The GPC chart of the phenol resin (1) is shown in Fig. 3. GPC was carried out on the phenol resin (1), and the number average molecular weight (Mn) was 2,051, the weight average molecular weight (Mw) was 7,855, and the polydispersity (Mw/Mn) was 3.83.

[Synthesis Example 3] <Synthesis of phenolic phenol resin>

31.3 g of a red powder novolak type phenol resin (phenolic resin (2)) was obtained in the same manner as in Synthesis Example 2 except that the amount of the glutaraldehyde was changed to 4.0 g (0.02 mol). The GPC chart of the phenol resin (2) is shown in Fig. 4. GPC of the phenol resin (2) showed a number average molecular weight (Mn) = 1,889, a weight average molecular weight (Mw) = 6,721, and a polydispersity (Mw/Mn) = 3.56.

[Synthesis Example 4] <Synthesis of phenolic phenol resin>

A red powder of a novolac type phenol resin (phenolic resin (3)) (34.1 g) was obtained in the same manner as in Synthesis Example 2 except that the amount of the glutaraldehyde was changed to 20.0 g (0.1 mol). The GPC chart of the phenol resin (3) is shown in Fig. 5. GPC of the phenol resin (3), the number average molecular weight (Mn) = 1,504, weight average molecular weight (Mw) = 5,412, polydispersity (Mw /Mn) = 3.60.

[Comparative Synthesis Example 1] Synthesis of <(non-soft) phenolic phenol resin>

To the four-necked flask having a capacity of 300 mL in which a cooling tube was attached, a phenolic trinuclear compound (1) obtained in Synthesis Example 1 (1) (17.4 g (0.05 mol), and 92% paraformaldehyde 1.6 g (0.05 mol) were added. Further, 15 mL of 2-ethoxyethanol and 15 mL of acetic acid were dissolved in a mixed solvent of 2-ethoxyethanol and acetic acid to dissolve the phenolic trinuclear compound (1) and paraformaldehyde. Then, while cooling in an ice bath, 10 mL of sulfuric acid was added to the reaction solution in the four-necked flask, and then the mixture was heated to 80 ° C in an oil bath and heated for 4 hours, and stirred while being reacted. Water was added to the reaction solution after completion of the reaction to carry out a reprecipitation operation, thereby obtaining a crude product. After the crude product was redissolved in acetone, the reprecipitation operation was carried out using water. The product obtained by the reprecipitation operation was subjected to filtration and separation, and vacuum-dried to obtain 16.8 g of a red powder of a novolac type phenol resin (phenolic resin (4)). The GPC chart of the phenol resin (4) is shown in Fig. 6. GPC was carried out on the phenol resin (4), and as a result, the number average molecular weight (Mn) was 1,994, the weight average molecular weight (Mw) was 7,603, and the polydispersity (Mw/Mn) was 3.81.

[Comparative Synthesis Example 2] Synthesis of <(soft) cresol novolac resin>

To a four-necked flask having a capacity of 300 mL equipped with a cooling tube, 13.0 g (0.12 mol) of m-cresol, 8.6 g (0.08 mol) of p-cresol, and 16.0 g (0.08 mol) of 50% glutaraldehyde were added. 15 mL of 2-ethoxyethanol and 15 mL of acetic acid were dissolved in m-cresol, p-cresol and glutaraldehyde in a mixed solvent of 2-ethoxyethanol and acetic acid. Then, while cooling in an ice bath, 10 mL of sulfuric acid was added to the reaction solution in the four-necked flask, and then 92% of paraformaldehyde (3.3 g (0.1 mol)) was added, and the temperature was raised to 80 ° C in an oil bath. After heating for 10 hours, the reaction was carried out while stirring. Water was added to the reaction solution after completion of the reaction to carry out a reprecipitation operation, thereby obtaining a crude product. After the crude product was dissolved in acetone, the reprecipitation operation was carried out using water. The product obtained by the reprecipitation operation was subjected to filtration separation, and vacuum-dried to obtain 20.6 g of a phenol phenol resin (phenolic resin (5)) of an orange powder. The GPC chart of the phenol resin (5) is shown in Fig. 7. GPC was carried out on the phenol resin (5), and as a result, the number average molecular weight (Mn) was 2,150, the weight average molecular weight (Mw) was 9,571, and the polydispersity (Mw/Mn) was 4.45.

