JP2009191013A - Methylol phenol compound, resin composition using the same and cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curing agent (crosslinking agent) which can be used for producing a cured product being satisfactory in both mechanical characteristics and heat resistance of, a resin composition and a resin cured product. <P>SOLUTION: The resin composition comprises (a) a phenolic hydroxy group-containing resin and (b) a methylol phenol compound represented by general formula (I) (wherein R<SP>1</SP>-R<SP>4</SP>are each independently a hydrogen atom or a monofunctional organic group; X is a 1-20C alkylene chain; m and n are each a positive number of 1 to 4; p is an integer of 0 to 4-m; and q is an integer f 0 to 4-n). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a methylolphenol compound, a resin composition using the methylolphenol compound, and a cured product that is not brittle and has high heat resistance using the resin composition.

  Since methylolphenol compounds (resole resins) are highly reactive, they are used as curing agents for phenolic resins (novolak resins) as well as aldehydes and amines (see, for example, Patent Document 1). Utilizing such characteristics, methylolphenol compounds are also used as crosslinking agents for photosensitive polybenzoxazole resins. Such a photosensitive resin has excellent heat resistance, electrical characteristics, mechanical characteristics and the like, and is used for a surface protective film and an interlayer insulating film of a semiconductor element. In Patent Document 2, a bisphenol-type methylol compound having an alkylene bond or an ether bond has been studied in order to improve the mechanical properties of the cured photosensitive polybenzoxazole resin.

JP 7-309995 A JP 2007-79264 A

  The bisphenol-type methylol compound having an alkylene chain improves the mechanical properties (toughness) of the cured product due to the flexibility of the alkylene chain. However, there is a problem that the alkylene chain in the molecule causes a decrease in heat resistance.

  The present invention was made in order to solve the conventional problems as described above, and a curing agent (crosslinking agent) capable of achieving both mechanical properties and heat resistance of a cured product, a resin composition, And a cured resin product.

  In order to solve the above problems, the present inventors have conducted extensive research. As a result, when a bisphenol-type methylol compound having an amide bond and an alkylene chain is used as a curing agent, the mechanical properties and heat resistance of the cured product are compatible. As a result, the present invention has been completed.

  That is, the methylolphenol compound of the present invention is represented by the general formula (I).

（式中、Ｒ^１〜Ｒ^４は各々独立に水素原子又は一価の有機基を示し、Ｘは炭素数１から２０までのアルキレン鎖であり、ｍおよびｎはそれぞれ独立に１から４までの正数であり、ｐは０から４−ｍの整数であり、ｑは０から４−ｎの整数である。）

(Wherein R ^{1 to} R ⁴ each independently represent a hydrogen atom or a monovalent organic group, X is an alkylene chain having 1 to 20 carbon atoms, and m and n are each independently 1 to 4) (It is a positive number, p is an integer from 0 to 4-m, and q is an integer from 0 to 4-n.)

  In addition, the resin composition of the present invention is characterized by comprising (a) a resin having a phenolic hydroxyl group and (b) a methylolphenol compound represented by the general formula (I).

  Moreover, in the resin composition of this invention, it is preferable that said (a) resin which has a phenolic hydroxyl group is a phenol resin.

  Moreover, in the resin composition of this invention, it is preferable that (a) resin which has a phenolic hydroxyl group is a compound which has a repeating unit represented by general formula (II).

（式中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す。）

(In the formula, U represents a tetravalent organic group, and V represents a divalent organic group.)

  Moreover, in the resin composition of this invention, it is preferable to mix | blend 1-50 weight part of said (b) component with respect to 100 weight part of said (a) component.

  Moreover, in the resin composition of this invention, it is preferable that the said resin composition further contains (c) o-quinonediazide compound.

  In the resin composition of the present invention, 1 to 50 parts by weight of the component (b) and 5 to 100 parts by weight of the component (c) are blended with 100 parts by weight of the component (a). It is preferable that

  Moreover, in the hardened | cured material of this invention, it is a hardened | cured material formed by hardening | curing the said resin composition, It is characterized by the above-mentioned.

  The methylolphenol compound according to the present invention is novel, having an amide bond and an alkylene chain. The resin composition according to the present invention contains a methylolphenol compound having an amide bond and an alkylene chain as a curing agent, and the cured product is excellent in mechanical properties and heat resistance.

  Furthermore, the resin composition according to the present invention further contains a photosensitizer, and the methylolphenol compound of the present invention has an adverse effect on the difference in dissolution rate (dissolution contrast) between the exposed portion and the unexposed portion of the developer. Excellent sensitivity and resolution. Furthermore, the cured product is excellent in mechanical properties and heat resistance.

Hereinafter, embodiments of a methylolphenol compound, a resin composition, and a cured product according to the present invention will be described in detail. In addition, this invention is not limited by this embodiment.
[Methylolphenol compounds]
First, the methylol phenol compound according to the present invention will be described.
The methylolphenol compound according to the present invention is represented by the following general formula (I).

（式中、Ｒ^１〜Ｒ^４は各々独立に水素原子又は一価の有機基を示し、Ｘは炭素数１から２０までのアルキレン鎖であり、ｍおよびｎはそれぞれ独立に１から４までの正数であり、ｐは０から４−ｍの整数であり、ｑは０から４−ｎの整数である。）

(Wherein R ^{1 to} R ⁴ each independently represent a hydrogen atom or a monovalent organic group, X is an alkylene chain having 1 to 20 carbon atoms, and m and n are each independently 1 to 4) (It is a positive number, p is an integer from 0 to 4-m, and q is an integer from 0 to 4-n.)

In the above formula (I), R ¹ is a hydrogen atom or a monovalent organic group, and more specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, s- A butyl group, a t-butyl group, etc., a C1-C20 alkyl group, a C1-C20 perfluoroalkyl group, an allyl group, a vinyl group, a cyclopentyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, Fluorine group, chlorine group, bromine group, iodine group, silyl group, acyl group, methoxy group and the like.

In the above formula (I), R ² is a hydrogen atom or a monovalent organic group, and more specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, s- A butyl group, a t-butyl group, etc., a C1-C20 alkyl group, a C1-C20 perfluoroalkyl group, an allyl group, a vinyl group, a cyclopentyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, Fluorine group, chlorine group, bromine group, iodine group, silyl group, acyl group, methoxy group and the like.

