JP2011075987A - Resin composition and method for forming cured relief pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin which is curable at low temperature and excels in pattern forming properties, and to provide method for forming a cured relief pattern. <P>SOLUTION: A resin composition includes a polymer compound having a repeating unit represented by the general formula (1A) or (1B); and a benzoxazine compound, where Ar<SB>1</SB>, Ar<SB>2</SB>and Ar<SB>4</SB>each independently represents a trivalent to hexavalent organic group including 6 to 30C, wherein the organic group may have a substituent; Ar<SB>3</SB>represents a bivalent to hexavalent organic group including 6 to 30C, wherein the organic group may have a substituent; Y<SB>1</SB>, Y<SB>2</SB>, Y<SB>3</SB>and Y<SB>4</SB>each independently represents an acidic group or an acidic group protected by an acidolysis group; Z represents a linking group and may be connected to at least one of Ar<SB>1</SB>and Ar<SB>2</SB>to form a ring, a, b, and f each independently represents an integer from 1 to 4; c represents an integer from 0 to 4; and n1 and n2 represent repeating numbers from 2 to 3,000. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition and a method for forming a cured relief pattern. In particular, for example, the present invention relates to a resin composition suitable as a surface protective film or an interlayer insulating film for a semiconductor device, a planarizing film or an interlayer insulating film for a display device, and a method for forming a cured relief pattern.

  A polyimide resin is used for a surface protective film and an interlayer insulating film of a semiconductor device in terms of having heat resistance, electrical characteristics, mechanical characteristics, and the like. Among them, the photosensitive polyimide precursor composition is applied to a substrate, and then subjected to patterning with actinic light, development, imidization treatment by heating, and the like, so that a surface protective film of a semiconductor device, an interlayer insulating film, etc., and a display device Since a flattening film, an interlayer insulating film, and the like can be easily formed, the process can be greatly shortened as compared with the non-photosensitive polyimide precursor composition.

  However, the photosensitive polyimide precursor composition needs to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution in the developing process. Countermeasures are required.

  In response to this, a heat-resistant photosensitive resin material using a photosensitive polyimide precursor or a photosensitive polybenzoxazole precursor that can be developed with an alkaline aqueous solution in the same manner as a photoresist has been disclosed in recent years (for example, Patent Document 1). However, the photosensitive resin composition in which naphthoquinone diazide is added to a photosensitive polyimide precursor or a photosensitive polybenzoxazole precursor has insufficient dissolution inhibiting effect on alkaline aqueous solution of naphthoquinone diazide, and the dissolution rate in alkali and Therefore, it is difficult to achieve both, and therefore the pattern formability is insufficient.

In addition, there has been a demand for a process for forming a surface protective film layer of an electronic material and a cured resin film as an interlayer insulating film at a lower temperature. Conventionally, polyimides and polybenzoxazoles have required high temperatures such as around 350 ° C., but polyimides and polybenzoxazoles that can be dehydrated and closed at temperatures below 250 ° C. have been disclosed in order to enable curing at low temperatures. (For example, Patent Document 2).
For the purpose of curing at low temperature, it is disclosed that a benzoxazine compound is blended with polyimide or a polyimide precursor and thermally cured at a low temperature (for example, Patent Documents 3 and 4).
Moreover, a polyether polymer compound having an acidic group or a protected acidic group in the polymer side chain is disclosed (for example, Patent Document 5).

JP 2004-133088 A JP 2008-224984 A WO2004-9708 JP 2004-93816 A JP 2009-98681 A

  In view of the above situation, it is an object of the present invention to provide a resin composition that is low-temperature curable and excellent in pattern formability and a method for forming a cured relief pattern.

As a result of intensive studies, the present inventors have found that the above object of the present invention can be achieved by the following means.
<1> A resin composition containing a polymer compound having a repeating unit represented by the following general formula (1A) or (1B) and a benzoxazine compound:

(In the formula, Ar ₁ , Ar ₂ , and Ar ₄ each independently represent a trivalent to hexavalent organic group having 6 to 30 carbon atoms, and the organic group may be substituted with a substituent. Ar ₃ Represents a divalent to hexavalent organic group having 6 to 30 carbon atoms, and the organic group may be substituted with a substituent, and Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently an acidic group. Alternatively, it represents an acidic group protected with an acid-decomposable group, Z represents a linking group, and may form a ring with at least one of Ar ₁ and Ar _2. a, b, and f are each independently 1-4. C represents an integer of 0 to 4. n1 and n2 are the number of repetitions, and 2 to 5000).
<2> The resin composition according to <1>, wherein the benzoxazine compound is represented by the following general formula (5):

(In the formula, R ₉ and R ₁₀ represent an organic group having 1 to ₁₀ carbon atoms, R ₁₁ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Y represents a single bond, —C (CH ₃ ) _2. - group, -CO- group, -O -, - S -, - SO ₂ - group, -CH ₂ - group, -C _{(CF 3) 2} - group, or a group represented by the following general formula (6) Represents;);

(Wherein R ₁₂ represents an organic group having 1 to 10 carbon atoms, R ₁₃ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ₁₄ represents a methylene group or a p-xylylene group. M represents 1 to 10). Indicates an integer).
<3> The resin composition according to <1>, wherein the benzoxazine compound is represented by the following general formula (7):

(Wherein R ₁₅ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ₁₆ represents an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group. ).
<4> In the general formula (1A) or (1B), the acidic group protected by the acidic group or the acid-decomposable group is a group represented by the following general formula (y1) <1> to <3> The resin composition according to any one of:

(In the formula, A, .B .P _g is representing a hydrogen atom or an acid-decomposable group represents a single bond or a (t + 1) -valent linking group is part showing acidity is protected by an acid decomposable group P _g And t represents an integer of 1 to 5.)
<5> The resin composition according to <4>, wherein the acidic group is a COOH group or an OH group.
<6> The resin composition according to any one of <1> to <5>, wherein the acid value is 100 mgKOH / g or more.
<7> The resin composition according to any one of <1> to <6>, wherein 20 mol% to 80 mol% of the acidic group is protected with an acid-decomposable group.
<8> The polymer compound represented by the general formula (1A) or (1B) is represented by the monomer represented by the following general formula (2A) or (2B) and the general formula (3), respectively. The resin composition according to any one of <1> to <7>, which is obtained by condensation polymerization with a monomer:

(Wherein Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Z, a, b, c, and f are the same as those in the general formula (1A) or (1B) R ₁ and R ₂ each independently represent a hydrogen atom or a silyl group, and X ₁ and X ₂ each independently represent a leaving group.
<9> The linking group represented by Z is a single bond, an alkylene group having 1 to 20 carbon atoms, —O—, —S—, —SO ₂ — group, —CO— group, —N (R ₁₁ ) — group. (R ₁₁ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms), or any one of <1> to <8> which is a group formed by combining these The resin composition described in 1.
<10> The resin composition according to any one of <1> to <9>, further including a photosensitizer.
<11> The resin composition according to <10>, wherein the photosensitive agent is a photoacid generator.
<12> The resin composition according to any one of <1> to <11>, which contains a crosslinking agent.
<13> The process of apply | coating the resin composition as described in any one of <10>-<12> on a board | substrate, the process of exposing, the process of developing using the aqueous alkali solution or the organic solvent is included. A method for forming a cured relief pattern.

ADVANTAGE OF THE INVENTION According to this invention, the formation method of the resin composition and the cured relief pattern which were excellent in heat resistance and insulation, low temperature curability, and excellent in pattern formation property are provided.
Therefore, according to the present invention, a heat-resistant and insulating cured relief pattern with excellent resolution can be formed at a low temperature.

Hereinafter, the present invention will be described in detail.
1. High molecular compound The high molecular compound which has a repeating unit represented by general formula (1A) or (1B) used for the resin composition of this invention is demonstrated.

(Here, Ar ₁ , Ar ₂ , Ar ₄ each independently represents a trivalent to hexavalent organic group having 6 to 30 carbon atoms, and the organic group may be substituted with a substituent. Ar ₃ Represents a divalent to hexavalent organic group having 6 to 30 carbon atoms, and the organic group may be substituted with a substituent, and Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently an acidic group. Alternatively, it represents an acidic group protected with an acid-decomposable group, Z represents a linking group, and may form a ring with at least one of Ar ₁ and Ar _2. a, b, and f are each independently 1-4. C represents an integer of 0 to 4. n1 and n2 are the number of repetitions, and 2 to 5000).

1) Polymer compound having a repeating unit represented by the general formula (1A) The polymer compound having a repeating unit represented by the general formula (1A) used in the present invention may be any compound having the repeating unit. It may be synthesized by any synthesis method.
The polymer compound having a repeating unit represented by the general formula (1A) in the present invention is preferably a monomer represented by the following general formula (2A) and a monomer represented by the general formula (3) Is obtained by condensation polymerization.

Ar ₁ , Ar ₂ , Ar ₃ , Y ₁ , Y ₂ , Y ₃ , Z, a, b, and c have the same meaning as in general formula (1A). R ₁ and R ₂ each independently represents a hydrogen atom or a silyl group. X ₁ and X ₂ each independently represent a leaving group.

The organic group represented by Ar ₁ , Ar ₂ , or Ar ₃ is preferably a group represented by the following general formula (4a) or (4b) including the following (Y) d or (Y) e.

In the case of showing the aspect of the general formula (2A), Ar ₁ corresponds to-(L ₁ -ML ₂ )-, and one or more of L ₁ , M and L ₂ are substituted with Y. ing. In the case of showing the aspect of the general formula (3), Ar ₃ corresponds to -L _3- , and Y is substituted in L ₃ .
Here, L ₁ , L ₂ , and L ₃ are a heterocyclic ring having 5 to 30 carbon atoms, an aromatic carbocyclic ring having 6 to 30 carbon atoms (for example, a benzene ring, a naphthalene ring, etc.), and a fat having 3 to 30 carbon atoms. Represents a group carbon ring (cyclopropane ring, cyclobutane ring, cyclopentane ring, etc.), and L ₁ and L ₂ may be the same or different. M represents a (d + 2) -valent linking group. Specific examples of M include a single bond and an alkylene group having 1 to 20 carbon atoms (which may have a substituent, such as methylene, ethylene, hexafluoroisopropylidene),- _{O -, - S -, -} SO 2 -, - CO -, - N (R 11) -, or a group formed by combining _{these, R 11} is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or, An acyl group having 1 to 10 carbon atoms is represented. When General Formula (4a) or (4b) represents Ar ₁ or Ar ₂ , Y is synonymous with Y ₁ or Y ₂ in General Formula (2A), d and e are a, b in General Formula (2A) It is synonymous with. When General Formula (4a) or (4b) represents Ar ₃ , Y is synonymous with Y ₃ in General Formula (3), and d and e are synonymous with c in General Formula (3). Further, in the general formula (4a), Y is, M, it is sufficient to bind to any of the _{L 1} and _{L 2,} when having a plurality of Y, either they are the same M, of _{L 1} and _{L 2} Or may be bonded to any _{one of} M, L ₁ and L ₂ , respectively.

(Monomer represented by general formula (2A))
In the general formula (2A), Ar ₁ and Ar ₂ are trivalent to hexavalent organic groups having 6 to 30 carbon atoms, preferably aromatic rings or aliphatic groups, more preferably 6 to 6 carbon atoms. 24 is a 3-6 valent aromatic ring or an aliphatic group, and more preferably a 3-6 valent aromatic ring or an aliphatic group having 6 to 20 carbon atoms.