[Examples 1 to 3, Comparative Examples 1 to 2]

For the phenolic resins (1) to (5) synthesized in Synthesis Examples 2 to 4 and Comparative Synthesis Examples 1 and 2, as shown in Table 1, a phenol resin and a sensitizer (manufactured by Toyo Kasei Kogyo Co., Ltd.) were produced. P-200"; 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol 1 molar with 1,2 -naphthoquinone-2-diazide-5-sulfonyl chloride 2 molar condensate) and PGMEA were mixed at 28/12/60 (parts by mass) and dissolved, and then subjected to a 0.2 μm membrane filter. Filtration was carried out to obtain a photosensitive composition. The coating film was prepared using these compositions, and alkali developability, sensitivity, resolution, heat resistance (Tg), substrate followability, and flexibility were evaluated based on the following. The evaluation results are shown in Table 1.

<alkali developability evaluation>

The photosensitive composition was applied onto a 5 inch silicon wafer by 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 twin film having a coating film. circle. The obtained wafer was immersed in an alkali developer (2.38% aqueous solution of tetramethylammonium hydroxide) for 60 seconds, and then dried on a hot plate at 110 ° C for 60 seconds. The film thickness of the coating film of the photosensitive composition was measured before and after immersion in the developer immersion, and the value obtained by dividing the difference by the thickness by 60 was used as the evaluation result of alkali developability (ADR (Å/sec)). . In the case of exposure, PEB (Post) was carried out at 140 ° C for 60 seconds after irradiation with a g, h, and i-ray lamp (a versatile lamp manufactured by Oxtail Electric Co., Ltd.) to expose it to 100 mJ/cm ² . Exposure Bake, post-exposure baking, was used to obtain wafers, and the ADR alkali developability was evaluated using the wafer. The film thickness of the coating film was measured using a film thickness meter ("F-20" manufactured by FILMETRICS Co., Ltd.).

<sensitivity evaluation>

On a 5 inch ruthenium wafer having a coating film obtained by coating a photosensitive composition with a thickness of about 20 μm and drying it, the adhesion pitch is 1:1 to 10 μm corresponding to the resist pattern. After the mask, it was found that the exposure amount (Eop exposure amount) of 3 μm can be faithfully reproduced by the g, h, and i-ray lamps.

<Resolution Evaluation>

A photomask was placed on a 5 inch wafer of a coating film obtained by applying a photosensitive composition and dried, and a g, h, and i-ray lamp (a universal lamp manufactured by Oxtail Electric Co., Ltd.) was used at 200 mJ/ The cm ² was irradiated to make it photosensitive. The coated film after the irradiation was developed and dried in the same manner as in <Evaluation of alkali developability>. The pattern state of the resist pattern on the developed wafer was evaluated using a laser microscope (VK-X200) manufactured by Ens. In the evaluation system, the L/S=5 μm resolver can be set to “○”, and the L/S=5 μm resolution cannot be set to “×”.

<Evaluation of heat resistance>

The evaluation of heat resistance was evaluated by the glass transition temperature (Tg) of the coating film. Specifically, the photosensitive composition was applied onto a 5 inch silicon wafer by 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 coating film.矽 Wafer. The resin composition was scraped from the obtained wafer, and the glass transition temperature was measured. The glass transition temperature was measured by a differential scanning calorimeter (DSC) (manufactured by TA Instrument Co., Ltd., product name: Q100) under a nitrogen atmosphere at a temperature range of -100 to 200 ° C and a temperature rise temperature of 10 ° C /min. Enter Line scan, the measurement result is set to the glass transition temperature.

<Substrate followability evaluation>

The photosensitive composition was applied onto a 5 inch silicon wafer by a spin coater to a thickness of about 50 μm, and dried on a hot plate at 110 ° C for 300 seconds. A laser microscope (VK-X200) manufactured by Enns was used to observe whether or not the surface of the obtained film was cracked. In the evaluation, the person who did not observe the crack was set to "○", and the person who observed the crack was set to "X".

<softness>

The photosensitive composition was applied onto a polyimine film having a thickness of 50 μm by a spin coater to a thickness of about 5 μm, and dried on a hot plate at 110 ° C for 300 seconds. The obtained film-form coating film was bent by 180 degrees, and the state of the curved portion was observed using a laser microscope (VK-X200) manufactured by Ens. In the evaluation, the person who did not observe the crack was set to "○", and the person who observed the crack was set to "X".