In the above formula (I), R ³ is a hydrogen atom or a monovalent organic group, and more specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, s- A butyl group, a t-butyl group, etc., a C1-C20 alkyl group, a C1-C20 perfluoroalkyl group, an allyl group, a vinyl group, a cyclopentyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, A methoxyethyl group, a methoxymethyl group, an ethoxymethyl group, and the like;

In the above formula (I), R ⁴ is a hydrogen atom or a monovalent organic group, and more specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, s- A butyl group, a t-butyl group, etc., a C1-C20 alkyl group, a C1-C20 perfluoroalkyl group, an allyl group, a vinyl group, a cyclopentyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, A methoxyethyl group, a methoxymethyl group, an ethoxymethyl group, and the like;

  In the above formula (I), p is an integer from 0 to 4-m (m is described later), q is an integer from 0 to 4-n (n is described later), and more specifically 0 or 1.

  In the above formula (I), m is a positive number from 1 to 4, and is preferably 1 to 2 from the balance of the stability of the compound, the ease of synthesis, and the mechanical properties and heat resistance of the cured resin. N is a positive number from 1 to 4, and is preferably 1 or 2 from the balance of stability of the compound, ease of synthesis, and mechanical properties and heat resistance of the cured resin.

Further, in the above formula (I), the substitution position of the substituent R ³ OCH ₂ — or R ⁴ OCH ₂ — is not limited, but from the viewpoint of ease of synthesis and reactivity as a curing agent, ortho of a phenolic hydroxyl group. Is preferred.

  In the above formula (I), X is an alkylene chain having 1 to 20 carbon atoms, and more specifically, methylene, 1,1-ethylene, 1,2-ethylene, 1,3-propylene, , 2-propylene, 2,2-propylene (isopropylidene), 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9 -Nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 1,13-tridecylene, 1,14-tetradecylene and the like.

  In the present invention, the alkylene chain may be linear or branched. A part of the alkylene chain may be a carbon-carbon double bond. In the above formula (I), the substitution position of the substituent —NHCO—X—CONH— is not limited, and may be any of the ortho position, the meta position, and the para position of the phenolic hydroxyl group.

  Although there is no restriction | limiting in the synthesis | combining method of the methylol phenol compound by this invention shown to the said general formula (I), Specifically, the synthesis method shown to following formula (III) can be mentioned.

  First, a dicarboxylic acid or dicarboxylic acid chloride having an alkylene chain is allowed to act on a substituted or unsubstituted aminophenol to synthesize an intermediate bisphenol compound. Here, the substituted or unsubstituted aminophenol is added in the range of 1.5 to 3.0 moles with respect to 1 mole of the dicarboxylic acid or dicarboxylic acid chloride having an alkylene chain. The reaction temperature is appropriately selected within the range of -20 ° C to 200 ° C. The reaction time is appropriately selected within the range of 1 minute to 1 week. In addition, a solvent is preferably used for the reaction, and a hydrocarbon solvent, a halogen solvent, an ether solvent, a ketone solvent, an amide solvent, or the like is used. Furthermore, a catalyst can be used for the reaction, and a mineral acid, an organic acid, an alkaline base, an organic base, a dehydrating condensing agent, or the like is used. The reactive organism can proceed to the next step without isolation. Further, it can be purified by neutralization, extraction, recrystallization, distillation, chromatography or the like.

  Next, the target methylolphenol compound is synthesized by allowing formaldehyde or an equivalent thereof (such as a hydrate or a cyclic trimer) to act on the bisphenol compound obtained in the above-described step. Here, formaldehyde or an equivalent thereof is added in the range of 0.5 to 10 moles per mole of the intermediate bisphenol compound. The reaction temperature is appropriately selected within the range of 0 ° C to 100 ° C. The reaction time is appropriately selected within the range of 1 minute to 1 month. In addition, a solvent may be used for the reaction, and water, a hydrocarbon solvent, a halogen solvent, an alcohol solvent, an ether solvent, a ketone solvent, an ester solvent, an amide solvent, a sulfoxide solvent, or the like is used. Furthermore, a catalyst can be used for the reaction, and a mineral acid, an organic acid, an alkaline base, an organic base, or the like is used. Reactive organisms are purified by neutralization, extraction, recrystallization, distillation, chromatography, etc. as necessary.

The methylol group of the obtained methylolphenol compound is etherified by a known method as necessary.
The product may be a compound having a single methylol group substitution position or number of substituents, or may be a mixture of compounds having different methylol group substitution positions or different numbers of substituents.

[Resin composition]
Next, the resin composition according to the present invention will be described.
The resin composition according to the present invention is a resin composition containing (a) a resin having a phenolic hydroxyl group and (b) a methylolphenol compound represented by the following general formula (I). Hereinafter, each component contained in the resin composition will be described.

（式中、Ｒ^１〜Ｒ^４は各々独立に水素原子又は一価の有機基を示し、Ｘは炭素数１から２０までのアルキレン鎖であり、ｍおよびｎはそれぞれ独立に１から４までの正数であり、ｐは０から４−ｍの整数であり、ｑは０から４−ｎの整数である。）

(Wherein R ^{1 to} R ⁴ each independently represent a hydrogen atom or a monovalent organic group, X is an alkylene chain having 1 to 20 carbon atoms, and m and n are each independently 1 to 4) (It is a positive number, p is an integer from 0 to 4-m, and q is an integer from 0 to 4-n.)

<(A) component>
The component (a) is a resin having a phenolic hydroxyl group in the molecule. Specific examples thereof include phenol resin, polybenzoxazole precursor (poly (hydroxyamide)), poly (hydroxyphenylene) ether, polynaphthol, poly (hydroxystyrene) and the like.

  Among these, a phenol resin (especially a novolak type phenol resin) is preferable because of cost reduction and small volume shrinkage at the time of curing. A polybenzoxazole precursor (poly (hydroxyamide)) is preferred because of its excellent heat resistance and electrical properties (insulating properties).

(Phenolic resin)
As a phenol resin, what is obtained by condensing (reaction) a phenol derivative and aldehydes in presence of catalysts, such as an acid or a base, can be used, for example. Among these, a phenol resin obtained when an acid catalyst is used is particularly referred to as a novolac type phenol resin.