In the general formulas (1A) and (2A), specific examples of Ar ₁ and Ar ₂ include heterocycles having 5 to 30 carbon atoms and aromatic carbocycles having 6 to 30 carbon atoms (for example, benzene ring, naphthalene ring, etc.) And aliphatic carbocycles having 3 to 30 carbon atoms (cyclopropane ring, cyclobutane ring, cyclopentane ring, etc.). Here, Ar ₁ and Ar ₂ may be the same or different. Among these, as Ar ₁ and Ar ₂ , an aromatic carbocyclic ring having 6 to 30 carbon atoms (for example, a benzene ring or a naphthalene ring) is preferable.

In the general formulas (1A) and (2A), Z represents a linking group, for example, a single bond or an alkylene group having 1 to 20 carbon atoms (which may have a substituent, methylene, ethylene, hexafluoroisopropylidene. Etc.), —O—, —S—, —SO ₂ —, —CO—, —N (R ₁₁ ) —, or a group formed by combining these, R ₁₁ is a hydrogen atom, having 1 to 10 carbon atoms An alkyl group or an acyl group having 1 to 10 carbon atoms is represented. Z may be trivalent to tetravalent, and in that case, it may form a ring with Ar ₁ or Ar ₂ as in the compounds a-16, a-17, and a-18 described later. Among them, as Z, an alkylene group having 1 to 20 carbon atoms (which may have a substituent, such as methylene, ethylene, hexafluoroisopropylidene), -O-, -S-, -SO2-, -CO- Is preferred.

In general formula ((2A), R ₁ and R ₂ are each independently a hydrogen atom, a silyl group (a silyl group having 1 to 10 carbon atoms, such as triethoxysilyl, methyldiethoxysilyl, trivinylsilyl). Preferably, it is a silyl group having a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, more preferably a silyl group having a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, particularly preferably hydrogen. Is an atom.

In the general formulas (1A) and (2A), Ar ₁ and Ar ₂ may each independently have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom). , A bromine atom, or an iodine atom), a linear, branched, or cyclic alkyl group (an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, methyl, t-butyl, cyclopentyl, cyclohexyl, adamantyl, Biadamantyl, diamantyl, etc.), alkynyl group (C2-C10 alkynyl group, ethynyl, phenylethynyl, etc.), aryl group (C6-C10 aryl group, phenyl, 1-naphthyl, 2-naphthyl, etc.) ), Acyl group (acyl group having 1 to 10 carbon atoms, acetyl, benzoyl, etc.), aryloxy group (aryloxy group having 6 to 10 carbon atoms, phenoxy) ), Arylsulfonyl group (C6-C10 arylsulfonyl group, phenylsulfonyl, etc.), alkoxy group (C1-C10 alkoxy group, methoxy group, ethoxy group, propoxy group, etc.), nitro group, cyano Group, silyl group (C1-C10 silyl group, triethoxysilyl, methyldiethoxysilyl, trivinylsilyl, etc.), alkoxycarbonyl group (C2-C10 alkoxycarbonyl group, methoxycarbonyl, etc.), And a carbamoyl group (a carbamoyl group having 1 to 10 carbon atoms, such as carbamoyl, N, N-dimethylcarbamoyl). These substituents may be further substituted with another substituent.

Although the specific example of a monomer represented by general formula (2A) below is shown, it is not limited to these. Specific examples of the monomer in the case where R ₁ and R ₂ are hydrogen atoms are shown below, but when R ₁ and R ₂ are silyl groups, preferred examples are those in which the hydrogen atoms are replaced with silyl groups. It is.

(Monomer represented by the general formula (3))
In General Formula (3), Ar ₃ is a 2-6 valent organic group having 6 to 30 carbon atoms, preferably an aromatic ring or an aliphatic group, more preferably a 2-6 valent having 6 to 24 carbon atoms. An aromatic ring or an aliphatic group, more preferably a 6- to 20-valent aromatic ring or aliphatic group having 6 to 20 carbon atoms. Specific examples of Ar ₃ include benzene ring, pyridine ring, naphthalene ring, cyclohexane ring, tetrahydronaphthalene ring, hexane, heptane, octane, nonane, decane and the like.

In the general formula (3), X ₁ and X ₂ each independently represent a leaving group. X ₁ and X ₂ are preferably a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a group containing a nitrogen atom such as a nitro group, a mesyl group, a tosyl group, and more preferably a fluorine atom. , Chlorine atom, bromine atom, iodine atom, nitro group, tosyl group, more preferably fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, particularly preferably fluorine atom, chlorine atom, nitro group. It is a group.
Ar ₃ may have a substituent other than X ₁ , X ₂ , and Y, and examples of the substituent are the same as those exemplified as the substituent of the group represented by Ar ₁ or Ar _2. .

  Although the specific example of a monomer represented by General formula (3) below is shown, it is not limited to these.

(About acidic groups)
In the general formulas (1A), (2A), and (3A), an acidic group protected with an acidic group or an acid-decomposable group represented by Y ₁ , Y ₂ , or Y ₃ will be described.
The acidic group protected with an acidic group or an acid-decomposable group in the present invention is preferably represented by the general formula (y1).

In the formula, A represents a single bond or a (t + 1) -valent linking group. _Pg represents a hydrogen atom or an acid-decomposable group. B represents a partial structure of the acidic group site showing acidity by acid-decomposable groups P _g is protected. t represents an integer of 1 to 5, preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

The acidic group (BH) which P _g is generated by decomposition (desorption), preferably a pKa of 15 or less, more preferably 2 to 12. Specific examples of the acidic group include —OH, —COOH, —SO ₃ H, —SO ₂ NH ₂ , —SO ₂ NHR ₁₂ (R ₁₂ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom. represents a 10 acyl _{group), -. C (CF 3} ) 2 -OH and the like, _{preferably, -OH, -COOH, -SO 2 NH} 2, and -C _{(CF 3)} in 2 -OH More preferably -OH and -COOH.

Specific examples of the linking group A include a single bond, an alkylene group having 1 to 20 carbon atoms, —O—, —S—, —SO ₂ —, —CO—, —N (R ₁₃ ) —, or a combination thereof. (N + 1) -valent group in which n-1 arbitrary hydrogen atoms are removed from a divalent group formed in the above manner, R ₁₃ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Represents an acyl group.

Acid-decomposable group represented by P _g is not particularly limited as long as it can generate an acid group by the action of an acid, together with the hetero atom contained in the acid group, acid decomposition of ethers, esters, acetals, ketals Typical are groups capable of forming silyl ethers or silyl esters.

Specific examples of the acid-decomposable group represented by P _g, the tertiary alkyl group (tertiary alkyl group of 4 to 15 carbon atoms, preferably a tertiary alkyl group having 4 to 13 carbon atoms, for example, t- Examples thereof include a butyl group, a t-amyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, and a 1-ethylcyclohexyl group), and an alkoxyalkyl group or an aryloxyalkyl group represented by the following general formula (y2).

In the general formula (y2), R ₂₀ is an alkyl group (C1-C10, preferably C1-C4 alkyl group such as methyl, ethyl, propyl, etc.) or an aryl group (C6-C6). 20 represents an aryl group such as phenyl or naphthyl, and R ₂₁ and R ₂₂ are each a hydrogen atom or an alkyl group (an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, for example, methyl , Ethyl, propyl, etc.) or an aryl group (an aryl group having 6 to 20 carbon atoms, such as phenyl, naphthyl, etc.).
In one preferred embodiment, R ₂₀ , R ₂₁ and R ₂₂ are all alkyl groups. In that case, R ₂₀ and R ₂₁ , R ₂₁ and R ₂₂ may be bonded to each other to form a carbocycle.
In another preferred embodiment, one of R ₂₁ and R ₂₂ is a hydrogen atom, and the other of R ₂₁ and R ₂₂ and R ₂₀ are both aryl groups.

Examples of preferred P _g, t-butyl group, t-amyl group, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-ethyl cyclohexyl group, a methoxymethyl group, an alkoxyalkyl group such as an ethoxyethyl group, Examples include a tetrahydropyranyl group, a tetrahydrofuranyl group, an alkoxy-substituted tetrahydropyranyl group, an alkoxy-substituted tetrahydrofuranyl group, a benzyl group, a p-methoxybenzyl group, a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group.

  In general formula (1A), (2A), (3), a and b each independently represent an integer of 1 to 4, and c represents an integer of 0 to 4. n1 is a repetition number, and is 2-5000. Preferably, a and b each independently represent an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably an integer of 1 to 2. n1 becomes like this. Preferably, it is 3-3000, More preferably, it is 5-2000, More preferably, it is 10-1000.

2) Polymer compound having a repeating unit represented by the general formula (1B) The polymer compound having a repeating unit represented by the general formula (1B) used in the present invention may be any compound having the repeating unit. It may be synthesized by any synthesis method.
The polymer compound having a repeating unit represented by the general formula (1B) in the present invention is preferably a monomer represented by the following general formula (2B) and a single monomer represented by the general formula (3). It is obtained by condensation polymerization with a body.

In the formula, each Ar ₄ independently represents a 3 to 6-valent organic group having 6 to 30 carbon atoms, and the organic group may be substituted with a substituent. Y ₄ represents an acidic group protected with an acidic group or an acid-decomposable group. f represents an integer of 1 to 4. R ₁ and R ₂ each independently represents a hydrogen atom or a silyl group.

In the general formulas (1B) and (2B), Ar ₄ is selected from the same group as the organic group described above for Ar ₁ or Ar ₂ in the general formula (1A), and a preferable range is the same as that of Ar ₁ or Ar ₂ . is there. Y ₄ is selected from the same group as the acidic group protected with the acidic group or acid-decomposable group described above for Y ₁ or Y ₂ in the general formula (1A), and the preferred range is the same as in Y ₁ or Y ₂ It is.

Although the specific example of a monomer represented by general formula (2B) below is shown, it is not limited to these. Specific examples of the monomer in the case where R ₁ and R ₂ are hydrogen atoms are shown below, but when R ₁ and R ₂ are silyl groups, preferred examples are those in which the hydrogen atoms are replaced with silyl groups. It is.

  The polymer compound having a repeating unit represented by the general formula (1A) or (1B) in the present invention has a high dissolution rate in an alkali developer when forming a relief pattern, and from the viewpoint of obtaining high productivity, an acid value. Is preferably 100 mgKOH / g or more. When the acid value is less than 100 mgKOH / g, the development speed becomes slow and the productivity of the semiconductor device decreases, and when the acid value is too high, the image tends to blur in the lithography process. / G to 500 gKOH / g is more preferable. More preferably, it is 150 gKOH / g-450 mgKOH / g, Most preferably, it is 200 gKOH / g-400 mgKOH / g.

  The acid value of the polymer compound having a repeating unit represented by the general formula (1A) or (1B) in the present invention is such that when a part or all of the acidic group is protected by a protecting group, the protecting group is It represents the acid value in the removed state. That is, the acid value of the polymer compound (A) in the present invention means the total of free acidic groups and acidic groups protected by a protecting group.

  The acidic group in the present invention is preferably protected by 1 to 100 mol% by a protecting group. More preferably, 10 mol% to 90 mol%, still more preferably 20 mol% to 80 mol% is protected.

