JP2018197307A - Dendrimer type resin and resist material - Google Patents

Abstract

To provide a dendrimer type resin having excellent developability, heat resistance and fluidity, and a resist material.SOLUTION: A dendrimer type resin that is a reaction product between a special polyhydric phenol compound (A) and a divinyl compound (B). The dendrimer type resin having a ratio ((OH)/(V)) of a mol number (OH) of phenolic hydroxyl groups in a reaction raw material and a mol number (V) of vinyl groups in the divinyl compound (B) in the range of 1/1 to 1/0.1. A photosensitive composition contains the dendrimer type resin and a photoacid generating agent.SELECTED DRAWING: None

Description

  The present invention relates to a dendrimer type resin excellent in developability, heat resistance and fluidity, a photosensitive composition using the same, a curable composition, and a resist material.

  In the field of photoresists, various resist pattern forming methods that have been subdivided according to applications and functions have been developed one after another, and accordingly, the required performance for resist resin materials has become sophisticated and diversified. For example, a resin material for forming a pattern requires high developability for forming a fine pattern accurately and with high production efficiency on a highly integrated semiconductor. In applications called underlayer films, antireflection films, BARC films, hard masks, etc., dry etching resistance, low reflectivity, and high fluidity that can be applied to uneven substrate surfaces are required. In addition, in applications such as resist permanent films, toughness such as substrate followability is required in addition to high heat resistance. Furthermore, from the viewpoint of quality and reliability, long-term storage stability in various environments around the world is one of the important performances.

  The phenolic hydroxyl group-containing resin most widely used for photoresist applications is of the cresol novolac type, but it is not capable of meeting the performance requirements of today's increasingly sophisticated and diversified markets, developability and heat resistance, Further improvements in various properties such as fluidity have been demanded (see Patent Document 1).

JP-A-2-55359

  Therefore, the problem to be solved by the present invention is to provide a dendrimer type resin excellent in developability, heat resistance and fluidity, a photosensitive composition, a curable composition and a resist material using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that a dendrimer type resin, which is a reaction product of a polynuclear phenol compound and a divinyl compound, is excellent in developability, heat resistance and fluidity. The present invention has been completed.

  That is, the present invention provides the following structural formula (1)

［式中ｋは０又は１である。Ｒ^１は置換基を有していてもよい脂肪族炭化水素基、アルコキシ基、ハロゲン原子の何れかであり、ｌは０又は１〜５の整数である。Ｒ^２は置換基を有していてもよい脂肪族炭化水素基、アルコキシ基、ハロゲン原子の何れかであり、ｍは０又は１〜４の整数である。Ｒ^３は水素原子又は置換基を有していてもよい脂肪族炭化水素基である。ｎは１又は２である。］
で表される化合物（Ａ）と、ジビニル化合物（Ｂ）との反応物であるデンドリマー型樹脂に関する。

[Wherein k is 0 or 1; R ¹ is an aliphatic hydrocarbon group which may have a substituent, an alkoxy group, or a halogen atom, and l is an integer of 0 or 1-5. R ² is an aliphatic hydrocarbon group which may have a substituent, an alkoxy group, or a halogen atom, and m is 0 or an integer of 1 to 4. R ³ is a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. n is 1 or 2. ]
It is related with the dendrimer type resin which is a reaction material of the compound (A) represented by these, and a divinyl compound (B).

  The present invention further relates to a photosensitive composition containing the dendrimer type resin and a photoacid generator.

  The present invention further relates to a curable composition containing a dendrimer type resin and a curing agent.

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

  The present invention further relates to a resist material using the dendrimer type resin.

  ADVANTAGE OF THE INVENTION According to this invention, the dendrimer type resin excellent in developability, heat resistance, and fluidity | liquidity, the photosensitive composition using this, a curable composition, and a resist material can be provided.

FIG. 1 is a GPC chart of the compound (A-1) obtained in Production Example 1. FIG. 2 is a ¹³ C-NMR chart of the compound (A-1) obtained in Production Example 1. FIG. 3 is a GPC chart of the compound (A-2) obtained in Production Example 2. FIG. 4 is a ¹³ C-NMR chart of the compound (A-2) obtained in Production Example 2. FIG. 5 is a GPC chart of the dendrimer type resin (1) obtained in Example 1. FIG. 6 is a GPC chart of the dendrimer type resin (2) obtained in Example 2. FIG. 7 is a GPC chart of the dendrimer type resin (3) obtained in Example 3. FIG. 8 is a GPC chart of the dendrimer type resin (4) obtained in Example 4. FIG. 9 is a GPC chart of the dendrimer type resin (5) obtained in Example 5. FIG. 10 is a GPC chart of the dendrimer type resin (6) obtained in Example 6.

Hereinafter, the present invention will be described in detail.
The dendrimer type resin of the present invention has the following structural formula (1)

［式中ｋは０又は１である。Ｒ^１は置換基を有していてもよい脂肪族炭化水素基、アルコキシ基、ハロゲン原子の何れかであり、ｌは０又は１〜５の整数である。Ｒ^２は置換基を有していてもよい脂肪族炭化水素基、アルコキシ基、ハロゲン原子の何れかであり、ｍは０又は１〜４の整数である。Ｒ^３は水素原子又は置換基を有していてもよい脂肪族炭化水素基である。ｎは１又は２である。］
で表される化合物（Ａ）と、ジビニル化合物（Ｂ）との反応物であることを特徴とする。

[Wherein k is 0 or 1; R ¹ is an aliphatic hydrocarbon group which may have a substituent, an alkoxy group, or a halogen atom, and l is an integer of 0 or 1-5. R ² is an aliphatic hydrocarbon group which may have a substituent, an alkoxy group, or a halogen atom, and m is 0 or an integer of 1 to 4. R ³ is a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. n is 1 or 2. ]
It is a reaction material of the compound (A) represented by these, and a divinyl compound (B), It is characterized by the above-mentioned.

In the compound (A), R ¹ in the structural formula (1) is any one of an aliphatic hydrocarbon group, an alkoxy group, and a halogen atom which may have a substituent. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Regarding the aliphatic hydrocarbon group which may have the substituent, the aliphatic hydrocarbon group may be any of a straight chain type, a branched structure, and an alicyclic structure. In addition, the structure may have either an unsaturated group or not, and the number of carbon atoms is not particularly limited. Examples of the substituent on the aliphatic hydrocarbon group include the alkoxy group, halogen atom, amino group, hydroxyl group, carboxy group, and alkylcarbonyl group. Among them, l is preferably 0 because it becomes a dendrimer type resin which is further excellent in heat resistance and fluidity.