  Examples of the phenol derivative used for obtaining the phenol resin include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, and m-butylphenol. P-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, Alkylphenols such as 3,4,5-trimethylphenol, alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol, alkenylphenols such as vinylphenol and allylphenol, and aralkylphenols such as benzylphenol Alkoxycarbonylphenol such as methoxycarbonylphenol, arylcarbonylphenol such as benzoyloxyphenol, halogenated phenol such as chlorophenol, polyhydroxybenzene such as catechol, resorcinol, pyrogallol, bisphenol such as bisphenol A and bisphenol F, α- or β -Naphthol derivatives such as naphthol. Further, methylolated products of the above phenol derivatives such as bishydroxymethyl-p-cresol may be used as the phenol derivative.

  Examples of the phenol derivative include hydroxyalkylphenols such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol and p-hydroxyphenyl-4-butanol, hydroxyalkylcresols such as hydroxyethylcresol, and bisphenol. Monoethylene oxide adducts, alcoholic hydroxyl group-containing phenol derivatives such as bisphenol monopropylene oxide adducts, p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid, hydroxy Also included are carboxyl group-containing phenol derivatives such as benzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid and diphenolic acid.

Furthermore, the phenol resin may be a condensation polymerization product of the above-described phenol derivative and a compound other than phenol such as m-xylene. In this case, the molar ratio of the compound other than phenol to the phenol derivative used for the condensation polymerization is preferably less than 0.5.
Compounds other than the above-described phenol derivatives and phenol compounds are used singly or in combination of two or more.

  Examples of aldehydes include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, acetone and glyceraldehyde. Examples of aldehydes include glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate, pyruvic acid, repric acid. 4-acetyl butyric acid, acetone dicarboxylic acid, and 3,3′-4,4′-benzophenone tetracarboxylic acid. Further, a formaldehyde precursor such as paraformaldehyde or trioxane may be used. These are used singly or in combination of two or more.

(Polybenzoxazole precursor)
The polybenzoxazole precursor is a polyamide having a phenolic hydroxyl group (poly (hydroxyamide)), and specifically, a compound having a repeating unit represented by the following general formula (II).

（式中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す。）

(In the formula, U represents a tetravalent organic group, and V represents a divalent organic group.)

  The poly (hydroxyamide) represented by the general formula (II) is finally converted into polybenzoxazole having excellent heat resistance, mechanical properties, and electrical properties by dehydration and ring closure at the time of curing.

In the present invention, the compound (polyamide) having a repeating unit represented by the general formula (II) can be generally synthesized from a dicarboxylic acid derivative and a hydroxy group-containing diamine. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the diamines. As the dihalide derivative, a dichloride derivative is preferable.
The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorination reaction of carboxylic acid can be used.

  As a method of synthesizing the dichloride derivative, it can be synthesized by reacting the dicarboxylic acid derivative and the halogenating agent in a solvent, or reacting in an excess halogenating agent and then distilling off the excess. As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

  The amount of these halogenating agents to be used in a solvent is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol, relative to 1.0 mol of the dicarboxylic acid derivative. Preferably, when making it react in a halogenating agent, 4.0-50 mol is preferable and 5.0-20 mol is more preferable. The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

  The reaction between the dichloride derivative and the diamine is preferably performed in an organic solvent in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used. As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used. The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

(Aminophenol)
Here, in formula (II), the tetravalent organic group represented by U is generally a residue derived from dihydroxydiamine that reacts with dicarboxylic acid to form a polyamide structure, and is a tetravalent aromatic group. A group having 6 to 40 carbon atoms is preferable, and a tetravalent aromatic group having 6 to 40 carbon atoms is more preferable. As the tetravalent aromatic group, a residue of diamine having a structure in which all four bonding sites are present on the aromatic ring and each of the two hydroxy groups is located at the ortho position of the amine is preferable.

  Such diamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 2,2-bis (3-amino-4- Hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2, 2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1, 1,3,3,3-hexafluoropropane, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene, 9,9-bis {4- (3-amino-4-hydro) Ciphenoxy) phenyl} fluorene, 1,3-bis (3-amino-4-hydroxyphenyl) adamantane, 1,3-bis {4- (3-amino-4-hydroxyphenoxy) phenyl} adamantane, 2,2- Examples include bis (3-amino-4-hydroxyphenyl) adamantane, 2,2-bis {4- (3-amino-4-hydroxyphenoxy) phenyl} adamantane, but are not limited thereto. These compounds can be used alone or in combination of two or more.

Among the above diamines, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) ) Sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2, Like 2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, bis (aromatic orthohydroxylamine) is sp ³ carbon atom, sulfur atom, Diamines bonded to atoms such as oxygen atoms are molecules with moderate flexibility, and are characterized by dehydration and ring closure at relatively low temperatures, and are also resistant to heat from aromatic groups. It is more preferable at the point which has the property.

  A part of the aminopheno can be replaced with a diamine having no phenolic hydroxyl group. Examples of such diamines include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p. -Phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4 As an aromatic diamine compound such as-(4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene, and other diamines containing a siloxane skeleton, LP-7100, X-22- 161AS, X-22-161A, X-2 -161B, X-22-161C, and X-22-161E (both Shin-Etsu Chemical Co., Ltd., trade name), but like, but is not limited thereto. These compounds can be used alone or in combination of two or more.

(Dicarboxylic acid)
In the general formula (II), the divalent organic group represented by V is a residue derived from dicarboxylic acid that reacts with diamine to form a polyamide structure, and is preferably a divalent aromatic group. The number of carbon atoms is preferably 6 to 40, and more preferably a divalent aromatic group having 6 to 40 carbon atoms. As the divalent aromatic group, those in which two bonding sites are both present on the aromatic ring are preferred.

  Examples of such dicarboxylic acids include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 4,4′-dicarboxybiphenyl. 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 9,9-bis (4-carboxyphenyl) fluorene, 9,9-bis {4- (3 Or 4-carboxyphenoxy) phenyl} fluorene, 1,3-bis (4-carboxyphenyl) adaman 1,3-bis {4- (3 or 4-carboxyphenoxy) phenyl} adamantane, 2,2-bis (4-carboxyphenyl) adamantane, 2,2-bis {4- (3 or 4-carboxyphenoxy) ) Aromatic dicarboxylic acids such as phenyl} adamantane, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, and other aliphatic systems Examples thereof include, but are not limited to, dicarboxylic acids. These compounds can be used alone or in combination of two or more.