The acid value of the polymer compound in the present invention can be measured by the following method.
0.2 g of the polymer is dissolved in 20 mL of tetrahydrofuran, and titrated with a 0.1N KOH methanol solution, and the consumption of KOH per 1 g of resin (mgKOH / g) is determined. Phenolphthalein is used as the indicator.

  By controlling the acid value of the polymer compound having a repeating unit represented by the general formula (1A) or (1B) in the present invention, the alkali development rate of the obtained resin composition can be improved. The reduction rate of the film with respect to a 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution that is a typical alkaline developer is preferably 150 nm / second or more, more preferably 200 nm / second or more, and even more preferably 300 nm / second or more. It is.

As a method of controlling the acid value in the polymer compound having a repeating unit represented by the general formula (1A) or (1B), the ratio of Y ₁ , Y ₂ , Y ₃ in the general formula (1) is changed. Can be achieved.

Although there is no restriction | limiting in particular in the molecular weight of the high molecular compound which has a repeating unit represented by general formula (1A) or (1B) in this invention, Since it is excellent in the alkali dissolution rate and the mechanical property of a film | membrane, general formula (1 The number of repeating units represented by n is 2 to 5000, preferably 3 to 3000, and more preferably 5 to 2000.
The molecular weight of the polymer compound having a repeating unit represented by the general formula (1A) or (1B) in the present invention is preferably 1,000 to 500,000 in terms of weight average molecular weight, more preferably 3,000 to 300,000. Preferably, 5,000-200,000 is more preferable. In the present invention, the molecular weight is measured by gel permeation chromatography and can be determined using a standard polystyrene calibration curve.

  The polymer compound in the present invention can be obtained by polymerizing the monomer represented by the general formula (2A) or (2B) and the monomer represented by the general formula (3). The polymerization of the monomer represented by the general formula (2A) or (2B) and the monomer represented by the general formula (3) is preferably performed in a solvent. The solvent used in the polymerization reaction of the monomers represented by the general formulas (2A) or (2B) and (3) can dissolve the raw material monomer at a necessary concentration, and can be obtained from the obtained polymer. Any material that does not adversely affect the characteristics of the film to be formed may be used. For example, alcohol solvents such as water, methanol, ethanol, propanol, etc., ketone solvents such as acetone, alcohol acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, Ester solvents such as methylbenzoate, ether solvents such as dibutyl ether, anisole, tetrahydrofuran, toluene, xylene, mesitylene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, isopropylbenzene, 1,4-diisopropyl Benzene, t-butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-triethylbenzene, 1,3,5-tri-t-butylbenzene, 4-t Aromatic hydrocarbon solvents such as butyl-orthoxylene, 1-methylnaphthalene and 1,3,5-triisopropylbenzene, amide solvents such as N-methylpyrrolidinone and dimethylacetamide, carbon tetrachloride, dichloromethane, chloroform, 1 , 2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, and other halogen-based solvents, and hexane, heptane, octane, cyclohexane, and other aliphatic hydrocarbon-based solvents.

  Among these, more preferred solvents are tetrahydrofuran, γ-butyrolactone, anisole, toluene, xylene, mesitylene, isopropylbenzene, t-butylbenzene, 1,3,5-tri-t-butylbenzene, 1-methylnaphthalene, 1 Amide solvents such as 1,3,5-triisopropylbenzene, N-methylpyrrolidinone, dimethylacetamide, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, particularly preferred Is an amide solvent such as N-methylpyrrolidinone and dimethylacetamide. These may be used alone or in admixture of two or more.

  The boiling point of the organic solvent used for the polymerization reaction is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 150 ° C. or higher.

  The concentration of the solute in the reaction solution is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 10% by mass to 20% by mass.

  The inorganic salt used in the production of the polymer of the present invention is not particularly limited as long as it can convert the monomer of the general formula (2A) or (2B) into a nucleophilic metal salt in the reaction system. A compound that generates an alkali metal salt of a monomer represented by the general formula (2A) or (2B) is preferable. Accordingly, the alkali metal salt of the monomer represented by the general formula (2A) or (2B) can be separately synthesized and used, or the reaction can be carried out while forming a salt before or simultaneously with the polymerization reaction. Examples of the alkali metal salt include lithium, sodium, potassium, and the like, and potassium and sodium are particularly preferable. Examples of the metal compound used for forming the alkali salt include hydroxides, carbonates, bicarbonates, and the like, and hydroxides and carbonates are particularly preferable. Therefore, potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate are preferable in order to form the alkali salt of the monomer represented by the general formula (2A) or (2B). The inorganic salts used in the present invention may be used alone or in combination of two or more.

  The amount of these alkali metal salts used varies depending on the type, and also varies depending on the substrate, but it is 1 to 8 moles based on the amount of the monomer represented by the general formula (2A) or (2B). A range is preferred. More preferably, it is the range of 2-4 times mole. When the amount of the alkali metal salt is 1 mol or less with respect to the amount of the monomer represented by the general formula (2A) or (2B), the amount of the monomer represented by the general formula (2A) or (2B) The alkali metal salt cannot be produced sufficiently, and it is difficult to obtain a high molecular weight polymer compound. Further, an excess amount of 8 times mole or more is not economically advantageous.

  The actual polymerization reaction in the production of the polymer compound of the present invention can be carried out in various forms shown below. For example, in the presence of (I) a polymerization solvent, a monomer represented by the general formula (2A) or (2B), an alkali metal salt, and an azeotropic dehydration solvent are added, and represented by the general formula (2A) or (2B). A method in which a monomer represented by the general formula (2A) or (2B) is added and polymerized after the formation of an alkali metal salt of the monomer to be azeotropically dehydrated, (II) the presence of a polymerization solvent Below, the monomer represented by the general formula (2A) or (2B), the alkali metal salt, the azeotropic dehydration solvent, and the monomer represented by the general formula (3) are added, and azeotropic dehydration is performed. A method of performing polymerization while producing an alkali metal salt of a monomer represented by the general formula (3), (III) separately from an alkali metal salt of a monomer represented by the general formula (2A) or (2B) And a method in which the monomer represented by the general formula (3) is added and polymerized in the presence of a polymerization solvent, and (IV) A method in which an aqueous solution of an alkali metal salt of a monomer represented by the formula (2A) or (2B) is added to a polymerization solvent, and the monomer represented by the general formula (3) is further added together with an azeotropic solvent to perform polymerization. Etc.

  As is apparent from the examples of the polymerization methods described above, azeotropic dehydration uses an azeotropic solvent azeotropic with water as necessary. Examples include aromatic hydrocarbons such as benzene, toluene and xylenes, as well as halogenated aromatic hydrocarbons such as chlorobenzene and o-dichlorobenzene, which are particularly limited if azeotroped with water. is not. The amount of azeotropic solvent used can be determined from the amount of water present in the reaction system and the azeotropic composition. In dehydration using an azeotropic solvent, water is distilled together with the azeotropic solvent, the distillate is cooled and condensed, and water and the azeotropic solvent are separated into two layers. If the separated azeotropic solvent layer is refluxed to the reaction system, the azeotropic solvent is effectively used, so that dehydration can be completed without using a large excess of azeotropic solvent. The time required for azeotropic dehydration also varies depending on the amount of water present in the reaction system, the amount of azeotropic solvent to be used, etc., but in terms of practical use, it is preferably performed within 10 hours, and further completed within 5 hours. More preferably.

Optimum conditions for the polymerization reaction in the present invention vary depending on the type and concentration of the solvent, but the reaction temperature is preferably 0 ° C to 230 ° C, more preferably 100 ° C to 230 ° C, and particularly preferably 140 ° C to At 200 ° C., the reaction time is preferably in the range of 1 hour to 50 hours, more preferably 2 hours to 40 hours, and particularly preferably 3 hours to 30 hours.
Moreover, it is preferable to make it react in inert gas atmosphere (for example, nitrogen, argon, etc.) in order to suppress the oxidative decomposition of a high molecular compound. It is also preferable to polymerize under light-shielding conditions in order to suppress unwanted photoreactions.

  The monomers represented by the general formula (2A) or (2B) and (3) may be used individually by 1 type each when synthesizing a polymer compound, or one type is used and the other type is used. Two or more kinds may be used, and two or more kinds may be used respectively.

  In addition, a monomer represented by the general formula (2A) or (2B) when the polymer compound is synthesized using the monomer represented by the general formula (2A) or (2B) and (3) The charging ratio with the monomer represented by the general formula (3) may be any charging ratio as long as the target product can be synthesized.

  A preferable charging ratio between the monomer represented by the general formula (2A) or (2B) and the monomer represented by the general formula (3) is a simple formula represented by the general formula (2A) or (2B). The molar ratio of the monomer to the monomer (3) represented by the general formula (3) is preferably in the range of 0.6 to 1.4. More preferably, it is in the range of 0.8 to 1.2. In particular, for the purpose of obtaining a high molecular weight polymer compound, the above molar ratio should be close to 1, and conversely, the above molar ratio. When the polymerization is carried out outside this range, it becomes difficult to obtain a high molecular weight polymer compound.

  The polymer compound having a repeating unit represented by the general formula (1A) or (1B) of the present invention is represented by the monomer represented by the general formula (2A) or (2B) and the general formula (3). The monomer represented by the following general formula (2C) or (2D) is not condensed with the monomer represented by the general formula (3B). It can also be obtained by polymerization.

Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Z, a, b, c, and f are as defined in general formulas (1A) and (1B). R ₁ , R ₂ , X ₁ and X ₂ are also synonymous with those in the general formulas (2A), (2B) and (3).

  The reaction conditions for the condensation polymerization of the monomer represented by the general formula (2C) or (2D) and the monomer represented by the general formula (3B) are the above-described general formula (2A) or (2B). It is the same as the conditions which carry out the polycondensation of the monomer represented, and the monomer represented by General formula (3), The preferable range is also the same.

<Method of protecting acidic group with acid-decomposable group>
In order to protect an acidic group with an acid-decomposable group, various methods can be used. For example, as the monomer (2A), (2B), or (3) used for the polymerization, those in which the acidic groups Y ₁ , Y ₂ , Y ₃ are previously protected with an acid-decomposable group can be used. Alternatively, after polymerizing the polymer compound, the acidic group can be protected with an acid-decomposable group.
Preferably, after polymerization, the acidic group of the polymer compound is protected with an acid-decomposable group. As a method for protecting the acidic group of a polymer compound with an acid-decomposable group, a polymer compound having an acid group is reacted with an alcohol or a halogen compound having a protecting group as described above by acid or basic catalysis. Can be easily protected by.

  It is preferable to protect 1 mol% to 100 mol% of the acidic group with an acid-decomposable group, because of its excellent solubility in alkali and excellent relief pattern formation and resolution. More preferably, 10 mol% to 90 mol%, and still more preferably 20 mol% to 80 mol% are protected with an acid-decomposable group.

In the present invention, in addition to the monomer represented by the general formula (2A) or (2B) and the monomer represented by the general formula (3), a third monomer is copolymerized. May be. The third monomer is not particularly limited as long as it can be introduced into the general formula (1), but is introduced for the purpose of controlling mechanical properties such as tensile strength and heat resistance of the resulting polymer. Is possible.
The following monomers can be used as the third monomer.