As a result, the coating film (Examples 1 to 3) containing the photosensitive composition of the phenol resin (1) to (3) which is the novolac type phenol resin of the present invention has an ADR of 1600 Å/sec or more after exposure, and alkali development It has good properties, high sensitivity and resolution, high glass transition temperature, 160 ° C or higher, good heat resistance, and excellent substrate followability and softness. On the other hand, the coating film (Comparative Example 1) containing a photosensitive composition of a phenol resin (4) which is a novolac type phenol resin synthesized using only a monoaldehyde as a bridging agent has alkali developability, sensitivity, resolution, and heat resistance. Excellent in properties, but poor substrate followability and softness. In addition, the coating film (Comparative Example 2) containing a photosensitive composition of a phenol resin (5) which is a cresol novolak resin which is synthesized by using a polyaldehyde as a bridging agent, is excellent in substrate followability and flexibility, but is alkali-developed. Sex, sensitivity, resolution and heat resistance are not sufficient.

Claims (14)

A novolac type phenol resin which is one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2) in the presence of an acid catalyst The above phenolic trinuclear compound (A), monoaldehyde (B) and polyaldehyde (C) are reacted to obtain: In the formula (1), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 8 carbon atoms which may have a substituent; when a plurality of R ¹ are present, the same may be the same Alternatively, when there are a plurality of R ² , the same may be the same or different. When there are multiple R ³ , the same may be the same or different; p and q are each an integer of 1 to 4, respectively. r is an integer from 0 to 4, and s is 1 or 2; wherein the sum of r and s is 5 or less]; [In the formula (2), R ¹ , R ² , R ³ , p and q are the same as the formula (1), and t is an integer of 0 to 5]. The novolac type phenol resin according to claim 1, wherein the polyaldehyde (C) is an aliphatic dialdehyde. The novolac type phenol resin according to claim 2, wherein the aliphatic dialdehyde is glutaraldehyde or adipaldehyde. The novolac type phenol resin according to any one of claims 1 to 3, wherein the monoaldehyde (B) is formaldehyde. The novolac type phenol resin according to any one of claims 1 to 3, wherein the monoaldehyde (B) and the polyaldehyde (C) reacted with the phenolic trinuclear compound (A) The amount used is 1/0.01 to 1/1.5 in terms of mass ratio [(B)/(C)]. The novolac type phenol resin according to any one of claims 1 to 3, wherein the phenolic trinuclear compound (A) is selected from the group consisting of the following general formulae (1-1), (1-2), (1) a compound of one or more of the group consisting of -7), (1-8), (1-13), (1-14), (2-1) or (2-2): In the formula, R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 8 carbon atoms which may have a substituent; and a plurality of R ^{1 's} may be the same or different from each other, and a plurality of R may be present. ² can be the same or different from each other. When there are multiple R ³ cases, they may be the same or different; r1 represents an integer from 0 to 4, r2 represents an integer from 0 to 3, and t represents an integer from 0 to 5] . The novolac type phenol resin according to any one of claims 1 to 3, which has a structural unit (I-1) selected from the following general formula (I-1), and the following general formula (I- 2) The structural unit (I-2) shown, the structural unit (II-1) represented by the following general formula (II-1), and the structural unit represented by the following general formula (II-2) (II- 2) One or more structural parts of the group formed as a repeating unit: [In the formula (I-1), R ¹ and R ² are the same as the formula (1), and R ⁴ represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent]; [In the formula (I-2), R ¹ and R ² are the same as the formula (1), and R ⁴ is the same as the formula (I-1)]; [In the formula (II-1), R ¹ and R ² are the same as the formula (1), and R ⁴ is the same as the formula (I-1)]; In the formula (II-2), R ¹ and R ² are the same as the formula (1), and R ⁴ is the same as the formula (I-1). A novolac type phenol resin according to claim 7 wherein R ¹ and R ² are each a methyl group. A novolac type phenol resin according to item 7 of the patent application, which has a structural unit represented by the formula (I-1) or a structural unit represented by the formula (II-1) as a repeating unit, and a weight average molecular weight It is 5,000~25,000. A novolac type phenol resin according to claim 7 which has a structural unit represented by the formula (I-2) or a structural unit represented by the formula (II-2) as a repeating unit, and a weight average molecular weight It is 1,000~5,000. A photosensitive composition comprising the novolac type phenol resin and the sensitizer according to any one of claims 1 to 10. A resist material comprising the photosensitive composition of claim 11 of the patent application. A coating film comprising the photosensitive composition of claim 11 of the patent application. A resist coating film comprising the resist material of claim 12 of the patent application.