Among the above dicarboxylic acids, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxy As in tetraphenylsilane, bis (4-carboxyphenyl) sulfone, and 2,2-bis (p-carboxyphenyl) propane, bis (aromatic carboxylic acid) is an atom such as sp ³ carbon atom, sulfur atom, oxygen atom, etc. The dicarboxylic acids bonded to are more preferable because they are molecules having moderate flexibility and are characterized in that dehydration ring closure occurs at a relatively low temperature and also have heat resistance derived from an aromatic group.

  Further, although dicarboxylic acids of the following formulas (IV) and (V) are not aromatic, they can be cited as preferred examples in that dehydration and ring closure occurs at a relatively low temperature because they are molecules having moderate flexibility.

（式中、Ｚは炭素数１〜６の炭化水素基を表す。）

(In the formula, Z represents a hydrocarbon group having 1 to 6 carbon atoms.)

  Furthermore, dicarboxylic acids represented by the following formula (VI) can also be exemplified.

（式中、Ｚは炭素数１〜６の炭化水素基であり、Ｍは単結合又は２価の基又は原子、例えば−ＣＨ_２−，−Ｃ（ＣＨ_３）_２−，−Ｏ−，−Ｓ−，−ＳＯ_２−，−ＣＯ−，−（ＣＦ_３）_２−等であり、Ｘは下記の一般式（ＶＩＩ）で表される。）

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, M is a single bond or a divalent group or atom, for example, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, — S—, —SO ₂ —, —CO—, — (CF ₃ ) ₂ — and the like, and X is represented by the following general formula (VII).

（式中、ｎは１〜６の整数を表す。）

(In the formula, n represents an integer of 1 to 6.)

In General Formula (VIII), R ¹¹ and R ¹⁶ are each independently a divalent organic group, R ^{12 to} R ¹⁵ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and m is 1 to 100. Represents an integer. Examples of the divalent organic group of R ¹¹ and R ^{16 and} the monovalent organic group of R ^{12 to} R ¹⁵ include a hydrocarbon group having 1 to 10 carbon atoms (an alkyl group, an alkylene group, etc.), an alkyl ether group, and a fluoroalkyl group. Group, fluoroalkyl ether group, phenyl group and the like, and the repeating unit number a is 1 to 100.

  Although there is no restriction | limiting in the molecular weight of (a) component, In consideration of the physical property of a hardened | cured material, compatibility, and the solubility with respect to a developing solution when using as a photosensitive resin, it is 1,000-1,000,000 in a weight average molecular weight. Is preferable, and 1,000 to 100,000 is more preferable. Here, the molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

<(B) component>
The component (b) is a methylolphenol compound, which acts as a curing agent and reacts with, or bridges with, a resin having a phenolic hydroxyl group at the time of curing. The methylolphenol compound used in the present invention is represented by the general formula (I).

（式中、Ｒ^１〜Ｒ^４は各々独立に水素原子又は一価の有機基を示し、Ｘは炭素数１から２０までのアルキレン鎖であり、ｍおよびｎはそれぞれ独立に１から４までの正数であり、ｐは０から４−ｍの整数であり、ｑは０から４−ｎの整数である。）

(Wherein R ^{1 to} R ⁴ each independently represent a hydrogen atom or a monovalent organic group, X is an alkylene chain having 1 to 20 carbon atoms, and m and n are each independently 1 to 4) (It is a positive number, p is an integer from 0 to 4-m, and q is an integer from 0 to 4-n.)

  Since the methylolphenol compound used in the present invention has an alkylene chain in the molecule, it is excellent in mechanical properties (toughness and flexibility) of the cured product. Moreover, since it has an amide bond at the same time, the heat resistance of the cured product is also excellent.

In the above formula (I), R ¹ is a hydrogen atom or a monovalent organic group, and more specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, s- A butyl group, a t-butyl group, etc., a C1-C20 alkyl group, a C1-C20 perfluoroalkyl group, an allyl group, a vinyl group, a cyclopentyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, Fluorine group, chlorine group, bromine group, iodine group, silyl group, acyl group, methoxy group and the like.

In the above formula (I), R ² is a hydrogen atom or a monovalent organic group, and more specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, s- A butyl group, a t-butyl group, etc., a C1-C20 alkyl group, a C1-C20 perfluoroalkyl group, an allyl group, a vinyl group, a cyclopentyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, Fluorine group, chlorine group, bromine group, iodine group, silyl group, acyl group, methoxy group and the like.

In the above formula (I), R ³ is a hydrogen atom or a monovalent organic group, and more specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, s- A butyl group, a t-butyl group, etc., a C1-C20 alkyl group, a C1-C20 perfluoroalkyl group, an allyl group, a vinyl group, a cyclopentyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, A methoxyethyl group, a methoxymethyl group, an ethoxymethyl group, and the like;

In the above formula (I), R ⁴ is a hydrogen atom or a monovalent organic group, and more specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, s- A butyl group, a t-butyl group, etc., a C1-C20 alkyl group, a C1-C20 perfluoroalkyl group, an allyl group, a vinyl group, a cyclopentyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, A methoxyethyl group, a methoxymethyl group, an ethoxymethyl group, and the like;

In the above formula (I), p is an integer from 0 to 4-m (m is described later), q is an integer from 0 to 4-n (n is described later), and more specifically 0 or 1.
In the above formula (I), m is a positive number from 1 to 4, and is preferably 1 to 2 from the balance of the stability of the compound, the ease of synthesis, and the mechanical properties and heat resistance of the cured resin. N is a positive number from 1 to 4, and is preferably 1 or 2 from the balance of stability of the compound, ease of synthesis, and mechanical properties and heat resistance of the cured resin.

Further, in the above formula (I), the substitution position of the substituent R ³ OCH ₂ — or R ⁴ OCH ₂ — is not limited, but from the viewpoint of ease of synthesis and reactivity as a curing agent, ortho of a phenolic hydroxyl group. Is preferred.

  In the above formula (I), X is an alkylene chain having 1 to 20 carbon atoms, and more specifically, methylene, 1,1-ethylene, 1,2-ethylene, 1,3-propylene, , 2-propylene, 2,2-propylene (isopropylidene), 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9 -Nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 1,13-tridecylene, 1,14-tetradecylene and the like.