  The charging ratio of the third monomer is preferably in the range of 0.001 to 0.7 in terms of molar ratio with respect to all monomers. More preferably, it is 0.005-0.5, More preferably, it is 0.0.01-0.3.

  Although the specific example of the high molecular compound which has a repeating unit represented by general formula (1A) or (1B) used for the resin composition of this invention below is shown, this invention is not limited to these. .

2. Benzoxazine Compound The benzoxazine compound used in the present invention is a compound having at least one dihydrooxazine ring condensed with an aromatic hydrocarbon ring, and particularly if it is cured by a ring-opening polymerization reaction of this dihydrooxazine ring. There is no restriction | limiting, A well-known benzoxazine compound etc. can be utilized. Preferred examples of the aromatic hydrocarbon ring condensed with the dihydrooxazine ring include a benzene ring and a naphthalene ring, and these aromatic hydrocarbon rings have an alkyl group having 3 or less carbon atoms such as a methyl group or a substituent such as halogen. It may be, but those having no substituent are preferable.

  A dihydrooxazine ring condensed with a benzene ring is called a dihydrobenzoxazine ring, a compound containing the dihydrooxazine ring is called a dihydrobenzoxazine compound, and a dihydrooxazine ring condensed with a naphthalene ring is called a dihydronaphthoxazine ring. A compound containing this is called a dihydronaphthoxazine compound. All of these are included in the benzoxazine compound in the present invention.

  The benzoxazine compound is easy to mix with the polymer compound having a repeating unit represented by the general formula (1A) or (1B) in the present invention and has excellent heat resistance after curing. The dihydrobenzoxazine compound represented by (5) or the dihydronaphthoxazine compound represented by the general formula (7) is desirable.

In the formula, R ₉ and R ₁₀ represent an organic group having 1 to ₁₀ carbon atoms, and R ₁₁ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Y is a single bond, —C (CH ₃ ) ₂ — group, —CO— group, —O—, —S—, —SO ₂ — group, —CH ₂ — group, —C (CF ₃ ) ₂ — group. Or a group represented by the following general formula (6).

In the formula, R ₁₂ represents an organic group having 1 to 10 carbon atoms, R ₁₃ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R ₁₄ represents a methylene group or a p-xylylene group. m shows the integer of 1-10.

In the formula, R ₁₅ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ₁₆ represents an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group.

R ₉ and R ₁₀ are each an organic group having 1 to ₁₀ carbon atoms, preferably an alkyl group, a phenyl group, or an alkylphenyl group.
R ₁₁ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group. Y is a single bond, —C (CH ₃ ) ₂ — group, —CO— group, —O—, —S—, —SO ₂ — group, —CH ₂ — group, —C (CF ₃ ) ₂ — group. Or a group represented by formula (6), preferably —C (CH ₃ ) ₂ —. R ₁₅ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ₁₆ represents an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group. R ₁₂ represents an organic group having 1 to 10 carbon atoms, preferably an alkyl group, a phenyl group, or an alkylphenyl group. R ₁₃ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, but is a hydrogen atom or an alkyl group, R ₁₄ represents a methylene group or a p-xylylene group, and n represents an integer of 1 to 10.

  Desirable benzoxazine compounds used in the present invention may be composed only of the compounds represented by the above general formula (5) or general formula (7), and may be compounds containing a small amount of a partial polymer thereof. It may be a mixture thereof. In addition, it may contain a small amount of impurities, partially ring-opened products, unreacted products, etc. that are produced as by-products during the production of the benzoxazine compound.

The dihydrobenzoxazine compound used in the present invention can be produced by a known method. As an example of a preferable reaction raw material, there are a phenol compound, a primary amine and an aldehyde represented by the following general formula.
a) Phenol compound: HO—Ar ₃₀ or HO—Ar ₄₀ —OH
b) Primary amine: R—NH ₂
c) Aldehyde: R'-CHO

Here, Ar ₃₀ is a monovalent aromatic group, and Ar ₄₀ is a divalent aromatic group, but is preferably a polycyclic aromatic group having two or more rings, such as a halogen or an alkyl group. Although it may have a substituent, it has at least one hydrogen that can be substituted in the ortho position with respect to the OH group.
R is a monovalent aliphatic or aromatic organic group, preferably an aromatic group, and may have a substituent such as halogen. Moreover, it is also preferable that it is a polycyclic aromatic group of 2 or more rings. Preferably, it is a C1-C10 alkyl group, a cyclohexyl group, a phenyl group, or a substituted phenyl group.
R ′ is hydrogen or a monovalent aliphatic or aromatic organic group, preferably hydrogen or a lower alkyl group.

  An example of a reaction for obtaining a dihydrobenzoxazine compound from a phenol compound, a primary amine and an aldehyde is shown below.

It can be understood from the above reaction formula that various dihydrobenzoxazine compounds can be obtained by changing the phenol compound, primary amine or aldehyde. For example, when obtaining the dihydrobenzoxazine compound represented by the general formula (5), the following compounds are used as raw materials as the phenol compound, primary amine and aldehyde. In the following formula, φ represents p-phenylene, and R ₉ and R ₁₀ may be the same.
a) Phenol compound: HO-φ-Y-φ-OH
b) Primary amine: R ₉ —NH ₂ or R ₁₀ —NH ₂
c) Aldehyde: R ₁₁ —CHO

  In order to synthesize the dihydrobenzoxazine compound used in the present invention, the primary amine is (0.8 to 1.2) × y mol, preferably (0. 9-1.1) xy moles can be used and the aldehyde can be reacted using (1.6-2.4) xy moles, preferably (1.8-2.2) xy moles. desirable.

  Examples of the phenol compound used as a raw material of the dihydrobenzoxazine compound include phenols, polyfunctional phenols, bisphenols, 1,1,1-tris (4-hydroxyphenyl) in which hydrogen is bonded to at least one of the ortho positions. And trisphenols such as ethane. Preferably, it is a compound having two or more phenolic hydroxyl groups in one molecule from the viewpoint of thermosetting properties. Specific examples of polyfunctional phenols include catechol, resorcinol, hydroquinone, and bisphenols include bisphenol A, bisphenol S, bisphenol F, and hexafluorobisphenol A. Examples of the phenol resin include phenol novolac resin, resol resin, phenol-modified xylene resin, alkylphenol resin, melamine phenol resin, polybutadiene-modified phenol resin, and the like. These can be used alone or in combination of two or more.

As the primary amine, aliphatic amines such as methylamine, butylamine, and cyclohexylamine, and aromatic amines such as aniline, toluidine, and anisidine can be used, and these can be used alone or in combination of two or more.
As the aldehyde, the aldehyde can be used, but when formaldehyde is used, it can be used in any form as a formalin aqueous solution or as paraformaldehyde.

  Specific examples of the dihydrobenzoxazine compound include the following dihydrobenzoxazine compounds. However, it is not limited to these, 1 type (s) or 2 or more types can be used.

  Further, as the benzoxazine compound used in the present invention, a thermosetting resin having a dihydronaphthoxazine ring can also be used. This dihydronaphthoxazine compound can be used alone as a benzoxazine compound, or can be used in combination with the dihydrobenzoxazine compound as described above. A specific method for producing a dihydronaphthoxazine compound is the same as the above-mentioned dihydrobenzoxazine compound. After reacting by a method of gradually adding a primary amine to formaldehyde, a compound having a naphthol-based hydroxyl group is added, and 20 minutes Keep at 70 ° C. to 120 ° C. for ˜24 hours. At this time, an organic solvent can also be used as needed. After the reaction, the product is isolated and purified by a synthetic chemical technique such as extraction, and a volatile component such as condensed water is removed by drying to obtain the desired dihydronaphthoxazine compound.

  Specific examples of the dihydronaphthoxazine compound include the following compounds. However, the present invention is not limited to these.

  The benzoxazine compound in the present invention causes a ring-opening polymerization reaction by heating, and forms a cross-linked structure having excellent characteristics while generating a phenolic hydroxyl group without generating a volatile component. This cured product exhibits low hygroscopicity, high glass transition temperature, high strength and high elastic modulus, and low cure shrinkage, and is excellent in flame retardancy. The benzoxazine compound may be a single compound before curing, may be a mixture containing a small amount of side reaction products, or may be a partially polymerized oligomer. In the invention, the term “benzoxazine compound” includes both cases.

  The content of the benzoxazine compound in the resin composition of the present invention is 1% by mass to 70% by mass with respect to the polymer compound having a repeating unit represented by the general formula (1A) or (1B). preferable. More preferably, it is 5 mass%-50 mass%, More preferably, it is 10 mass%-35 mass%.

3. Resin Composition The resin composition of the present invention contains a polymer compound having a repeating unit represented by the general formula (1A) or (1B) and a benzoxazine compound.
In addition, the resin composition of the present invention preferably contains a photosensitizer, a crosslinking agent, a sensitizer, a thermal acid generator, an adhesion promoter, a solvent, and the like.
Particularly preferably, the resin composition of the present invention contains a photosensitizer and is a photosensitive resin composition. More preferably, it is a photosensitive resin composition containing a crosslinking agent.
These will be described in detail below.

(Photosensitive agent)
The photosensitive agent used in the present invention refers to a compound that imparts a function of forming an image by exposure to the photosensitive resin composition and / or gives a trigger for the function. Specific examples include compounds that generate an acid upon exposure (photoacid generator), photosensitive quinonediazide compounds, and dihydropyridine compounds. Two or more of these photosensitizers can be used in combination. Moreover, a sensitizer etc. can also be used together for sensitivity adjustment.

(1) Photoacid generator The photoacid generator is used as a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a microresist. Known compounds that generate an acid upon irradiation with actinic rays or radiation and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates. Preferred photosensitizers include imide sulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate, which are compounds that generate sulfonic acid.

  Further, a group capable of generating an acid upon irradiation with actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the resin, for example, US Pat. No. 3,849,137, German Patent No. 3914407. Description and JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853 And compounds described in JP-A 63-146029, etc. can be used.

  Further, compounds capable of generating an acid by light described in each specification such as US Pat. No. 3,779,778 and European Patent 126,712 can also be used.

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be exemplified.

In general formulas (ZI) to (ZIII), R _{201 to} R ₂₀₇ each independently represents an organic group. The number of carbons in the organic group R ₂₀₁ to R ₂₀₇ are ranges of 1 to 30, preferably from 1 to 20. Two members out of R _{201 to} R ₂₀₇ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
X ⁻ represents a non-nucleophilic anion, preferably sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{— and the} like. An organic anion having a carbon atom is preferable.
Preferable organic anions include organic anions represented by the following general formula.

In the above general formula, Rc ₁ represents an organic group.
Examples of the organic group for Rc ₁ include those having 1 to 30 carbon atoms, and preferably an alkyl group, a cycloalkyl group, an aryl group, or a plurality thereof, which may be substituted, is a single bond, —O—, — _{CO 2 -, - S -,} - SO 3 -, - SO 2 N (Rd 1) - can be exemplified linked group a linking group such as.

Rd ₁ represents a hydrogen atom or an alkyl group.
Rc ₃ , Rc ₄ and Rc ₅ each independently represents an organic group.
Examples of the organic group of Rc ₃ , Rc _4, and Rc ₅ include the same organic groups as those of Rc ₁ , preferably a C 1-4 perfluoroalkyl group.
Rc ₃ and Rc ₄ may be bonded to form a ring.
Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group, a cycloalkylene group, and an arylene group. Preferably it is a C2-C4 perfluoroalkylene group.