R ² in the structural formula (1) is any one of an optionally substituted aliphatic hydrocarbon group, an alkoxy group, and a halogen atom, and specific examples thereof are exemplified as R ¹ . And the like. Among them, an aliphatic hydrocarbon group is preferable because it becomes a dendrimer-type resin that is further excellent in heat resistance and fluidity, more preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a methyl group, Particularly preferred is an ethyl group, a propyl group or a butyl group. Further, m is preferably an integer of 1 to 4, and more preferably 1 or 2.

R ³ in the structural formula (1) is a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. Specific examples of the aliphatic hydrocarbon group which may have a substituent include those exemplified as the aforementioned R ¹ . Among them, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms is preferable because it becomes a dendrimer-type resin having further excellent heat resistance and fluidity, and a hydrogen atom, a methyl group, an ethyl group, a propyl group, More preferably, it is one of butyl groups.

  The compound (A) can be produced, for example, by subjecting a phenol compound (a1) and an aromatic aldehyde compound (a2) to a condensation reaction. Commercial products such as “TrisP-HAP” [1,1,1-tris (4-hydroxyphenyl) ethane] manufactured by Honshu Chemical Industry Co., Ltd. may be used. Hereinafter, an example of the manufacturing method in the case of manufacturing by making a phenol compound (a1) and an aromatic aldehyde compound (a2) carry out a condensation reaction is demonstrated.

  In the phenol compound (a1), for example, one or more of hydrogen atoms on the aromatic nucleus of phenol or phenol is substituted with an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, an alkoxy group, a halogen atom, or the like. Compounds. These may be used alone or in combination of two or more. Among them, a phenol compound having an aliphatic hydrocarbon group having 1 to 6 carbon atoms is preferable because it becomes a dendrimer type resin having further excellent heat resistance and fluidity, and is any one of a methyl group, an ethyl group, a propyl group, and a butyl group. More preferred are phenolic compounds having The number of aliphatic hydrocarbon groups on the aromatic nucleus is preferably 1 to 4, and preferably 1 or 2. In particular, it is preferable to use 2,5-xylenol as the phenol compound (a1).

  In the aromatic aldehyde compound (a2), for example, in addition to benzaldehyde and phthalaldehyde, one or more of hydrogen atoms on the aromatic nucleus are aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, alkoxy groups, hydroxyl groups , An amino group, an alkylcarbonyl group, a compound substituted with a halogen atom, and the like. Moreover, the substitution position with the formyl group or hydroxyl group on the aromatic nucleus is not particularly limited, and any compound may be used. These aromatic aldehyde compounds (a2) may be used alone or in combination of two or more. Among them, hydroxybenzaldehyde or phthalaldehyde is preferable because it becomes a dendrimer-type resin having an excellent balance of heat resistance, fluidity, and developability.

  The reaction ratio between the phenol compound (a1) and the aromatic aldehyde compound (a2) is that the target compound (A) can be obtained in high yield and high purity, so that 1 mol of the phenol compound (a1) is obtained. The formyl group in the aromatic aldehyde compound (a2) is preferably in the range of 0.2 to 0.7 mol, and more preferably in the range of 0.3 to 0.5.

  The reaction between the phenol compound (a1) and the aromatic aldehyde compound (a2) is preferably performed under acid catalyst conditions. Examples of the acid catalyst used here include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used alone or in combination of two or more. Among these, sulfuric acid and paratoluenesulfonic acid are preferable from the viewpoint of excellent catalytic activity.

  The reaction of the phenol compound (a1) and the aromatic aldehyde compound (a2) may be performed in an organic solvent as necessary. Examples of the solvent used here 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 recall ethyl methyl ether and ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane and tetrahydrofuran; glycol esters such as ethylene glycol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like Examples include ketones. These solvents may be used alone or in combination of two or more kinds.

  The reaction of the phenol compound (a1) and the aromatic aldehyde compound (a2) is performed, for example, in a temperature range of 60 to 140 ° C. and for 0.5 to 20 hours.

  After completion of the reaction, for example, the reaction product is put into the poor solvent (S1) of the compound (A) and the precipitate is filtered off. Then, the solubility of the compound (A) is high and the poor solvent ( Unreacted phenol compound (a1), aromatic aldehyde compound (a2), acid catalyst used, etc. are removed from the reaction product by re-dissolving the precipitate obtained in the solvent (S2) mixed with S1) Thus, the purified compound (A) can be obtained.

  When the reaction between the phenol compound (a1) and the aromatic aldehyde compound (a2) is carried out in an aromatic hydrocarbon solvent such as toluene or xylene, the reaction product is heated to 80 ° C. or higher and the compound (A ) In an aromatic hydrocarbon solvent and cooled as it is, the crystals of the compound (A) can be precipitated.

  The poor solvent (S1) used for purification of the compound (A) is, for example, water; monoalcohols such as methanol, ethanol, propanol, ethoxyethanol; fats such as n-hexane, n-heptane, n-octane, cyclohexane Aromatic hydrocarbons such as toluene and xylene. These may be used alone or in combination of two or more. Of these, water, methanol, and ethoxyethanol are preferred because of the excellent solubility of the acid catalyst.

  On the other hand, the solvent (S2) is, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, , 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, polyol such as 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, ethylene glycol ethyl methyl ether, ethylene glycol 1,3-dioxane, cyclic ethers and 1,4-dioxane; glycol ethers Roh phenyl ether glycol esters such as ethylene glycol acetate; acetone, methyl ethyl ketone, and ketones such as methyl isobutyl ketone. These may be used alone or in combination of two or more. Especially, when water or monoalcohol is used as the poor solvent (S1), it is preferable to use acetone as the solvent (S2).

  After completion of the reaction, a higher purity compound (A) can be obtained by purifying the reaction product by washing with water, reprecipitation or the like. The degree of purification of the compound (A) is not particularly limited, but the purity of the compound (A) is determined from the area ratio of the GPC chart because the performance of the dendrimer type resin such as fluidity, heat resistance and developability is further improved. The calculated value is preferably 90% or more, and more preferably 95% or more.