  In the present invention, the alkylene chain may be linear or branched. A part of the alkylene chain may be a carbon-carbon double bond. In the above formula (I), the substitution position of the substituent —NHCO—X—CONH— is not limited, and may be any of the ortho position, the meta position, and the para position of the phenolic hydroxyl group. Further, the compound may have a single methylol group substitution position and number of substituents, or may be a mixture of compounds having different methylol group substitution positions and number of substituents and methylene chains (X in formula (I)). Good.

  In the resin composition of the present invention, the blending amount of the component (b) is based on the physical properties of the cured product and in consideration of the photosensitive characteristics when used as a photosensitive resin, with respect to 100 parts by weight of the component (a). 1-50 weight part is preferable and 3-30 weight part is more preferable.

<(C) component>
In the resin composition of the present invention, in addition to the components (a) and (b), (c) an o-quinonediazide compound may be blended. This o-quinonediazide compound is a photosensitizer and has a function of generating carboxylic acid upon irradiation with light and increasing the solubility of the irradiated portion in an alkaline aqueous solution. Since both the components (a) and (b) of the present invention have a phenolic hydroxyl group in the molecule, solubility in an alkaline aqueous solution can be expected. Therefore, by combining (c) in addition to the components (a) and (b), an alkaline aqueous solution developing positive photosensitive resin is obtained.

  The o-quinonediazide compound used in the present invention can be obtained, for example, by subjecting o-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent. Examples of the o-quinonediazide sulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. Etc. can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,3,4-trihydroxybenzophenone. 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4, 3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro -1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2, -a] indene, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane can be used.

  Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl sulfide. , O-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3- Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis ( 3-amino-4-hydroxyphenyl) hexafluo Propane, and bis (4-amino-3-hydroxyphenyl) hexafluoropropane can be used.

  The o-quinonediazide sulfonyl chloride and the hydroxy compound and / or amino compound may be blended so that the total of hydroxy group and amino group is 0.5 to 1 equivalent with respect to 1 mol of o-quinonediazide sulfonyl chloride. preferable. A preferred ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95. A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 10 hours.

  As the reaction solvent, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used. Examples of the dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

  In the resin composition of the present invention, the blending amount of the component (c) is 5 to 100 with respect to 100 parts by weight of the component (a) in terms of the difference in dissolution rate between the exposed part and the unexposed part and the allowable range of sensitivity. Part by weight is preferable, and 8 to 40 parts by weight is more preferable. Moreover, when (b) component is considered, it is preferable to mix | blend (b) component 1-50 weight part and (c) component 5-100 weight part with respect to (a) component 100 weight part.

<Solvent>
In the present invention, a solvent may be blended in addition to the components (a) to (c) described above. The solvent is used to improve the compatibility of each component or to give processability. Solvents include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N, N -Dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, methyl ethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol Examples thereof include monobutyl ether and dipropylene glycol monomethyl ether.
These solvents can be used alone or in combination of two or more. The amount of the solvent is not particularly limited, but it is generally preferable to adjust the solvent so that the proportion of the solvent in the photosensitive resin composition is 20 to 90% by weight.

[Cured product]
Next, the cured product according to the present invention will be described.
A cured product can be obtained by heat-treating the above-described resin composition of the present invention. Although there is no restriction | limiting in the heating temperature in a heat processing process, Preferably it is 300 degrees C or less, More desirably, it is 250 degrees C or less, More desirably, it is the range of 140-200 degreeC.
Further, the heat treatment is performed using a quartz tube furnace, a hot plate, rapid thermal annealing, an infrared curing furnace, and a microwave curing furnace, and can be selected in the air or in an inert atmosphere such as nitrogen.

The heat treatment time in the heat treatment step of the present invention is the time until the resin composition is cured, but is preferably about 5 hours or less in view of work efficiency.
In addition, the shape of the hardened | cured material of this invention does not have a restriction | limiting, such as a thin film form, plate shape, or block shape. Moreover, the hardened | cured material of this invention may be formed independently or on the surface or inside of equipment.
As described above, the cured product of the present invention is obtained. Since the cured product of the present invention uses the methylolphenol compound of the present invention, it is excellent in mechanical properties (toughness and flexibility) and heat resistance.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.
(Synthesis Example 1)
Synthesis of N, N′-bis (4-hydroxyphenyl) -1,3-diamidepropane (2) 12.0 g of p-Aminophenol was placed in a 100 ml two-necked flask and dissolved in 50 ml of NMP. Next, 16.7 ml of Et ₃ N was added, and finally 6.40 ml of Glutaryl dichloride (1) was added dropwise. The mixture was stirred at room temperature (25 ° C.) for 74 hours.
NMP was distilled off under reduced pressure, water was added to the residue, and suction filtration was performed with a membrane filter. The filtrate was dissolved in methanol and dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was filtered off, the solvent was distilled off by a rotary evaporator. Then, it reprecipitated with ethanol / hexane. By suction filtration, 12.3 g (yield 78%) of pale purple powder N, N′-bis (4-hydroxyphenyl) -1,3-diamidepropane (2) was obtained. Melting point 231-234 ° C. (literature value 232-235 ° C.). See the following formula (IX) and Table 1 below.
¹ H-NMR (CD ₃ OD, 500 MHz); δ (ppm) = 6.72 (4H, d, J = 9.0 Hz, Ar—H), 7.32 (4H, d, J = 9.0 Hz) _{Ar-H), 2.05 (2H} , quintet, -CH 2 -), 2.41 (4H, t, -CH 2 -).

Example 1
Synthesis of N, N′-bis {4-hydroxy-3,5-bis (hydroxymethyl) phenyl} -1,3-diamidopropane (3) [methylolphenol compound]

6.29 g of N, N′-bis (4-hydroxyphenyl) -1,3-diamidepropane (2) was put in a 500 ml eggplant-shaped flask and dissolved in 300 ml of MeOH. 15.2 ml of 10% NaOHaq was added, and 7.44 ml of 37% HCHOaq was added under ice cooling. The progress of the reaction was confirmed by silica gel TLC (AcOEt: MeOH = 3: 1). As necessary, 7.44 ml (100 mmol) of 37% HCHOaq was added once, 14.9 ml (200 mmol) was added three times, and 29.8 ml (400 mmol) was added three times. After reacting at room temperature (25 ° C.) for 181 hours, the mixture was stirred at 50 ° C. for 85 hours.
The mixture was neutralized with 10% HClaq under ice cooling. The solvent was distilled off. Dissolved in methanol and the undissolved precipitate was filtered off. Further, the solvent was distilled off.
The product was separated into two types from a 2-substituted product to a 4-substituted product and from a 3-substituted product to a 4-substituted product by silica gel column chromatography (developing solvent AcOEt: MeOH = 9: 1). Red oily substance N, N′-bis {4-hydroxy-3,5-bis (hydroxymethyl) phenyl} -1,3-diamidepropane (3), 1.78 g and 1.42 g, respectively (crude yield 37 %). See the following formula (X) and Table 2 below.
FIG. 1 shows a ¹ H-NMR (CD ₃ OD) spectrum of N, N′-bis {4-hydroxy-3,5-bis (hydroxymethyl) phenyl} -1,3-diamidepropane (3).