The organic group of Rc ₁ and Rc _{3 to} Rc ₅ is preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. Further, Rc ₃ and Rc ₄ are preferably bonded to form a ring, so that the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved, which is preferable.

  Of these, at least one of the aryl groups of the triarylsulfonium salt preferably has an electron-withdrawing group as a substituent, and the sum of Hammett values of substituents bonded to the aryl skeleton is greater than 0.18. Is preferred.

  Here, the electron-withdrawing group means a substituent having a Hammett value (Hammet substituent constant σ) larger than 0. In the present invention, from the viewpoint of increasing sensitivity, the sum of Hammett values of substituents bonded to the aryl skeleton in the photoacid generator is preferably 0.18 or more, more preferably greater than 0.46. More preferably, it is larger than 0.60.

  The Hammett value represents the degree of electron withdrawing property of a cation having a triarylsulfonium salt structure, and there is no particular upper limit from the viewpoint of increasing sensitivity, but from the viewpoint of reactivity and stability. , More than 0.46 and less than 4.0, more preferably more than 0.50 and less than 3.5, and particularly preferably more than 0.60 and less than 3.0.

In addition, the Hammett value in the present invention uses the numerical value described in Naoki Inamoto, edited by Chemistry Seminar 10 Hammett's Rule-Structure and Reactivity (1983, published by Maruzen Co., Ltd.).
Examples of the electron-withdrawing group introduced into the aryl skeleton include a trifluoromethyl group, a halogen atom, an ester group, a sulfoxide group, a cyano group, an amide group, a carboxyl group, and a carbonyl group. The Hammett values of these substituents are shown below. A trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), a halogen atom [eg, —F (m: 0.34, p: 0.06), —Cl (m: 0. 37, p: 0.23), -Br (m: 0.39, p: 0.23), -I (m: 0.35, p: 0.18)], an ester group (for example, -COCH 3 , O: 0.37, p: 0.45), sulfoxide group (for example, —SOCH ₃ , m: 0.52, p: 0.45), cyano group (—CN, m: 0.56, p: 0.66), an amide group (for example, —NHCOCH ₃ , m: 0.21, p: 0.00), a carboxyl group (—COOH, m: 0.37, p: 0.45), a carbonyl group (— CHO, m: 0.36, p: 0.43) and the like. The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value. For example, (m: 0.50) means that the Hammett value when the substituent is introduced at the meta position is 0.50. Indicates that

Among these substituents, nonionic substituents such as a halogen atom and a halogenated alkyl group are preferable from the viewpoint of hydrophobicity. Among them, —Cl is preferable from the viewpoint of reactivity, and imparts hydrophobicity. from the viewpoint, -F, -CF 3, -Cl, -Br are preferable.

  These substituents may be introduced into any one of the three aryl skeletons of the triarylsulfonium salt structure, or may be introduced into two or more aryl skeletons. Moreover, the substituent introduced into each of the three aryl skeletons may be one or plural. In the present invention, the sum of Hammett values of substituents introduced into these aryl skeletons is preferably more than 0.18, more preferably more than 0.46. The number of substituents to be introduced is arbitrary. For example, only one substituent having a particularly large Hammett value (for example, a Hammett value exceeding 0.46 alone) may be introduced into one position of an aryl skeleton having a triarylsulfonium salt structure. Moreover, for example, a plurality of substituents introduced and the sum of the Hammett values exceeding 0.46 may be introduced.

As described above, since the Hammett value of the substituent varies depending on the position of introduction, the sum of Hammett values in the photoacid generator according to the present invention is determined by the type of substituent, the introduction position, and the number of introductions. Become.
The Hammett value is usually expressed in the m-position and p-position, but in the present invention, the substituent effect at the o-position is calculated as the same value as the p-position as an index of electron withdrawing. Preferred substitution positions are preferably m-position and p-position, and most preferably p-position, from the viewpoint of synthesis.

  Preferred in the present invention is a sulfonium salt that is tri- or more substituted with a halogen atom, and most preferred is a sulfonium salt that is tri-substituted with a chloro group, specifically, each of the three aryl skeletons. A halogen atom, most preferably a triarylsulfonium salt structure in which —Cl is introduced, is preferable, and a structure in which —Cl is substituted at the p-position is more preferable.

  Examples of the sulfonate anion included in the triarylsulfonium salt contained in the resin composition of the present invention include an arylsulfonate anion and an alkanesulfonate anion, which are substituted with a fluorine atom or an organic group having a fluorine atom. An anion is preferred.

Compounds having a triarylsulfonium salt structure are disclosed in, for example, J. Org. Am. Chem. Soc. 112 (16), 1990; 6004-6015, J.A. Org. Chem. 1988; It can be easily synthesized by the methods described in 5571-5573, WO02 / 081439A1 pamphlet, or European Patent (EP) No. 1113005.
Although a specific example is given below, it is not limited to these.

Among the compounds that generate an acid upon irradiation with actinic rays or radiation, preferred compounds (photoacid generators) include pKa as strong as 2 or less as a generated acid, alkyl or arylcarboxylic acid substituted with sulfonic acid or an electron withdrawing group. Acid, disulfonylimide substituted with an electron withdrawing group, and the like are preferable. Examples of the electron withdrawing group include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.
Examples of the photoacid generator include N-hydroxyimide sulfonate compounds and oxime sulfonates.

  Preferred imide sulfonate compounds as photoacid generators include compounds of the following general formula.

In the formula, C ₁ (carbon atom) and C ₂ (carbon atom) are bonded by a single bond or a double bond, and R ₅₁ or R ₅₂ may be the same or different, and the following (1) to (4) (1) each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group (2) a monocyclic or polycyclic ring that may contain one or more heteroatoms together with C ₁ and C ₂ Form. (3) Represents a residue containing (4) N-sulfonyloxyimide, which forms a condensed aromatic ring containing C ₁ and C ₂ .

R ₅₃ represents an alkyl group, a halogenated alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a camphor group.
In the general formula (PA-5), when R ₅₁ and R ₅₂ correspond to the case of (1), the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Examples thereof include alkyl groups having 1 to 4 carbon atoms such as tert-butyl group. Examples of the cycloalkyl group include those having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. Examples of the aryl group include those having 6 to 14 carbon atoms such as phenyl group, tolyl group, xylyl group, mesityl group, and naphthyl group. When R ₅₁ and R ₅₂ correspond to the case of (2), for example, the following partial structure can be given.

When R ₅₁ and R ₅₂ correspond to the case of (3), for example, the following partial structure can be given.

When R ₅₁ and R ₅₂ correspond to the case of (4), so-called at least two N-sulfonyloxyimide residues are a single bond at the portion of R ₅₁ and R ₅₂ having the partial structures of (1) to (3) above. Or the thing couple | bonded with the following bivalent organic groups can be mention | raise | lifted. However, the following linking groups are used alone or in combination of two or more.
[Divalent organic _{group]: -O -, - S -,} - SO -, - SO 2 -, - NH -, - CO -, - CO 2 -, - NHSO 2 -, - NHCO -, - NHCO 2 −

_Examples of the alkyl group for R ₅₃ include linear or branched alkyl groups having 1 to 20 carbon atoms. Preferred is a linear or branched alkyl group having 1 to 16 carbon atoms, and more preferred is one having 1 to 12 carbon atoms. In the case of an alkyl group having 21 or more carbon atoms, sensitivity and resolving power decrease, which is not preferable. Examples of the halogenated alkyl group include those in which one or two or more hydrogen atoms of the alkyl group are halogenated. Examples of the halogen atom to be substituted include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred are a fluorine atom, a chlorine atom and a bromine atom, and particularly preferred is a fluorine atom. However, the halogen atom to be substituted may be plural types per molecule. The cyclic alkyl group includes a cycloalkyl group having 3 to 12 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, and a polycyclic substituent such as a norbornyl group, an adamantyl group, and a tricyclodecanyl group. Can give. Examples of the alkenyl group include linear or branched alkenyl groups having 1 to 20 carbon atoms. Preferred is a linear or branched alkenyl group having 1 to 16 carbon atoms, and more preferred is one having 1 to 12 carbon atoms. In the case of an alkenyl group having 21 or more carbon atoms, sensitivity and resolving power decrease, which is not preferable.

_Examples of the aryl group of R ₅₃ include a phenyl group and a naphthyl group, and examples of the aralkyl group include a benzyl group. Examples of the substituent of the aryl group and the aralkyl group include a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a tert-butyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a phenyl group, a toluyl group, Aryl group such as xylyl group, mesityl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, sec-butoxy group, tert-butoxy group and other lower alkoxy groups, vinyl group, allyl group, propenyl group, butenyl group, etc. And an acyl group such as alkenyl group, formyl group and acetyl group, and halogen atoms such as hydroxy group, carboxy group, cyano group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom. Preferably, a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, cyclohexyl group, phenyl group, toluyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, sec-butoxy Group, lower alkoxy group such as tert-butoxy group, halogen atom such as cyano group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom. Two or more kinds of substituents on the aryl group and the aralkyl group may be used.

  Specific examples of these compounds are shown below, but are not limited thereto.

  Preferred examples of the oxime sulfonate compound as the photoacid generator include compounds of the following general formula (PA-6).

In General Formula (PA-6), R ₆₁ and R ₆₂ are each independently an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or a cycloalkenyl group, which may have a substituent having 1 to 16 carbon atoms. Represents an aryl group, a heteroaryl group or a cyano group which may have a substituent. R61 and R62 are alkylene chain, alkenylene chain, alkynylline chain, which may have a substituent having 2 to 8 carbon atoms, or phenylene, freelene, thienylene, -O which may have a substituent. It may be bonded to R ₆₁ or R _{62 of the} compound represented by another general formula (PA-6) through a linking chain containing —, —S—, —N—, and —CO—. R ₆₃ represents an alkyl group, a cycloalkyl group, or an aryl group which may have a substituent, which may have a substituent having 1 to 16 carbon atoms.

Examples of the alkyl group having 1 to 16 carbon atoms in R _{61 to} R ₆₃ include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, t-amyl group, alkyl groups such as n-hexyl group, n-octyl group, i-octyl group, n-decyl group, undecyl group, dodecyl group, hexadecyl group, trifluoromethyl group, perfluoropropyl group, perfluorobutyl group, perfluoro-t- Examples thereof include a butyl group, a perfluorooctyl group, a perfluoroundecyl group, and a 1,1-bistrifluoromethylethyl group.

Examples of the alkenyl group for R ₆₁ and R ₆₂ include allyl group, methallyl group, vinyl group, methylallyl group, 1-butenyl group, 3-butenyl group, 2-butenyl group, 1,3-pentadienyl group, 5-hexenyl group, A 2-oxo-3-pentenyl group, a decapentaenyl group, a 7-octenyl group and the like can be mentioned.
Examples of the alkynyl group in R ₆₁ and R ₆₂ include an ethynyl group, a propargyl group, a 2-butynyl group, a 4-hexynyl group, a 2-octynyl group, a phenylethynyl group, and a cyclohexylethynyl group.

Examples of the cycloalkyl group in R _{61 to} R ₆₃ include those having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.