In the present invention, the purity of the compound (A) is a value calculated from the area ratio of a chart obtained by GPC measurement under the following conditions. Further, the molecular weight and polydispersity (Mw / Mn) of the resin described later are values measured by GPC measurement under the following conditions.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF803” (8.0 mmФ ×) manufactured by Showa Denko KK 300 mm) + “Shodex KF804” (8.0 mmФ × 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: Filtered 0.5% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)
Standard sample: Monodispersed polystyrene below (Standard sample: Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation

  When producing the dendrimer-type resin of the present invention, the compound (A) may be a single structure alone or a plurality of compounds having different structures may be used in combination. Moreover, you may use together other phenolic hydroxyl-containing compound (A ') other than the said compound (A). Examples of the other phenolic hydroxyl group-containing compound (A ′) include phenol, cresol, xylenol, phenylphenol, dihydroxybenzene, biphenol, bisphenol, naphthol, and dihydroxynaphthalene. These may be used alone or in combination of two or more. When the other phenolic hydroxyl group-containing compound (A ′) is used, the effects of the present invention are sufficiently exerted, so the total of the compound (A) and the other phenolic hydroxyl group-containing compound (A ′). In 100 parts by mass, the compound (A) is preferably used at a rate of 70 parts by mass or more, more preferably 90 parts by mass or more.

  As long as the divinyl compound (B) is a compound having two vinyl groups in the molecule, other specific structures are not particularly limited, and a wide variety of compounds can be used. As an example, the following structural formula (2)

（式中Ｒ^４は置換基を有していてもよい炭化水素基である。Ｘは直接結合、酸素原子、硫黄原子の何れかである。）
で表される化合物等が挙げられる。

(In the formula, R ⁴ is a hydrocarbon group which may have a substituent. X is a direct bond, an oxygen atom or a sulfur atom.)
The compound etc. which are represented by these are mentioned.

Examples of R ⁴ in the structural formula (2) include an aliphatic hydrocarbon group which may have a substituent, a (poly) (cyclo) alkylene ether structure, and an aromatic ring-containing structure. Regarding the aliphatic hydrocarbon group which may have the substituent, the aliphatic hydrocarbon group may be any of a straight chain type, a branched structure, and an alicyclic structure. In addition, the structure may have either an unsaturated group or not, and the number of carbon atoms is not particularly limited. Examples of the substituent on the aliphatic hydrocarbon group include the alkoxy group, halogen atom, amino group, hydroxyl group, carboxy group, and alkylcarbonyl group. Specific examples of the aliphatic hydrocarbon group which may have a substituent include alkylene groups such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a normal hexylene group; a cyclohexylene group and the like. Cycloalkylene group; Cycloalkanedialkylene group such as cyclohexanedimethylene group and cyclohexanediethylene group: Alkyldicycloalkylene group such as methyldicyclohexylene group, ethyldicyclohexylene group, and propyldicyclohexylene group; And a structural site in which one or more of these are substituted with an alkoxy group, a halogen atom, an amino group, a hydroxyl group, a carboxy group, an alkylcarbonyl group, or the like.

  The (poly) (cyclo) alkylene ether structure is a structure in which two or more (cyclo) alkylene groups are linked by an oxygen atom, and the following structural formula (3)

（式中Ｒ^５は置換基を有していてもよいアルキレン基又はシクロアルキレン基であり、ｐは１以上の整数である。）
で表される構造等が挙げられる。Ｒ^５の具体例としては、メチレン基、エチレン基、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ノルマルヘキシレン基等のアルキレン基；シクロヘキシレン基等のシクロアルキレン基；これらが有する水素原子の一つ乃至複数がアルコキシ基やハロゲン原子、アミノ基、水酸基、カルボキシ基、アルキルカルボニル基等で置換された構造部位等が挙げられる。

(In the formula, R ⁵ is an alkylene group or a cycloalkylene group which may have a substituent, and p is an integer of 1 or more.)
The structure etc. which are represented by these are mentioned. Specific examples of R ⁵ include alkylene groups such as methylene group, ethylene group, methylene group, ethylene group, propylene group, butylene group, pentylene group and normal hexylene group; cycloalkylene groups such as cyclohexylene group; Examples thereof include structural sites in which one or more hydrogen atoms are substituted with an alkoxy group, a halogen atom, an amino group, a hydroxyl group, a carboxy group, an alkylcarbonyl group, or the like.

The aromatic ring-containing structure is an arylene group such as a phenylene group, a naphthylene group, or a biphenylene group; an arenedialkylene group such as a benzenedimethylene group, a benzenediethylene group, or a benzenedipropylene group; a methylbiphenylene group, an ethylbiphenylene group, or a propylbiphenylene. An alkyldiarylene group such as a group; a (poly) arylene ether structure in which R ⁵ is an arylene group in the structural formula (3); one or more of hydrogen atoms on these aromatic nuclei are an alkyl group, alkoxy group, halogen Examples thereof include structural sites substituted with an atom, amino group, hydroxyl group, carboxy group, alkylcarbonyl group, and the like.

Especially, since it becomes a dendrimer type resin excellent in sensitivity when used in combination with a photoacid generator, R ⁴ in the structural formula (2) may be an aliphatic hydrocarbon group which may have a substituent or It is preferably a (poly) (cyclo) alkylene ether structure, more preferably a cycloalkanedialkylene group or a structural moiety in which R ⁵ is an alkylene group having 2 to 4 carbon atoms in the structural formula (3). .

  In the dendrimer type resin of the present invention, the reaction conditions for reacting the compound (A), the divinyl compound (B), and the other phenolic hydroxyl group-containing compound (A ′) used as necessary are not particularly limited. However, as an example, a method of reacting these raw materials under a temperature condition of about 25 to 100 ° C. under acid catalyst conditions can be mentioned.

  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 may be used alone or in combination of two or more.

  The reaction rate of the reaction raw material is appropriately adjusted according to the consumption performance of the resulting dendrimer-type resin, but the number of moles of phenolic hydroxyl group (OH) in the reaction raw material and vinyl in the divinyl compound (B). The ratio [(OH) / (V)] to the number of moles (V) of the group is preferably in the range of 1/1 to 1 / 0.1, and in the range of 1 / 0.98 to 1 / 0.3. It is more preferable that Specifically, the number of moles (OH) of the phenolic hydroxyl group in the reaction raw material is the number of moles of the phenolic hydroxyl group in the compound (A) and the other phenolic hydroxyl group-containing compound (A ′). And the total number of moles of phenolic hydroxyl groups.

  The reaction for producing the dendrimer type resin may be carried out in an organic solvent. 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, 1, Polyols such as 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerol; 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 Glycol ethers such as ethyl ethyl ether and ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxolane, 1,3-dioxane, 1,4-dioxane and tetrahydrofuran; glycol esters such as ethylene glycol acetate; acetone; Examples thereof include ketones such as methyl ethyl ketone and methyl isobutyl ketone. These solvents may be used alone or in combination of two or more kinds.