(Reference Synthesis Example 1)
Synthesis of Suberic Acid Chloride (9) 17.4 g of Subic acid (8) was placed in a 200 ml three-necked flask. 72.6 ml of Thionyl chloride was added and refluxed for 2 hours.
Thionyl chloride added excessively was distilled off under reduced pressure. A brown liquid, 17.2 g (crude yield 81%) was obtained. See the following formula (XI) and Table 3 below.

(Synthesis Example 2)
Synthesis of N, N′-bis (4-hydroxyphenyl) -1,3-diamidohexane (10) 16.4 g of p-Aminophenol was placed in a 300 ml three-necked flask and dissolved in 120 ml of NMP. Next, 20.9 ml of Et ₃ N was added, and finally 17.2 g of suberic acid chloride (9) was added dropwise. Stir at room temperature (25 ° C.) for 18 hours.
NMP was distilled off under reduced pressure, water was added to the residue, and suction filtration was performed. Then, it reprecipitated with ethanol / hexane. By suction filtration, 23.5 g (yield 88%) of pink powder N, N′-bis (4-hydroxyphenyl) -1,3-diamidehexane (10) was obtained. Mp 218-222 ° C. See the following formula (XII) and Table 4 below.
¹ H-NMR (DMSO, 500 MHz); δ (ppm) = 6.64 (4H, d, J = 9.0 Hz, Ar—H), 7.32 (4H, d, J = 9.0 Hz, Ar— _{H), 1.29 (4H, quintet} , -CH 2 -), 1.56 (4H, quintet, -CH 2 -), 2.22 (4H, t, -CH 2 -).

(Example 2)
Synthesis of N, N′-bis {4-hydroxy-3,5-bis (hydroxymethyl) phenyl} -1,3-diamidohexane (11) [methylolphenol compound] N, N′-bis in a 1000 ml two-necked flask 14.3 g of (4-hydroxyphenyl) -1,3-diamidohexane (10) was added and 44.8 g of 10% KOHaq was added. Dissolved in 150 ml MeOH. 29.8 ml of 37% HCHOaq was added under ice cooling. Progress of the reaction was confirmed by silica gel TLC (AcOEt: MeOH = 14: 1). 37% HCHOaq 29.8 ml (400 mmol) was added once. The mixture was stirred at 50 ° C. for 233 hours.
The mixture was neutralized with 10% HClaq under ice cooling. The solvent was distilled off. Dissolved in methanol and the undissolved precipitate was filtered off. Further, the solvent was distilled off.
The 4-substituted product was separated from the 3-substituted product by silica gel column chromatography (developing solvent AcOEt: MeOH = 14: 1). N, N′-bis {4-hydroxy-3,5-bis (hydroxymethyl) phenyl} -1,3-diamidohexane (11), 2.89 g (crude yield 15%), was obtained as a brown oily substance. . See the following formula (XIII) and Table 5 below.
FIG. 2 shows the ¹ H-NMR (CD ₃ OD) spectrum of N, N′-bis {4-hydroxy-3,5-bis (hydroxymethyl) phenyl} -1,3-diamidohexane (11).

(Reference Synthesis Example 2)
Synthesis of dodecanedioic acid chloride (5) 12.5 g of dodecanedioic acid (4) was placed in a 200 ml three-necked flask. 39.4 ml of Thionyl chloride was added and refluxed for 3 hours.
Thionyl chloride added excessively was distilled off under reduced pressure. 13.5 g (crude yield 92%) of a yellow liquid was obtained. See the following formula (XIV) and Table 6 below.

(Synthesis Example 3)
Synthesis of N, N′-bis (4-hydroxyphenyl) -1,3-diamidedecane (6) 12.0 g of p-Aminophenol was placed in a 300 ml eggplant type flask and dissolved in 100 ml of NMP. Next, 16.7 ml of Et ₃ N was added, and finally, 12.7 ml of Dodecanedioyl dichloride (5) was added dropwise. The mixture was stirred at room temperature (25 ° C.) for 118 hours.
NMP was distilled off under reduced pressure, water was added to the residue, and suction filtration was performed. Reprecipitate with ethanol / hexane. By suction filtration, 14.2 g (yield 69%) of a brown powder was obtained. Melting point: 189-191 ° C. See the following formula (XV) and Table 7 below.
¹ H-NMR (CD ₃ OD, 500 MHz); δ (ppm) = 6.72 (4H, d, J = 8.5 Hz, Ar—H), 7.30 (4H, d, J = 8.5 Hz, _{Ar-H), 1.32~1.35 (12H} , m, -CH 2 -), 1.67 (4H, quintet, -CH 2 -), 2.29~2.37 (4H, dt, - CH ₂ -).

(Example 3)
Synthesis of N, N′-bis {4-hydroxy-3,5-bis (hydroxymethyl) phenyl} -1,3-diamidedecane (7) N, N′-bis (4-hydroxyphenyl) in a 500 ml eggplant type flask 8.25 g of -1,3-diamidedecane (6) was added, and 22.4 g of 10% KOHaq was added. Dissolved in 340 ml MeOH. 14.9 ml of 37% HCHOaq was added under ice cooling. Progress of the reaction was confirmed by silica gel TLC (AcOEt: MeOH = 19: 1). 4.9 ml (200 mmol) of 37% HCHOaq was added 8 times. The mixture was stirred at 50 ° C. for 548 hours.
The mixture was neutralized with 10% HClaq under ice cooling. The solvent was distilled off. Dissolved in methanol and the undissolved precipitate was filtered off. Further, the solvent was distilled off.
The 4-substituted product was separated from the 2-substituted product by three times of silica gel column chromatography (developing solvent, respectively, AcOEt: MeOH = 19: 1, AcOEt: MeOH = 24: 1, AcOEt: MeOH = 29: 1). 0.559 g (crude yield 5.2%) of yellow oily substance N, N′-bis {4-hydroxy-3,5-bis (hydroxymethyl) phenyl} -1,3-diamidedecane (7) was obtained. It was. See the following formula (XVI) and Table 8 below.
FIG. 3 shows the ¹ H-NMR (CD ₃ OD) spectrum of N, N′-bis {4-hydroxy-3,5-bis (hydroxymethyl) phenyl} -1,3-diamidedecane (7).