Examples of the cycloalkenyl group for R ₆₁ and R ₆₂ include a cyclobutenyl group, a cyclohexenyl group, a cyclopentadienyl group, a bicyclo [4.2.4] dodeca-3,7-dien-5-yl group, and the like.

Examples of the aryl group in R _{61 to} R ₆₃ include those having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group, which may have a substituent.

The above substituents include alkyl groups, cycloalkyl groups, alkoxy groups, halogen atoms (fluorine atoms, chlorine atoms, iodine atoms), cyano groups, hydroxy groups, carboxy groups, nitro groups, aryloxy groups, alkylthio groups, aralkyls. And groups represented by the following formula (1A).
Here, the alkyl group and the cycloalkyl group have the same meanings as described above. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group. Examples of the aralkyl group include a benzyl group, a naphthylmethyl group, a furyl group, and a thienyl group.

In the formula _{(1A), R 61} and _{R 62} have the same meanings as _{R 61} and _{R 62} in formula (PA-6).
Specific examples of the compound represented by the general formula (PA-6) are shown below, but the present invention is not limited thereto.

  Specific examples of more preferable oxime sulfonate compounds include the following (z66) to (z70).

  As a general formula of nitrobenzyl sulfonate preferable as a photoacid generator, a compound represented by the general formula (TA-9) can be given.

Z in this formula is an alkyl group having 1 to 30 carbon atoms, an aryl group, an alkylaryl group, a halogen-substituted alkyl group having 1 to 30 carbon atoms, a halogen-substituted aryl group, a halogen-substituted alkylaryl group, Nitro-substituted aryl group having 6 to 30 carbon atoms, nitro-substituted alkylaryl group, aryl group having 6 to 30 carbon atoms and halogen substituent, alkylaryl group having nitro substituent and halogen substituent and groups having the formula _{C 6 H 4 SO 3 CHR'C 6} H 4-m Q m (NO) 2 (R ' is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms, R ₉ is selected from a hydrogen atom, a methyl group, and a nitro-substituted aryl group having 6 to 30 carbon atoms, and each Q is a hydrocarbon group having 1 to 30 carbon atoms, Independently selected from a droxycarbonoxy group, NO ₂ , a halogen atom and an organosilicon group, the value of m is 0, 1 or 2 provided that Q is not an acidic group. R ₉ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 4 carbon atoms.
Specific examples of the compound represented by the general formula (TA-9) include the following compounds.

In the resin composition of the present invention, the blending amount of the photoacid generator is preferably 0.5 parts by mass to 30 parts by mass when the total amount of the polymer compound (A) is 100 parts by mass, and 2 parts by mass to 20 parts by mass. Part by mass is more preferable.
A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.

(2) Quinonediazide photosensitizer The o-quinonediazide photosensitizer as the quinonediazide photosensitizer 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. However, naphthoquinone-1,2-diazide-4-sulfonyl chloride is preferable in terms of sensitivity.

As the hydroxy compound, for example, hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4 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 [2,1-a] i Den, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane can be used.
Examples of the amino compound 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-amino3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino3-hydroxyphenyl) sulfone, bis (3-amino-4- Hydroxyphenyl) hexafluoropropane, bis (4 An 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 1/1 to 1 / 0.9. A preferable reaction temperature is 0 ° C. to 40 ° C., and a preferable reaction time is 1 hour to 24 hours.

  As the reaction solvent, solvents such as dioxane, 1,3-dioxolane, acetone, methyl ethyl ketone, tetrahydrofuran, chloroform, N-methylpyrrolidone, γ-butyrolactone and the like are used. Examples of the dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine, 4-dimethylaminopyridine and the like.

In the resin composition of the present invention, the amount of the quinonediazide photosensitizer is 1 mass when the total amount of the polymer compound is 100 mass parts in terms of the difference in dissolution rate between the exposed area and the unexposed area and the allowable range of sensitivity. Parts to 25 parts by mass are preferable, and 5 parts to 20 parts by mass are more preferable.
The amount of the photosensitizer other than the quinonediazide photosensitizer is preferably 0.1 parts by mass to 15 parts by mass, and more preferably 0.5 parts by mass to 10 parts by mass, when the total amount of the polymer compound is 100 parts by mass.

  Examples of quinonediazide photosensitizers include compounds having the following structures.

  In the formula, D is independently H or any of the following groups.

  However, at least 1 D should just be said quinonediazide group in each compound.

(Sensitizer)
When the resin composition of the present invention is a photosensitive resin composition containing a photosensitizer, it is preferable to add a sensitizer in order to promote the decomposition of the photosensitizer. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in the electronically excited state comes into contact with the photosensitizer, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the photosensitizer undergoes a chemical change and decomposes to generate radicals, acids, or bases.

  Examples of preferable sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.

  Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium), coumarins (for example, 7-diethylamino 4-methylcoumarin). Among them, an anthracene derivative is particularly preferable as a sensitizer.

  Preferable specific examples include (C-1) to (C-26) shown below, but are not limited thereto.

As the sensitizer as described above, a commercially available one may be used, or it may be synthesized by a known synthesis method.
The addition amount of the sensitizer is preferably 20 parts by mass to 200 parts by mass, and more preferably 30 parts by mass to 150 parts by mass with respect to 100 parts by mass of the photosensitive agent.

(Crosslinking agent)
In the present invention, it is preferable to use a crosslinking agent as a modifier.
Here, the crosslinking agent is a material that is crosslinked by an acid and polymers such as methylol group, alkoxymethyl group, a melamine compound substituted with at least one group selected from the acyloxymethyl groups, guanamine compound, glycoluril compound , Urea compounds, phenolic compounds or phenolic ether compounds, and epoxy compounds, oxetane compounds, thioepoxy compounds, isocyanate compounds, azide compounds, or compounds containing double bonds such as alkenyl ether groups. From the viewpoint of heat resistance, methylol-based crosslinking agents and melamine / glycoluril-based crosslinking agents are preferably used.

  Further, (1) a compound containing an alkoxymethyl group or acyloxymethyl group, (2) a compound containing a methacryloyl group or an acryloyl group, and (3) an epoxy compound or an oxetane compound are preferred.

(1) Compound containing alkoxymethyl group or acyloxymethyl group A compound containing an alkoxymethyl group or acyloxymethyl group may be added to the resin composition of the present invention. This compound is known to prevent pattern melting and heat shrinkage during curing without impairing lithography performance. In addition, it is known that chemical resistance can be improved when applied to a low-temperature curing process.

The alkoxymethyl group or acyloxymethyl group of the compound preferably has 2 to 5 carbon atoms, and more preferably 2 or 3 carbon atoms. In the case of an alkoxymethyl group, 2 carbon atoms are particularly preferred, and in the case of an acyloxymethyl group, 3 carbon atoms are particularly preferred.
1-10 are preferable, as for the total of the alkoxymethyl group and acyloxymethyl group which the said compound has, More preferably, it is 2-8, Most preferably, it is 3-6.
The molecular weight of the compound is preferably 1500 or less, and more preferably 180 to 1200.

As a compound containing an alkoxymethyl group or an acyloxymethyl group, an alkoxymethyl group or an acyloxymethyl group is (CL-1) a direct phenol derivative, and (CL-2) a compound in which a nitrogen atom is bonded, (CL-3) Examples thereof include compounds bonded to an aromatic carbon atom of a triazine derivative (melamine type).
Examples of the (CL-1) compound include compounds represented by the following general formula.

In the formula, R ₈ represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or an action of an acid. The group which decomposes | disassembles and produces an alkali-soluble group is shown. R ₇ represents each independently an alkyl group, a cycloalkyl group or an alkenyl group, E is representative of the m ₂ divalent linking group. Examples of the linking group include an alkylene group (eg, methylene, ethylene, propylene, etc.), a cycloalkylene group (eg, cyclohexylene, cyclopentylene, etc.), an arylene group (1,2-phenylene, 1,3-phenylene, 1,4- Phenylene, naphthylene, etc.), ether groups, carbonyl groups, ester groups, amide groups, and m ₂ valent groups obtained by removing m ₂ -2 of any hydrogen atom in a divalent group combining these groups. . When E is monovalent, a hydrogen atom, an alkyl group that is a monovalent group corresponding to the above divalent group, an aryl group, and the like can be given. The p 1, 2, q is 0 to 2, as _{m 2} 1 to 8, preferably 2 to 6.

The group capable of decomposing by an acid as R ₆ to generate an alkali-soluble group is a group that decomposes by the action of an acid to generate an alkali-soluble group such as a hydroxyl group or a carboxyl group, and is eliminated by the action of an acid, for example. group, or _{-C (R 4) 2 -COOR 5} (R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, _{R 5} is. represents a group capable of leaving by the action of acid).

Decomposing by the action of an acid, as a base to produce an alkali-soluble group, when R6 is a group capable of leaving by the action of an acid, by the action of an acid, by R ₆ itself is disengaged, resulting -OH is also R _{When 6} is —C (R ₄ ) ₂ —COOR ₅ , R ₅ is released by the action of an acid to produce —COOH.

Examples of the group capable of leaving by the action of an acid include an acetal group and a tertiary ester group.
Specific examples of the acetal group include alkoxyalkyl groups such as methoxymethyl group and ethoxyethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, alkoxy-substituted tetrahydropyranyl group, alkoxy-substituted tetrahydrofuranyl group and the like.

  Specific examples of the ester group include a t-butyl group, a t-amyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, and a 1-ethylcyclohexyl group.

  Specific examples of the compound having an alkoxymethyl group of (CL-1) include the following structures.

In addition, the compound which has an acyloxymethyl group can mention the compound which changed the alkoxymethyl group of the following compound into the acyloxymethyl group.
The compound having an alkoxymethyl group or acyloxymethyl in the molecule is not limited to the following compounds.

  Examples of the compound (CL-2) include compounds represented by the following general formula.

In the formula, R ₁₀₃ represents an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, R ₁₀ 1 and R ₁₀₂ represent a monovalent organic group, and R ₁₀₁ and R ₁₀₂ are bonded to each other. May form a 5- to 8-membered ring.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 of the methylol groups of tetramethylolglycoluril are methoxymethylated, or a mixture thereof, tetramethylolglycoluril Or a mixture thereof in which 1 to 4 of the methylol groups are acyloxymethylated. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, or a mixture thereof, tetramethoxyethyl urea, and the like.

Specific examples of the compound having an alkoxymethyl group include the following structures.
In addition, the compound which has an acyloxymethyl group can mention the compound which changed the alkoxymethyl group of the following compound into the acyloxymethyl group.

  The compound having an alkoxymethyl group or acyloxymethyl in the molecule is not limited to the following compounds.

A melamine compound can be mentioned as a compound of (CL-3). Specific examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, and a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, Examples thereof include compounds in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof.
As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available product or a compound synthesized by a known method may be used.

(2) Compound containing methacryloyl group or acryloyl group The resin composition of the present invention may use a compound containing a methacryloyl group or an acryloyl group for the purpose of improving film properties.
The compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of acrylic acid esters and methacrylic acid esters. It has been found that the addition of this compound improves the film properties. Therefore, a compound having 2 or more, more preferably 4 or more acryloyl groups and methacryloyl groups in one molecule is preferable.