  After completion of the reaction, the desired dendrimer type resin can be obtained by neutralizing with an amine compound or the like, and generating the resin by washing or reprecipitation.

  The weight average molecular weight (Mw) of the dendrimer type resin of the present invention is more preferably in the range of 3,000 to 50,000, since it will be more excellent in developability, heat resistance and fluidity. In addition, the polydispersity (Mw / Mn) is preferably in the range of 1.1 to 20, and more preferably in the range of 1.5 to 15.

  Since the dendrimer type resin of the present invention described in detail above is easily dissolved in a general-purpose organic solvent and has excellent heat resistance, there are various paints, adhesives, electric / electronic members, photoresists, liquid crystal alignment films, etc. Can be used for various purposes. Above all, it is particularly suitable for resist materials as an application that makes use of the characteristics that are excellent in developability, heat resistance and fluidity, and various resist members such as a resist underlayer film and a resist permanent film in addition to a general interlayer insulating film. Can be used. The dendrimer resin of the present invention is characterized by excellent dry etching resistance, storage stability, toughness and the like in addition to developability, heat resistance and fluidity.

  The photosensitive composition of the present invention contains the dendrimer resin of the present invention and a photoacid generator as essential components.

  As the photoacid generator, known and commonly used ones can be used without particular limitation. Specific examples of the photoacid generator include, for example, a sulfonium salt that is a salt of a sulfonium cation such as triarylsulfonium or triaralkylsulfonium and a sulfonate such as fluoroalkanesulfonate, arenesulfonate, or alkanesulfonate;

  An iodonium salt which is a salt of an iodonium cation such as diaryliodonium and a sulfonate such as fluoroalkanesulfonate, arenesulfonate, alkanesulfonate;

  Bissulfonyldiazomethane compounds such as bis (alkylsulfonyl) diazomethane, bis (cycloalkylsulfonyl) diazomethane, bis (perfluoroalkylsulfonyl) diazomethane, bis (arylsulfonyl) diazomethane, bis (aralkylsulfonyl) diazomethane;

  An N-sulfonyloxyimide compound comprising a combination of a dicarboxylic imide compound and a sulfonate such as fluoroalkanesulfonate, arenesulfonate, alkanesulfonate;

  Benzoin sulfonate compounds such as benzoin tosylate, benzoin mesylate, benzoin butane sulfonate;

  A polyhydroxyarene sulfonate compound in which all of the hydroxy groups of the polyhydroxyarene compound are substituted with a sulfonate such as fluoroalkanesulfonate, arenesulfonate, and alkanesulfonate;

Nitrobenzyl sulfonate compounds such as fluoroalkanesulfonic acid (poly) nitrobenzyl, arenesulfonic acid (poly) nitrobenzyl, alkanesulfonic acid (poly) nitrobenzyl;

  Fluoroalkanebenzyl sulfonate compounds such as fluoroalkanesulfonic acid (poly) fluoroalkanebenzyl, arenesulfonic acid (poly) fluoroalkanebenzyl, alkanesulfonic acid (poly) fluoroalkanebenzyl;

  A bis (arylsulfonyl) alkane compound;

  Bis-O- (arylsulfonyl) -α-dialkylglyoxime, bis-O- (arylsulfonyl) -α-dicycloalkylglyoxime, bis-O- (arylsulfonyl) -α-diarylglyoxime, bis-O -(Alkylsulfonyl) -α-dialkylglyoxime, bis-O- (alkylsulfonyl) -α-dicycloalkylglyoxime, bis-O- (alkylsulfonyl) -α-diarylglyoxime, bis-O- (fluoro Alkylsulfonyl) -α-dialkylglyoxime, bis-O- (fluoroalkylsulfonyl) -α-dicycloalkylglyoxime, bis-O- (fluoroalkylsulfonyl) -α-diarylglyoxime, bis-O- (aryl Sulfonyl) -α-dialkylnioxime, bis-O- (arylsulfonyl) -α-di Chloroalkylnioximes, bis-O- (arylsulfonyl) -α-diarylnioximes, bis-O- (alkylsulfonyl) -α-dialkylnioximes, bis-O- (alkylsulfonyl) -α-dicycloalkyldi Oxime, bis-O- (alkylsulfonyl) -α-diarylnioxime, bis-O- (fluoroalkylsulfonyl) -α-dialkylnioxime, bis-O- (fluoroalkylsulfonyl) -α-dicycloalkylnioxime Oxime compounds such as bis-O- (fluoroalkylsulfonyl) -α-diarylnioxime;

  Arylsulfonyloxyiminoarylacetonitrile, alkylsulfonyloxyiminoarylacetonitrile, fluoroalkylsulfonyloxyiminoarylacetonitrile, ((arylsulfonyl) oxyimino-thiophene-ylidene) arylacetonitrile, ((alkylsulfonyl) oxyimino-thiophene-ylidene) arylacetonitrile, ((Fluoroalkylsulfonyl) oxyimino-thiophene-ylidene) arylacetonitrile, bis (arylsulfonyloxyimino) arylene acetonitrile, bis (alkylsulfonyloxyimino) arylene acetonitrile, bis (fluoroalkylsulfonyloxyimino) arylene acetonitrile, aryl Fluoroalkanone-O (Alkylsulfonyl) oxime, aryl fluoro alkanone -O- (arylsulfonyl) oxime, modified oxime compounds such aryl fluoro alkanone -O- (fluoroalkylsulfonyl) oxime and the like. These may be used alone or in combination of two or more.

  Since the addition amount of these photo-acid generators becomes a photosensitive composition with high photosensitivity, it is used in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin solid content of the photosensitive composition. preferable.

  The photosensitive composition of the present invention may contain an organic base compound for neutralizing an 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. Organic base compounds include, for example, pyrimidine, (poly) aminopyrimidine, (poly) hydroxypyrimidine, (poly) amino (poly) hydroxypyrimidine, (poly) amino (poly) alkylpyrimidine, (poly) amino (poly) alkoxypyrimidine , (Poly) hydroxy (poly) alkylpyrimidine, pyrimidine compounds such as (poly) hydroxy (poly) alkoxypyrimidine; pyridine compounds such as pyridine, (poly) alkylpyridine, dialkylaminopyridine; polyalkanolamines, tri (hydroxyalkyl) Hydroxyalkyl group-containing amine compounds such as aminoalkanes and bis (hydroxyalkyl) iminotris (hydroxyalkyl) alkanes; and aminoaryl compounds such as aminophenols. These may be used alone or in combination of two or more. When these organic base compounds are added, the addition amount is preferably in the range of 0.1 to 100 mol%, and in the range of 1 to 50 mol%, with respect to the content of the photoacid generator. Is more preferable.