(Synthesis Example 4)
Synthesis of Phenol Resin As a phenol derivative, m-cresol and p-cresol were mixed at a mass ratio of 50:50. 54 parts by mass of formalin (aldehyde) was added to 216 parts by mass of this mixed solution, 2.2 parts by mass of oxalic acid (catalyst) was further added, and the mixture was stirred at 90 ° C. for 3 hours. Thereafter, the reaction solution was heated to 120 ° C. and stirred under reduced pressure for 3 hours to obtain a novolac type phenol resin having a weight average molecular weight of 10,000.

(Synthesis Example 5)
Synthesis of polybenzoxazole precursor In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4′-diphenyl ether dicarboxylic acid (30 mol%) and 90 g of N-methylpyrrolidone were charged. After cooling to ° C., 12.64 g of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether tetracarboxylic acid chloride. Next, in a 0.5 liter flask equipped with a stirrer and a thermometer, 87.5 g of N-methylpyrrolidone was charged, and 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1, After adding 3.30 g of 3,3,3-hexafluoropropane and stirring and dissolving, 8.53 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride Was added dropwise over 30 minutes, and stirring was continued for 30 minutes. The solution was poured into 3 liters of water, and the precipitate was collected, washed 3 times with pure water, and then dried under reduced pressure to obtain a polybenzoxazole precursor. The polymer had a weight average molecular weight of 14580 and a dispersity of 1.6 determined by GPC standard polystyrene conversion.

(Examples 4 to 9)
Preparation (blending) of resin composition, creation of cured product, and evaluation of properties [100] part by weight of resin having phenolic hydroxyl group [component (a)] (b) methylolphenol compound, (c) o-quinonediazite compound, (S) The solvent was blended in a predetermined amount shown in Table 9. This solution was subjected to pressure filtration using a 3 μm pore Teflon filter (registered trademark) to obtain resin composition solutions (M1 to M6).

  In addition, about Examples 4-9, the said (a)-(c), (s) component was mix | blended as shown in Table 9. That is, as the component (a), the phenol resin synthesized in Example 4 was used as A1, and the polybenzoxazole precursor synthesized in Example 5 was used as A2.

  (B) The component uses the methylolphenol compound synthesized in Example 1 as B1, the methylolphenol compound synthesized in Example 2 as B2, and the methylolphenol compound synthesized in Example 3 as B3. It was used.

  The component (c) is 1-naphthoquinone-2 of 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane as C1 -Diazide-5-sulfonic acid ester (Esterification rate of about 90%, trade name TPPA528 manufactured by AZ Electronic Materials) was used.

  As the component (s), ethyl lactate was used as S1, and γ-butyrolactone / propylene glycol monomethyl ether acetate = 90/10 (weight ratio) was used as S2.

Preparation method of hardened | cured material The solution (M1-M6) of the said resin composition was spin-coated on the silicon substrate, and it heated at 120 degreeC for 3 minute (s), and formed the coating film with a film thickness of 11-13 micrometers.
Curing was performed by the following methods to obtain a cured product having a thickness of about 10 μm.
(I) Using a vertical diffusion furnace (μ-TF manufactured by Koyo Thermo System), the coating film was heat-treated in nitrogen at a temperature of 250 ° C. (heating time: 1.5 hours) for 1 hour.
(Ii) Using a vertical diffusion furnace (μ-TF manufactured by Koyo Thermo System), the coating film was heat-treated in nitrogen at a temperature of 180 ° C. (heating time: 1.5 hours) for 1 hour.

Physical Properties of Cured Product The cured product having a thickness of about 10 μm cured by the above method was peeled from the silicon substrate, and the glass transition temperature (Tg) of the peeled cured product was measured with TMA / SS600 manufactured by Seiko Instruments Inc. Note that the width of the sample is 2 mm, the film thickness is 9 to 11 μm, and the distance between chucks is 10 mm. The load is 10 g, and the rate of temperature increase is 5 ° C./min. Moreover, the average breaking elongation (El) of the peel-cured product was measured by Shimadzu Autograph AGS-H100N. The width of the sample is 10 mm, the film thickness is 9 to 11 μm, and the distance between chucks is 20 mm. The pulling speed is 5 mm / min, and the measurement temperature is about room temperature (20 ° C. to 25 ° C.). Here, the average of five or more measured values for the cured product obtained under the same conditions is defined as “average elongation at break (El)”. Table 10 shows the curing conditions, Tg, and El.

Photosensitive properties The resin composition solution (M4 to M6) was spin-coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of 11 to 13 μm. Thereafter, reduction projection exposure was performed with i-line (365 nm) through a mask using an i-line stepper (FPA-3000iW manufactured by Canon). After the exposure, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide, and development was performed so that the remaining film thickness was about 70 to 90% of the initial film thickness. Thereafter, the film was rinsed with water, and the minimum exposure and resolution required for pattern formation were determined. The results are shown in Table 11.

解像度：開口している最小の正方形ホールパターンのサイズ
剥がれ：５μｍライン／スペースパターンが剥離しているかどうかを判断

Resolution: Size of the smallest open square hole pattern Peeling: Judges whether the 5 μm line / space pattern is peeled off

(Comparative Examples 1-4)
The methylolphenol compound (b), o-quinonediazite compound (c), and solvent (s) in predetermined amounts shown in Table 9 with respect to 100 parts by weight of the resin having the phenolic hydroxyl group in the above synthesis example (component (a)). And blended. This solution was subjected to pressure filtration using a 3 μm pore Teflon filter (registered trademark) to obtain resin composition solutions (M7 to M10). The blending amounts are also shown in Table 9.