  Preferred specific examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di ( (Meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanedio Such as rudi (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc. Polyfunctional alcohols obtained by addition reaction of ethylene oxide or propylene oxide and then (meth) acrylated, in Japanese Patent Publication Nos. 48-41708, 50-6034, 51-37193, etc. Described urethane acrylates; polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc .; epoxy resins and (meth) Such as multifunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

(3) Compound containing epoxy group or oxetanyl group In the resin composition of the present invention, a compound containing an epoxy group or oxetanyl group may be used for the purpose of improving film properties. The compound containing an epoxy group or an oxetanyl group is a compound generally called an epoxy resin or an oxetane resin.

  Examples of the epoxy resin include bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compounds.

  For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (manufactured by Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (manufactured by Daicel Chemical Industries, Ltd.) These similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel UC) may also be used.

  Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (manufactured by Tohto Kasei), Denacol EM-125, etc. (manufactured by Nagase Kasei), and biphenyl type 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl and the like.

  Examples of the alicyclic epoxy compound include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), Santo Tote ST. -3000, ST-4000, ST-5080, ST-5100 and the like (manufactured by Tohto Kasei). In addition, Epototo YH-434 and YH-434L, which are amine type epoxy resins, glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin can be used.

  Among these epoxy resins, preferably novolak type epoxy compounds and alicyclic epoxy compounds are preferable, and those having an epoxy equivalent of 180 to 250 are particularly preferable. Examples of such a material include Epicron N-660, N-670, N-680, N-690, YDCN-704L (manufactured by DIC) and EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.).

In the resin composition of this invention, you may contain 2 or more types of epoxy resins.
As the oxetane resin, Aron oxetane OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used. The oxetane resin can be used alone or mixed with an epoxy resin. In particular, when used in combination with an epoxy resin, the reactivity is high, which is preferable from the viewpoint of improving film properties.

These crosslinking agents can be used alone or in combination of two or more.
The addition amount of the crosslinking agent to the resin composition is preferably 1 part by mass to 20 parts by mass, and more preferably 3 parts by mass to 15 parts by mass when the total amount of the polymer compound is 100 parts by mass.

(Thermal acid generator)
In the present invention, a thermal acid generator may be used in order to improve film physical properties and the like at low temperature curing.
The thermal acid generator of the present invention is a compound that generates an acid by heat, and is usually a compound having a thermal decomposition point in the range of 130 ° C to 250 ° C, preferably 150 ° C to 220 ° C. It is a compound that generates a low nucleophilic acid such as sulfonic acid, carboxylic acid, disulfonylimide and the like.

  As the generated acid, sulfonic acid, an alkyl substituted with an electron withdrawing group or an arylcarboxylic acid having a strong pKa of 2 or less, disulfonylimide substituted with an electron withdrawing group, and the like are preferable. Examples of the electron withdrawing group include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

  As the thermal acid generator, a photoacid generator that generates an acid by the above-described exposure can be applied. Examples include onium salts such as sulfonium salts and iodonium salts, N-hydroxyimide sulfonate compounds, oxime sulfonates, o-nitrobenzyl sulfonates, and the like. Of these, N-hydroxyimide sulfonate compounds, oxime sulfonates, and o-nitrobenzyl sulfonates are preferred.

In the present invention, it is also preferable to use a sulfonic acid ester that does not substantially generate an acid by exposure to exposure light and generates an acid by heat.
The fact that acid is not substantially generated by exposure light exposure can be determined by no change in the spectrum by measuring IR spectrum and NMR spectrum before and after exposure of the compound.
The molecular weight of the sulfonate ester is generally 230 to 1000, preferably 230 to 800.
For example, the sulfonate ester represented by the following general formula (TA-10) can be given.

In the above formula, R13 and R14 are each independently an optionally substituted linear or branched or cyclic alkyl group having 1 to 10 carbon atoms or an optionally substituted carbon group having 6 to 20 carbon atoms. An aryl group of Examples of the substituent include a hydroxyl group, a halogen atom, a cyano group, a vinyl group, an acetylene group and a linear or cyclic alkyl group having 1 to 10 carbon atoms.
Preferable specific examples of the sulfonic acid ester include the following.

  As the sulfonic acid ester, a compound represented by the following general formula (TA-20) can be more preferably used from the viewpoint of heat resistance.

A represents a _{m 3} divalent linking group. R ₁₆ represents an alkyl group, an aryl group, an aralkyl group, or a cyclic alkyl group. R ₁₅ represents a hydrogen atom, an alkyl group, or an aralkyl group. m ₃ represents an integer of 2 to 8.

Linking group m ₃ valent The A, for example, an alkylene group (e.g. methylene, ethylene, propylene, etc.), a cycloalkylene group (cyclohexylene, cyclopentylene, etc.), an arylene group (1,2-phenylene, 1, 3-phenylene, 1,4-phenylene, naphthylene, etc.), ether group, carbonyl group, ester group, amide group, and any hydrogen atom of a divalent group such as a group obtained by combining these groups (m ₃ − 2) pieces m ₃ divalent group obtained by removing the like. The linking group as A generally has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

The alkyl group for R ₁₅ and R ₁₆ is generally an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. . Specific examples include methyl, ethyl, propyl, butyl, hexyl, octyl and the like.

The aralkyl group of R ₁₅ and _{R 16,} typically an aralkyl group having 7 to 25 carbon atoms, is preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 15 carbon atoms . Specific examples include benzyl, toluylmethyl, mesitylmethyl, phenethyl and the like.

The cyclic alkyl group for R ₁₆ is generally a cyclic alkyl group having 3 to 20 carbon atoms, preferably a cyclic alkyl group having 4 to 20 carbon atoms, more preferably a cyclic alkyl group having 5 to 15 carbon atoms. is there. Specific examples include cyclopentyl, cyclohexyl, norbornyl, camphor group and the like.

  The linking group as A may further have a substituent. The substituent is an alkyl group (an alkyl group having 1 to 10 carbon atoms, specifically methyl, ethyl, propyl, butyl, hexyl). Octyl, etc.), aralkyl groups (aralkyl groups having 7 to 15 carbon atoms, specifically benzyl, toluylmethyl, mesitylmethyl, phenethyl, etc.), aryl groups (aryl groups having 6 to 10 carbon atoms, specifically Are phenyl, toluyl, xylyl, mesityl, naphthyl, etc.), an alkoxy group (the alkoxy group may be linear, branched or cyclic, and is an alkoxy group having 1 to 10 carbon atoms, specifically, Methoxy, ethoxy, linear or branched propoxy, linear or branched butoxy, linear or branched pentoxy, cyclopentyloxy, cyclohexyloxy, etc.) A reeloxy group (an aryloxy group having 6 to 10 carbon atoms, specifically phenoxy, toluyloxy, 1-naphthoxy, etc.), an alkylthio group (which may be linear, branched or cyclic, the number of carbon atoms) 1 to 10 alkylthio groups, specifically methylthio, ethylthio, linear or branched propylthio, cyclopentylthio, cyclohexylthio), arylthio groups (arylthio groups having 6 to 10 carbon atoms, specifically phenylthio , Toluoylthio, 1-naphthylthio, etc.), acyloxy groups (acyloxy groups having 2 to 10 carbon atoms, specifically acetoxy, propanoyloxy, benzoyloxy, etc.), alkoxycarbonyl groups (alkoxycarbonyl having 1 to 10 carbon atoms) Groups such as methoxycarbonyl, ethoxycarbonyl, Or branched propoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, etc.), can be exemplified.

In General Formula (TA-20), R ₁₆ is preferably an alkyl group or an aryl group. R ₁₅ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a hydrogen atom.
Examples of the sulfonic acid ester that can be used in the present invention include the following specific compounds, but are not limited thereto.

  As the sulfonic acid ester usable in the present invention, a commercially available one may be used, or one synthesized by a known method may be used. The sulfonic acid ester can be synthesized, for example, by reacting a sulfonyl chloride or sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.

  The amount of the sulfonate ester added to the resin composition is a polymer compound (A) obtained by reacting the monomer represented by the general formula (2) with the monomer represented by the general formula (3). ) Is 100 parts by mass, 1 part by mass to 20 parts by mass is preferable, and 2 parts by mass to 15 parts by mass is particularly preferable.

(Adhesion promoter)
If necessary, an adhesion promoter such as an organosilicon compound, a silane coupling agent, and a leveling agent may be added to the resin composition in the present invention.

  Examples of these are, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl. Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, tris ( Acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like. When using an adhesion promoter for the resin composition, 0.1 to 20 parts by mass is preferable, and 0.5 to 10 parts by mass is more preferable with respect to 100 parts by mass of the polymer compound (a).

(solvent)
The solvent is not particularly limited as long as it can dissolve the resin composition of the present invention. However, in order to prevent the solvent from evaporating more than necessary at the time of application and causing the solid content of the resin composition to precipitate at the time of application, Boiling solvents are preferred.

  Preferred solvents include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, 3-methoxybutanol and cyclohexanone.

Further, a solvent having a high boiling point such as N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), propylene carbonate and the like may be used supplementarily.
However, if the solvent remains in the film after curing, sufficient film physical properties cannot be obtained. Therefore, it is not preferable that the solvent having a boiling point not lower than the curing temperature (high boiling point solvent) is 30% by mass or more in the solvent. The amount of the high-boiling solvent added is 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less.

4). Cured relief pattern forming method As a method of forming a cured relief pattern using the resin composition of the present invention, (1) the resin composition of the present invention is coated on a suitable substrate, and (2) the coated composition The substrate is baked (pre-baked), (3) exposed with actinic rays or radiation, (4) post-heated if necessary, (5) developed with an aqueous developer, (6) fully exposed if necessary, and ( 7) A cured relief pattern can be formed by heat curing (post-baking).
The coated and exposed substrate can be baked at an elevated temperature as needed prior to development. Further, the developed substrate may be rinsed before curing. After development, prior to thermosetting (post-baking), post-exposure can be performed as necessary.

  Thus, the resin composition of the present invention is applied on a semiconductor element or a glass substrate so that the thickness after heat curing becomes a predetermined thickness (for example, 0.1 μm to 30 μm), and prebaking, exposure, development, A relief pattern for a semiconductor device or a display device can be formed by heat curing.

Hereinafter, a method for forming a relief pattern will be described in more detail.
The resin composition of the present invention is coated on a suitable substrate. The substrate is, for example, a semiconductor or ceramic substrate such as a silicon wafer, glass, metal or plastic. In general, a silicon wafer is used for a semiconductor device, and a glass substrate is used for a display device. Coating methods include, but are not limited to, spray coating, spin coating, slit coating, offset printing, roller coating, screen printing, extrusion coating, meniscus coating, curtain coating, and dip coating.

  After coating, depending on the method, it is baked for several minutes to half an hour at an elevated temperature of about 70 ° C. to 130 ° C. to evaporate the remaining solvent. The resulting dried resin composition layer is then exposed to actinic rays or radiation in a preferred pattern through a mask. As actinic rays or radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used. The most preferred radiations are those having wavelengths of 436 nm (g-line), 405 nm (h-line) and 365 nm (i-line).

  It is advantageous to heat the substrate exposed to actinic rays or radiation to a temperature of about 70 ° C to 130 ° C. The exposed substrate is heated in this temperature range for a short time, generally a few seconds to a few minutes. This stage of the method is commonly referred to in the art as post-exposure baking.