  The photosensitive composition of the present invention may be used in combination with other resin (V) in addition to the dendrimer type resin of the present invention. Any other resin (V) may be used as long as it is soluble in an alkali developer or can be dissolved in an alkali developer by using it in combination with an additive such as a photoacid generator. it can.

  Examples of the other resin (V) include other phenol resins (V-1) other than the dendrimer type resin of the present invention, p-hydroxystyrene, and p- (1,1,1,3,3,3-hexa). Homopolymer or copolymer (V-2) of a hydroxy group-containing styrene compound such as (fluoro-2-hydroxypropyl) styrene, the hydroxyl group of the above (V-1) or (V-2) is a t-butoxycarbonyl group or Fats such as (V-3) modified with an acid-decomposable group such as benzyloxycarbonyl group, homopolymer or copolymer (V-4) of (meth) acrylic acid, norbornene compound and tetracyclododecene compound Examples thereof include an alternating polymer (V-5) of a cyclic polymerizable monomer and maleic anhydride or maleimide.

  Examples of the other phenol resin (V-1) include phenol novolak resin, cresol novolak resin, naphthol novolak resin, co-condensed novolak resin using various phenolic compounds, aromatic hydrocarbon formaldehyde resin-modified phenol resin, Cyclopentadiene phenol addition resin, phenol aralkyl resin (Zylok resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), Biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine-modified phenol resin (melamine, benzoguanamine, etc. There include linked polyhydric phenol compound) and an alkoxy group-containing aromatic ring-modified novolac resins (polyvalent phenolic compounds phenol nucleus and an alkoxy group-containing aromatic ring are connected by formaldehyde) phenolic resin or the like.

  Among the other phenol resins (V-1), a photosensitive composition having an excellent balance of developability, heat resistance, and fluidity is obtained, so that a cresol novolak resin or a co-condensed novolak of cresol and another phenolic compound is obtained. Resins are preferred. The cresol novolac resin or the co-condensed novolak resin of cresol and other phenolic compound specifically includes at least one cresol selected from the group consisting of o-cresol, m-cresol and p-cresol and an aldehyde compound. It is a novolak resin obtained as an essential raw material and appropriately used in combination with other phenolic compounds.

  When using the said other resin (V), the compounding ratio of the dendrimer type resin of this invention and other resin (V) can be arbitrarily adjusted with a desired use. For example, since the dendrimer type resin of the present invention is excellent in photosensitivity, resolution, heat resistance and the like when combined with a photosensitive agent, a photosensitive composition containing this as a main component is optimal for resist applications. At this time, the ratio of the dendrimer type resin of the present invention in the total of the resin components is preferably 60% by mass or more, and more preferably 80% by mass or more.

  Moreover, taking advantage of the excellent photosensitivity of the dendrimer type resin of the present invention, it can be used as a sensitivity improver. In this case, the blending ratio of the dendrimer type resin of the present invention and the other resin (V) is in the range of 3 to 80 parts by mass of the dendrimer type resin of the present invention with respect to 100 parts by mass of the other resin (V). It is preferable.

  The photosensitive composition of the present invention may further contain a photosensitizer used for ordinary resist materials. Examples of the photosensitive agent include compounds having a quinonediazide group. Specific examples of the compound having a quinonediazide group include, for example, an aromatic (poly) hydroxy compound, naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, orthoanthra Examples thereof include an ester compound with a sulfonic acid having a quinonediazide group such as quinonediazidesulfonic acid or a compound having a quinonediazide group such as an amidated product. One type of photosensitizer may be used alone, or two or more types may be used in combination. Since the compounding amount of the photosensitive agent in the photosensitive composition of the present invention is a photosensitive composition having excellent photosensitivity, it is 5 to 50 parts by mass with respect to 100 parts by mass in total of the resin solid content of the photosensitive composition. It is preferable that the ratio is

  The photosensitive composition of 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. As the surfactant, known ones can be used, and examples thereof include nonionic surfactants, fluorine-based surfactants, silicone-based surfactants, and the like. These may be used alone or in combination of two or more. It is preferable that the compounding quantity of surfactant is used in 0.001-2 mass parts with respect to 100 mass parts in total of the resin solid content in the photosensitive composition of this invention.

When the photosensitive composition of the present invention is used for resist applications, in addition to the dendrimer type resin and photoacid generator of the present invention, other phenol resins (V), photosensitive agents, surfactants, dyes as necessary. A photosensitive resist material can be obtained by adding various additives such as a filler, a cross-linking agent and a dissolution accelerator and dissolving in an organic solvent. The photosensitive resist material may be used as it is as a coating material, or may be used as a resist film obtained by applying a photosensitive resist material on a support film and removing the solvent. Examples of the support film used as a resist film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate, and may be a single layer film or a plurality of laminated films. The surface of the support film may be a corona-treated one or a release agent.

  The type of the organic solvent is not particularly limited. For example, 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 Dialkylene glycol dialkyl ethers such as diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; alkylene glycol alkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Cetate; ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone; cyclic ethers such as dioxane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyacetic acid Ethyl, 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, etc. These may be ester compounds, and these may be used alone or in combination of two or more.

  The said photosensitive resist material can be manufactured by mix | blending each said component and mixing using a stirrer etc. When the resist material contains a filler or a pigment, it can be produced by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three roll mill.

  Examples of a general photolithography method using the photosensitive resist material include the following methods. First, the photosensitive resist material is applied on an object to be photolithography such as a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, and prebaked at a temperature of 60 to 150 ° C. The coating method at this time may be any method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor blade coating and the like. Next, the resist pattern is formed by exposing through a resist pattern and developing with an alkali developer.

  When using the said photosensitive resist material for a resist permanent film | membrane use, it is preferable to contain a crosslinking agent with a photosensitive agent. Examples of the crosslinking agent used here are the same as those used in the curable composition described below. Examples of the method for forming the resist permanent film include the following methods. First, the photosensitive resist material is applied on an object such as a silicon substrate, a silicon carbide substrate, a gallium nitride substrate and the like to be subjected to photolithography, and prebaked at a temperature of 60 to 150 ° C. The application method is the same as that described above. Next, the resist pattern is exposed to light, further thermally cured at a temperature of 110 to 210 ° C., and then developed with an alkali developer to form a resist pattern. Or after exposure, you may develop with an alkaline developing solution first, and you may make it thermoset on the temperature conditions of 110-210 degreeC after that.