  In addition, about the comparative examples 1-4, the said (a) component uses the polybenzoxazole precursor A2 synthesize | combined by the phenol resin A1 synthesize | combined by the said synthesis example 4, or the said synthesis example 5, and the said (b) component is , Unused (none) or 2,2-bis {3,5-bis (hydroxymethyl) -4-hydroxyphenyl} -1,1,1,3,3,3-hexafluoropropane (Honshu Chemical Co., Ltd. product) The name TML-BPAF) β was used. The component (c) is unused (none) or 1 of 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane. -Naphthoquinone-2-diazide-5-sulfonic acid ester (esterification rate: about 90%, trade name TPPA528 manufactured by AZ Electronic Materials) C1 was used. As the component (s), ethyl lactate was used as S1, and γ-butyrolactone / propylene glycol monomethyl ether acetate = 90/10 (weight ratio) was used as S2.

  Then, the hardened | cured material was created similarly to Examples 4-9, and the physical property of hardened | cured material was measured. The results are also shown in Table 10. Further, for Comparative Examples 3 and 4, the photosensitivity characteristics were examined in the same manner as in Examples 7-9. The results are also shown in Table 11.

  The measurement results will be examined below. First, the physical properties of the cured product are summarized in Table 10. The cured product using the resin composition (M1 to M6) of the present invention has a Tg higher than the curing temperature, that is, 285 ° C or higher even when cured at 250 ° C. Tg was shown, and Tg of 200 ° C. or higher was exhibited even when cured at 180 ° C. In addition, despite the use of a phenol resin that is a relatively brittle resin, the cured products of the resin compositions M1, M2, and M6 using the methylolphenol compounds (B1 to B3) of the present invention as a curing agent are: El of 8% or more was shown. Furthermore, El of the hardened | cured material of resin composition M3-M5 which combined the polybenzoxazole and the methylol phenol of this invention became a high value with 25% or more.

  On the other hand, the cured products (Comparative Example 2 and Comparative Example 4) of the resin compositions M8 and M10 using a methylolphenolphenol compound β other than the methylolphenolphenol compound used in the present invention were brittle and the El decreased (relative to Example 5). Comparative Example 2 and Comparative Example 4 to Example 7). Furthermore, El of the hardened | cured material (comparative example 1 and comparative example 3) of the resin compositions M7 and M9 which do not contain a methylol phenol phenol compound fell significantly. In addition, about the hardened | cured material of the comparative example 1 and the comparative example 3, since a film | membrane fractures | ruptures during a measurement, Tg could not be measured by TMA.

  Photosensitivity characteristics are summarized in Table 11. As is clear from this, the resin compositions (M4 to M6) using the methylolphenol phenol compounds (B1 to B3) of the present invention have high sensitivity and resolution. On the other hand, the sensitivity and resolution of the resin composition (M10) using the methylolphenol phenol compound β other than the methylolphenolphenol compound used in the present invention were reduced (Comparative Example 4 with respect to Example 7 and Example 8). In addition, the sensitivity and resolution of the resin composition M9 not containing a methylolphenolphenol compound were also reduced (Comparative Example 3 with respect to Example 9). In Comparative Example 3 and Comparative Example 4, a narrow line / space pattern tends to peel off during development, but when the resin composition of the present invention was used, peeling of the pattern could not be confirmed.

  The methylolphenol compound according to the present invention is novel as it has an amide bond and an alkylene chain, and can be expected to have mechanical properties and heat resistance. Therefore, it is useful as a curing agent for resins having a phenolic hydroxyl group. Further, the resin composition according to the present invention contains a methylolphenol compound having an amide bond and an alkylene chain as a curing agent, and since the cured product is excellent in mechanical properties and heat resistance, a paint, an insulating material, a semiconductor device, It is useful for electronic parts such as display elements. Furthermore, the resin composition according to the present invention further contains a photosensitizer, and the methylolphenol compound of the present invention has an adverse effect on the difference in dissolution rate (dissolution contrast) between the exposed portion and the unexposed portion of the developer. Excellent sensitivity and resolution. Furthermore, the cured product is excellent in mechanical properties and heat resistance. Therefore, it is useful for electronic parts such as a heat-resistant photoresist, a semiconductor device, and a display element.

^{1 is} a ¹ H-NMR (CD ₃ OD) spectrum of N, N′-bis {4-hydroxy-3,5-bis (hydroxymethyl) phenyl} -1,3-diamidepropane (3). ^{1 is} a ¹ H-NMR (CD ₃ OD) spectrum of N, N′-bis {4-hydroxy-3,5-bis (hydroxymethyl) phenyl} -1,3-diamidohexane (11). ^{1 is} a ¹ H-NMR (CD ₃ OD) spectrum of N, N′-bis {4-hydroxy-3,5-bis (hydroxymethyl) phenyl} -1,3-diamidedecane (7).

Claims (8)

A methylolphenol compound represented by formula (I).

(Wherein R ^{1 to} R ⁴ each independently represent a hydrogen atom or a monovalent organic group, X is an alkylene chain having 1 to 20 carbon atoms, and m and n are each independently 1 to 4) (It is a positive number, p is an integer from 0 to 4-m, and q is an integer from 0 to 4-n.) A resin composition comprising (a) a resin having a phenolic hydroxyl group and (b) a methylolphenol compound represented by the general formula (I).

(Wherein R ^{1 to} R ⁴ each independently represent a hydrogen atom or a monovalent organic group, X is an alkylene chain having 1 to 20 carbon atoms, and m and n are each independently 1 to 4) (It is a positive number, p is an integer from 0 to 4-m, and q is an integer from 0 to 4-n.)   The resin composition according to claim 2, wherein the resin (a) having a phenolic hydroxyl group is a phenol resin. The resin composition according to claim 2, wherein the resin (a) having a phenolic hydroxyl group is a compound having a repeating unit represented by the general formula (II).

(In the formula, U represents a tetravalent organic group, and V represents a divalent organic group.)   The resin composition according to any one of claims 2 to 4, wherein 1 to 50 parts by weight of component (b) is blended with 100 parts by weight of component (a). .   (C) The resin composition according to any one of claims 2 to 5, further comprising an o-quinonediazide compound.   The resin according to claim 6, comprising 1 to 50 parts by weight of the component (b) and 5 to 100 parts by weight of the component (c) with respect to 100 parts by weight of the component (a). Composition.   Hardened | cured material formed by hardening | curing the resin composition of any one of Claims 2-7.

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