  Specific examples of the resist permanent film include a solder resist, a package material, an underfill material, a package adhesive layer of a circuit element, and an adhesive layer between a product circuit element and a circuit board in a semiconductor device. In thin displays represented by LCD and OELD, there are a thin film transistor protective film, a liquid crystal color filter protective film, a black matrix, a spacer, and the like.

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

  More specifically, the various novolak resins include 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 these other resins are used, the blending ratio of the dendrimer type resin of the present invention and the other resin (W) can be arbitrarily set according to the use, but the heat resistance and fluidity exhibited by the present invention can be achieved. It is preferable that the ratio of the other resin (W) is 0.5 to 100 parts by mass with respect to 100 parts by mass of the dendrimer-type resin of the present invention, since the excellent effect is exhibited more remarkably.

  The curing agent used in the present invention is not particularly limited as long as it is a compound capable of causing a curing reaction with the dendrimer type resin of the present invention, and various compounds can be used. Moreover, the curing method of the curable composition of the present invention is not particularly limited, and it can be cured by an appropriate method such as thermal curing or photocuring according to the type of curing agent or the type of curing accelerator described below. it can. Curing conditions such as the heating temperature and time in thermosetting, the type of light beam in photocuring and the exposure time are appropriately adjusted according to the type of curing agent, the type of curing accelerator described below, and the like.

  Specific examples of the curing agent include, for example, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, resol resins, epoxy compounds, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, and the like. Products, oxazoline compounds and the like.

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

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

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

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

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

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

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

  Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, 4,4'-oxybisazide, and the like.

Examples of the compound containing a double bond such as an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether. , Neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol 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 anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4 Aromatic acid anhydrides such as '-(isopropylidene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride And alicyclic carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, and trialkyltetrahydrophthalic anhydride.

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

  Since the compounding amount of the curing agent in the curable composition of the present invention is a composition having excellent curability, it is 0 with respect to 100 parts by mass in total of the dendrimer type resin of the present invention and the other resin (X). It is preferable that it is the ratio used as 5-50 mass parts.

  The curable composition of the present invention may contain a curing accelerator together with the curing agent. Examples of the curing accelerator include acid compounds such as acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, and manganese acetate, and the aforementioned photoacid generator. The curing accelerators may be used alone or in combination of two or more. It is preferable that the addition amount of a hardening accelerator is the range used as 0.1-10 mass% with respect to the resin solid content of a curable composition.

When the curable composition of the present invention is used for resist applications, in addition to the dendrimer-type resin and the curing agent of the present invention, other resins (Y), surfactants and dyes, fillers, crosslinks as necessary. A curable resist material can be obtained by adding various additives such as an agent and a dissolution accelerator and dissolving in an organic solvent. The curable resist material may be used as it is as a coating material, or a curable resist material applied on a support film and desolvated may be used as a resist film. Examples of the support film used as a resist film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate, and may be a single layer film or a plurality of laminated films. The surface of the support film may be a corona-treated one or a release agent.

  The type of the organic solvent is not particularly limited. For example, 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 Dialkylene glycol dialkyl ethers such as diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; alkylene glycol alkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Cetate; ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone; cyclic ethers such as dioxane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyacetic acid Ethyl, 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, etc. These may be ester compounds, and these may be used alone or in combination of two or more.

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

  When the curable resist material is used for a resist underlayer film application, as an example of a method for forming the resist underlayer film, for example, the curable resist material is subjected to photolithography such as a silicon substrate, a silicon carbide substrate, a gallium nitride base, etc. A resist underlayer film is formed by a method such as coating on a product, drying under a temperature condition of 100 to 200 ° C., and further heat curing under a temperature condition of 250 to 400 ° C. Next, a resist pattern is formed on this lower layer film by performing a normal photolithography operation, and a resist pattern by a multilayer resist method can be formed by performing a dry etching process with a halogen-based plasma gas or the like.

Hereinafter, the present invention will be described in more detail with specific examples. The number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (Mw / Mn) of the synthesized resin are measured by GPC under the following measurement conditions, and the purity of the compound is a GPC chart obtained under the following measurement conditions. The area ratio was calculated.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK + “Shodex KF802” (8.0 mmФ × 300 mm) manufactured by Showa Denko KK
+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ × 300 mm) + Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ × 300 mm)
Column temperature: 40 ° C
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.30” manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample: 0.5% by mass tetrahydrofuran solution filtered with a microfilter in terms of resin solids Injection volume: 0.1 mL
Standard sample: Monodispersed polystyrene below (Standard sample: Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation

^For the measurement of ¹³ C-NMR spectrum, “AL-400” manufactured by JEOL Ltd. was used, and the DMSO-d ₆ solution of the sample was analyzed for structural analysis. 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

Production Example 1 Production of Compound (A-1) A 2000 ml 4-necked flask equipped with a cooling tube was charged with 293.2 g of 2,5-xylenol and 122 g of 4-hydroxybenzaldehyde and dissolved in 500 ml of 2-ethoxyethanol. After adding 10 ml of sulfuric acid while cooling in an ice bath, the mixture was heated to 100 ° C. with a mantle heater and reacted for 2 hours. Water was added to the resulting reaction solution to reprecipitate the crude product. The crude product was dissolved in acetone and further reprecipitated with water, and then the precipitate was filtered and dried under vacuum to obtain 213 g of white crystalline compound (A-1). The purity of the compound (A-1) calculated from the GPC chart was 98.2%. A GPC chart of the compound (A-1) is shown in FIG. 1, and a ¹³ C-NMR chart is shown in FIG.

Production Example 2 Production of Compound (A-2) A 100 ml two-necked flask equipped with a cooling tube was charged with 73 g of 2,5-xylenol and 20 g of terephthalaldehyde and dissolved in 300 ml of 2-ethoxyethanol. 10 g of sulfuric acid was added while cooling in an ice bath, and then the reaction was carried out by heating in an oil bath at 80 ° C. for 2 hours. Water was added to the resulting reaction solution to reprecipitate the crude product. The precipitated crude product was dissolved in acetone and further reprecipitated with water, and then the precipitate was filtered and dried under vacuum to obtain 62 g of light red powder compound (A-2). The purity of the compound (A-2) calculated from the GPC chart was 98.2%. A GPC chart of the compound (A-2) is shown in FIG. 3, and a ¹³ C-NMR chart is shown in FIG.

Example 1 Production of Dendrimer Type Resin (1) Into a 1000 ml four-necked flask equipped with a cooling tube, 188 g of compound (A-1) and 318 g of cyclohexanedimethanol divinyl ether were charged and dissolved in 244 g of 1,2-dimethoxyethane. It was. After adding 0.02 g of 37 wt% hydrochloric acid, the mixture was heated to 40 ° C. and reacted for 24 hours. The resulting reaction solution was neutralized by adding triethylamine, and then water was added to reprecipitate the crude product. The crude product was dissolved in methanol and reprecipitated with water, and then the precipitate was separated by filtration and dried under vacuum to obtain 90.4 g of a yellow dendrimer type resin (1). A GPC chart of the dendrimer type resin (1) is shown in FIG. The number average molecular weight (Mn) of the dendrimer type resin (1) was 2,945, the weight average molecular weight (Mw) was 10,972, and the polydispersity (Mw / Mn) was 3.73.

Example 2 Production of Dendrimer Type Resin (2) 188 g of compound (A-1) and 254 g of cyclohexanedimethanol divinyl ether were charged into a 1000 ml four-necked flask equipped with a cooling tube and dissolved in 244 g of 1,2-dimethoxyethane. It was. After adding 0.02 g of 37 wt% hydrochloric acid, the mixture was heated to 40 ° C. and reacted for 24 hours. The resulting reaction solution was neutralized by adding triethylamine, and then water was added to reprecipitate the crude product. The crude product was dissolved in methanol and reprecipitated with water, and then the precipitate was separated by filtration and dried under vacuum to obtain 90.4 g of a yellow dendrimer type resin (2). A GPC chart of the dendrimer type resin (2) is shown in FIG. The number average molecular weight (Mn) of the dendrimer type resin (2) was 6,931, the weight average molecular weight (Mw) was 31,693, and the polydispersity (Mw / Mn) was 4.57.

Example 3 Production of Dendrimer Type Resin (3) A 1000 ml four-necked flask equipped with a cooling pipe was charged with 188 g of compound (A-1), 79 g of compound (A-2), and 273 g of triethylene glycol divinyl ether, It was dissolved in 347 g of 2-dimethoxyethane. After adding 0.02 g of 37 wt% hydrochloric acid, the mixture was heated to 40 ° C. and reacted for 24 hours. The resulting reaction solution was neutralized by adding triethylamine, and then water was added to reprecipitate the crude product. The crude product was dissolved in methanol and reprecipitated with water, and then the precipitate was separated by filtration and dried under vacuum to obtain 90.4 g of a yellow dendrimer type resin (3). A GPC chart of the dendrimer type resin (3) is shown in FIG. The number average molecular weight (Mn) of the dendrimer type resin (3) was 4,063, the weight average molecular weight (Mw) was 33,963, and the polydispersity (Mw / Mn) was 8.36.

Example 4 Production of Dendrimer Type Resin (4) A 1000 ml four-necked flask equipped with a cooling tube was charged with 188 g of compound (A-1), 79 g of compound (A-2) and 214 g of diethylene glycol divinyl ether, and 1,2- Dissolved in 347 g of dimethoxyethane. After adding 0.02 g of 37 wt% hydrochloric acid, the mixture was heated to 40 ° C. and reacted for 24 hours. The resulting reaction solution was neutralized by adding triethylamine, and then water was added to reprecipitate the crude product. The crude product was dissolved in methanol and reprecipitated with water, and then the precipitate was filtered and dried under vacuum to obtain 89.9 g of a yellow dendrimer type resin (4). A GPC chart of the dendrimer type resin (4) is shown in FIG. The number average molecular weight (Mn) of the dendrimer type resin (4) was 5,242, the weight average molecular weight (Mw) was 28,245, and the polydispersity (Mw / Mn) was 5.39.

Example 5 Production of Dendrimer Type Resin (5) A 1000 ml four-necked flask equipped with a cooling tube was charged with 188 g of compound (A-1), 79 g of compound (A-2), and 265 g of cyclohexanedimethanol divinyl ether, It was dissolved in 347 g of 2-dimethoxyethane. After adding 0.02 g of 37 wt% hydrochloric acid, the mixture was heated to 40 ° C. and reacted for 24 hours. The resulting reaction solution was neutralized by adding triethylamine, and then water was added to reprecipitate the crude product. The crude product was dissolved in methanol and further reprecipitated with water, and then the precipitate was filtered and dried under vacuum to obtain 90.2 g of a yellow dendrimer type resin (5). A GPC chart of the dendrimer type resin (5) is shown in FIG. The number average molecular weight (Mn) of the fudendrimer type resin (5) was 3,509, the weight average molecular weight (Mw) was 9,684, and the polydispersity (Mw / Mn) was 2.76.

Example 6 Production of Dendrimer Type Resin (6) A 1000 ml four-necked flask equipped with a cooling pipe was charged with 188 g of compound (A-1), 79 g of compound (A-2) and 318 g of cyclohexanedimethanol divinyl ether, It was dissolved in 347 g of 2-dimethoxyethane. After adding 0.02 g of 37 wt% hydrochloric acid, the mixture was heated to 40 ° C. and reacted for 24 hours. The resulting reaction solution was neutralized by adding triethylamine, and then water was added to reprecipitate the crude product. The crude product was dissolved in methanol and reprecipitated with water, and then the precipitate was separated by filtration and dried under vacuum to obtain 90.3 g of a yellow dendrimer type resin (6). A GPC chart of the dendrimer type resin (6) is shown in FIG. The number average molecular weight (Mn) of the dendrimer type resin (6) was 4,148, the weight average molecular weight (Mw) was 21,515, and the polydispersity (Mw / Mn) was 5.19.

Comparative Production Example 1 Production of Modified Novolak Resin (1 ′) A 2 L four-necked flask equipped with a stirrer and a thermometer was charged with 648 g of metacresol, 432 g of paracresol, 2.5 g of oxalic acid, and 492 g of 42% formaldehyde. The reaction was conducted by heating to 0 ° C. After dehydration and distillation by heating to 200 ° C. under normal pressure conditions, the mixture was further heated to 230 ° C. and distilled under reduced pressure for 6 hours to obtain 736 g of a light yellow solid intermediate novolak resin (1 ′). The number average molecular weight (Mn) of the intermediate novolak resin (1 ′) was 1,526, the weight average molecular weight (Mw) was 12,048, and the polydispersity (Mw / Mn) was 7.9.

  Into a 100 ml two-necked flask equipped with a condenser tube was charged 12.0 g of the intermediate novolak resin (1 ′) obtained in Example 1 and 1.0 g of triethylene glycol divinyl ether, and 50 g of 1,3-dioxolane was obtained. Dissolved in. After adding 0.01 g of 35 wt% hydrochloric acid aqueous solution, reaction was performed at 25 ° C. for 6 hours. After completion of the reaction, 0.1 g of triethylamine was added and further poured into 100 g of ion-exchanged water to precipitate the product. The precipitate was dried under reduced pressure at 80 ° C. and 1.3 kPa to obtain 12.4 g of a modified novolac resin (1 ′). The modified novolak resin (1 ') had a number average molecular weight (Mn) of 1,483, a weight average molecular weight (Mw) of 13,120, and a polydispersity (Mw / Mn) of 8.85.

Examples 7-12 and Comparative Example 1
About the dendrimer type resin obtained in Examples 1-6 and the modified novolak resin obtained in Comparative Production Example 1, the photosensitive composition was prepared in the following manner, and various evaluations were performed. The results are shown in Table 1.

Preparation of photosensitive composition 1.9 g of a dendrimer type resin or a modified novolak resin was dissolved in 8 g of propylene glycol monomethyl ether acetate, and 0.1 g of a photoacid generator was added and dissolved in this solution. This was filtered through a 0.2 μm membrane filter to obtain a photosensitive composition.
As the photoacid generator, “PAI-105” [trifluoromethylsulfonyloxyimino-α- (4-methoxyphenyl) acetonitrile] manufactured by Midori Chemical Co., Ltd. was used.

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

Evaluation of Photosensitivity The photosensitive composition obtained above was applied on a 5 inch silicon wafer with a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110 ° C. for 60 seconds. A mask corresponding to a resist pattern having a line-and-space ratio of 1: 1 and a line width of 1 to 10 μm set every 1 μm is brought into close contact with the wafer, and then a ghi line lamp (“Multi Light” manufactured by USHIO INC. )) Was used for irradiation with ghi rays, and heat treatment was performed at 140 ° C. for 60 seconds. Next, the film was immersed in an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a hot plate at 110 ° C. for 60 seconds.
The ghi-line exposure amount from 20 mJ / cm ² in the case of increased every 5 mJ / cm ^2, a line and space (L / S) = 1/ 1, an exposure amount capable of faithfully reproducing the line width 5 [mu] m (Eop (Exposure amount) was evaluated.

Evaluation of Resolution The photosensitive composition obtained above was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 μm, and dried on a hot plate at 110 ° C. for 60 seconds. A mask corresponding to a resist pattern having a line-and-space ratio of 1: 1 and a line width of 1 to 10 μm set every 1 μm is brought into close contact with the wafer, and then a ghi line lamp (“Multi Light” manufactured by USHIO INC. )) Was used to perform an alkali development operation by irradiating with 200 mJ / cm ^{2 of} ghi line. The pattern state is confirmed using a laser microscope (“VK-X200” manufactured by Keyence Corporation), and A can be resolved under the conditions of line and space (L / S) = 1/1 and line width of 7 μm. Line-and-space (L / S), 1/1 line width of 7 μm, which could not be resolved, was evaluated as B.

Evaluation of heat resistance The photosensitive composition obtained above was applied onto a 5-inch silicon wafer with a spin coater so as to have a thickness of about 1 μm, and dried on a hot plate at 110 ° C. for 60 seconds. A mask corresponding to a resist pattern having a line-and-space ratio of 1: 1 and a line width of 1 to 10 μm set every 1 μm is brought into close contact with the wafer, and then a ghi line lamp (“Multi Light” manufactured by USHIO INC. )) Was used to perform an alkali development operation by irradiating with 200 mJ / cm ^{2 of} ghi line. Use a laser microscope ("VK-X200" manufactured by Keyence Co., Ltd.) to check the pattern state and test what can be resolved under the conditions of line and space (L / S) = 1/1 and line width of 10 µm. A substrate was used. After the test substrate was heated on a hot plate at 120 ° C. for 180 seconds, the pattern state was confirmed with a laser microscope, and a line and space (L / S) = 1/1 and a line width of 10 μm were maintained. The case where the pattern shape was not broken and held was evaluated as B.

Examples 13 to 18 and Comparative Example 2
About the dendrimer type resin obtained in Examples 1-6 and the modified novolak resin obtained in Comparative Production Example 1, curable compositions were prepared in the following manner, and various evaluation tests were performed. The results are shown in Table 2.

Preparation of curable composition 1.6 g of dendrimer type resin or modified novolak resin and 0.4 g of curing agent (“1,3,4,6-tetrakis (methoxymethyl) glycoluril” manufactured by Tokyo Chemical Industry Co., Ltd.) This was dissolved in 3 g of monomethyl ether acetate and filtered through a 0.2 μm membrane filter to obtain a curable composition.

Evaluation of fluidity The curable composition obtained above was applied by a spin coater on a silicon wafer having a resist pattern (pattern width 80 nm, pitch width 240 nm, depth 200 nm) formed on the surface. The coating amount was adjusted so that the film thickness from the resist pattern surface was 100 nm. Heated on a hot plate at 400 ° C. for 2 minutes to obtain a cured coating film. When the surface of the coating film was observed using a scanning electron microscope ("SU3500" manufactured by Hitachi High-Tech) and a smooth surface without unevenness was formed, A, where unevenness due to the resist pattern was observed Evaluated as B.

Claims (6)

The following structural formula (1)

[Wherein k is 0 or 1; R ¹ is an aliphatic hydrocarbon group which may have a substituent, an alkoxy group, or a halogen atom, and l is an integer of 0 or 1-5. R ² is an aliphatic hydrocarbon group which may have a substituent, an alkoxy group, or a halogen atom, and m is 0 or an integer of 1 to 4. R ³ is a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. n is 1 or 2. ]
A dendrimer type resin that is a reaction product of the compound (A) represented by formula (I) and the divinyl compound (B). The ratio [(OH) / (V)] of the number of moles of phenolic hydroxyl group (OH) in the reaction raw material to the number of moles of vinyl group (V) in the divinyl compound (B) is 1/1/1/0. The dendrimer type resin according to claim 1, which is in a range of .1. A photosensitive composition comprising the dendrimer-type resin according to claim 1 and a photoacid generator. A curable composition comprising the dendrimer-type resin according to claim 1 or 2 and a curing agent. A cured product of the curable composition according to claim 4. A resist material using the dendrimer type resin according to claim 1.

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