  Next, the coating film is developed with an aqueous developer, and a relief pattern is formed. Aqueous developers include inorganic alkalis (eg, potassium hydroxide, sodium hydroxide, aqueous ammonia), primary amines (eg, ethylamine, n-propylamine), secondary amines (eg, diethylamine, di-n-propyl). Amines), tertiary amines (eg, triethylamine), alcohol amines (eg, triethanolamine), quaternary ammonium salts (eg, tetramethylammonium hydroxide, tetraethylammonium hydroxide), and alkaline solutions such as mixtures thereof There is. The most preferred developer is one containing tetramethylammonium hydroxide. In addition, an appropriate amount of surfactant may be added to the developer. Development can be carried out by dipping, spraying, paddling, or other similar development methods.

In some cases, the relief pattern is then rinsed using deionized water.
The relief pattern is exposed as a whole after development if necessary. It is preferred exposure energy of the entire surface exposure is the energy of ^{100mJ / cm 2 ~1000mJ / cm 2} . The entire surface exposure is preferable from the viewpoint of improving the transparency when used as a resin composition for a display device.

  The relief pattern is then heat cured to obtain a final pattern. Thermosetting is performed to form a film having high heat resistance, chemical resistance, and film strength. Common photosensitive polyimide precursor compositions have been heat cured at a temperature of about 300 ° C to 400 ° C. On the other hand, with the resin composition of the present invention, a film having film physical properties equal to or higher than that of a conventional photosensitive polyimide precursor composition can be obtained at less than 300 ° C., more specifically at 200 ° C. to 250 ° C.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.
The compound groups used in the examples and comparative examples are shown below.

First, a synthesis example of a polymer compound is shown.
(Synthesis Example 1)

N- methyl-2-pyrrolidone 195 mL, diphenol acid in toluene 97 mL (a-15; manufactured by Tokyo Kasei Kogyo (Co.)) 25.0g (87.3mmol), dichlorodiphenyl sulfone 25.1 g (b-2; Tokyo Kasei (Manufactured by Kogyo Co., Ltd.) (87.3 mmol) and potassium carbonate 36.2 g (261.9 mmol) were added and stirred at 150 ° C. for 4 hours, and then toluene was distilled off. Furthermore, the polymerization solution was obtained by reacting at 180 ° C. for 16 hours. After completion of the reaction, the inorganic salt was filtered off from the polymerization solution and poured into an aqueous hydrochloric acid solution to precipitate a polymer. The precipitated solid was washed with water and dried under reduced pressure at 50 ° C. to obtain 40 g of a polymer compound (A-1) having an acid value of 115 mgKOH / g. A new strong absorption at 1230 cm −1 in the IR spectrum confirmed the formation of an ether bond and the above reaction. The number average molecular weight of the polymer compound (A-1) was 7,000 as calculated from the ¹ H-NMR spectrum.

(Synthesis Example 2)

  Polymerization was carried out in the same manner by replacing diphenolic acid (a-15) in Synthesis Example 1 with 13.5 g (a-3; 87.3 mmol) of 3,5-dihydroxybenzoic acid, and a high acid value of 120 mgKOH / g A molecular compound (A-2) was synthesized.

(Synthesis Example 3)

  Diphenolic acid (a-15) in Synthesis Example 1 was added to 19.9 g (a-48; 87.3 mmol) of bisphenol A, and difluorodiphenylsulfone (b-2) was added to 16.7 g (b-) of 3,5-dichlorobenzoic acid. 30; 87.3 mmol), and the same polymerization was carried out to synthesize a polymer compound (A-3) having an acid value of 120 mgKOH / g.

(Synthesis Example 4)

  Polymerization was carried out in the same manner by changing the diphenolic acid (a-15) in Synthesis Example 1 to 23.8 g (a-30; 87.3 mmol) of 2-carboxybisphenol A, and a polymer compound having an acid value of 110 mgKOH / g ( A-4) was synthesized.

(Synthesis Example 5)

A stirring device equipped with a three-necked flask, N- methyl-2-pyrrolidone 195 mL, toluene 97 mL 5,5' thiodisalicylic acid (aa-2; manufactured by Tokyo Kasei Kogyo (Co.)) 26.7 g (87.3 mmol) , Difluorodiphenylsulfone 22.2 g (b-2; manufactured by Tokyo Chemical Industry Co., Ltd.) (87.3 mmol) and potassium carbonate 36.2 g (261.9 mmol) were added, and the mixture was stirred at 150 ° C. for 4 hours under a nitrogen stream. After that, toluene was distilled off. Furthermore, it reacted at 180 degreeC for 16 hours, and obtained the polymerization solution. After completion of the reaction, the inorganic salt was filtered off from the polymerization solution and poured into an aqueous hydrochloric acid solution to precipitate a polymer. The precipitated solid was washed with water and then dried under reduced pressure at 50 ° C. to obtain 41 g of Resin (A-5). The generation of an ether bond was confirmed by the occurrence of a new strong absorption at 1227 cm −1 in the IR spectrum, confirming the above reaction. The number average molecular weight of the polymer compound (A-5) was 7,000 as calculated from the ¹ H-NMR spectrum (manufactured by BRUKER). The acid value was 215 mgKOH / g.

(Synthesis Example 6)

  A polymer having an acid value of 390 mgKOH / g was obtained by performing polymerization in the same manner except that difluorodiphenylsulfone (b-2) in Synthesis Example 5 was replaced with 16.7 g (b-30; 87.3 mmol) of 3,5-dichlorobenzoic acid. Compound (A-6) was synthesized.

(Synthesis Example 7)

  5,5′-thiodisalicylic acid (aa-2; 87.3 mmol) in Synthesis Example 5 was converted to 23.9 g (aa-10; 87.3 mmol) of 2,2′-bis (2-carboxy-4-hydroxy) phenylmethane. ), Difluorodiphenylsulfone was polymerized in the same manner in place of 32.8 g (b-36; 87.3 mmol) of 3,3′-dicarboxy-4,4′-dichlorodiphenylsulfone, and the acid value was 380 mgKOH / The polymer compound (A-7) which is g was synthesized.

The benzoxazine compound was prepared by synthesizing the following commercially available compounds and commercially available compounds as raw materials.
(B-1); Ba type benzoxazine (trade name; manufactured by Shikoku Kasei Kogyo Co., Ltd.). In the present application, Compound No. It corresponds to (c-2).
(B-2); Bm type benzoxazine (trade name; manufactured by Shikoku Kasei Kogyo Co., Ltd.). In the present application, Compound No. It corresponds to (c-1).
(B-3); BS-BXZ (trade name; manufactured by Konishi Chemical Industry Co., Ltd.). In the present application, Compound No. It corresponds to c-12.
(B-4); Compound No. 1 in the present application was reacted with phenol novolak (OH equivalent = 200), aniline and paraformaldehyde according to a conventional method. c-21 was obtained.
(B-5); In the same manner as (B-4), Compound No. 1 in this application was prepared using 1,5-dihydroxynaphthalene as a raw material instead of phenol novolac. c-17 was obtained.

Synthesis examples of the photosensitizer used in the examples are shown below.
(Synthesis Example 8)
This is a synthesis of a photosensitizer (P-2).
The following phenol compound (BP-2) 21.6 g and 1,4-dioxane 200 mL were added to a three-necked flask equipped with a stirrer and a temperature controller, and dissolved until uniform. Next, 27 g of 1,2-naphthoquinonediazide-4-sulfonyl chloride was added and dissolved. The reaction vessel was cooled to 10 ° C. with ice water, and then 11.1 g of triethylamine was added dropwise over 1 hour. It stirred for 24 hours after completion | finish of dripping. After completion of the reaction, distilled water was added to dissolve the deposited salt, stirred for 30 minutes, neutralized with dilute hydrochloric acid, and crystallized in 1 L of distilled water. The precipitated dark yellow powder was collected by filtration. The residue was dissolved again in 200 mL of dioxane and crystallized in 1 L of distilled water. The precipitated filtrate was filtered, and the filtrate was washed with 1 L of distilled water and filtered to recover 39 g of the target product (P-2) as a dark yellow powder. As a result of analyzing the obtained (P-2) by high performance liquid chromatography (S1525 manufactured by Waters), the purity of the esterified product of the phenol compound (P-2) was 98% (detection wavelength: 254 nm).

(Synthesis Example 9)
This is a synthesis of a photosensitizer (P-3).
In the example described in Synthesis Example 8, the phenol compound used was changed to the following (BP-3), and the amount of 1,2-naphthoquinonediazide-4-sulfonyl chloride used was doubled as in the above Synthesis Example. The photosensitizer (P-3) was synthesized by the method described above. As a result of analyzing the obtained (P-3) by high performance liquid chromatography (S1525 manufactured by Waters), the purity of the esterified product of the phenol compound (P-3) was 97.5% (detection wavelength: 254 nm).

Example 1
<Preparation of resin composition>
70 parts by mass of the synthesized polymer compound (A-2), 25 parts by mass of the benzoxazine compound (B-1), 2,3,4-tris [-2-diazo-1 (2H) -naphthalenone-4-sulfonyloxy ] After dissolving 5 parts by mass of benzophenone (P-1) (manufactured by Toyo Gosei Kogyo Co., Ltd.) in 200 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), it was filtered through a 0.2 μm polytetrafluoroethylene filter, A resin composition was obtained.

<Characteristic evaluation>
(Alkali dissolution rate)
The resin composition on the solution was applied onto a silicon wafer using a spin coater and dried on a vacuum adsorption type hot plate at 120 ° C. for 60 seconds to obtain a resin film having a thickness of 1.0 μm. The alkali dissolution rate for a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution (23 ° C.) was measured using a dissolution rate monitor (DRM: manufactured by Perkin Elmer).

(Pattern formability)
After apply | coating the obtained resin composition on a silicon wafer using a spin coater, it dried at 125 degreeC for 3 minute (s) in oven, and obtained the coating film with a film thickness of 7 micrometers. By a high pressure mercury lamp through a glass mask in this coating film, i-ray (365 nm) of 100 mJ / cm ² (illuminance: 20mW / cm ²⁾ was irradiated, in 2.38 weight% of 25 ° C. at tetramethylammonium hydroxide aqueous solution The exposed portion was dissolved and removed by paddle development for 60 seconds, and rinsed with pure water for 20 seconds. Next, by measuring the thickness of the film at this time, the degree of film reduction in the unexposed area due to development was evaluated as the remaining film ratio. When the remaining film ratio is 90% or more, the pattern formability is good. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

A: Remaining film ratio is 95% or more
○: Remaining film ratio 90% or more to less than 95%
Δ: Remaining film ratio 80% or more and less than 90%
X: Remaining film rate less than 80%

(resolution)
After apply | coating the obtained resin composition on a silicon wafer using a spin coater, it dried at 125 degreeC for 3 minute (s) in oven, and obtained the coating film with a film thickness of 7 micrometers. The coating film i-line by a high pressure mercury lamp through a glass mask (365 nm) of 100 mJ / cm ² (illuminance: 20mW / cm ²⁾ was irradiated for 60 seconds 2.38 mass% tetramethylammonium hydroxide aqueous solution 25 ° C. The exposed area was dissolved and removed by paddle development, and rinsed with pure water for 20 seconds. As a result, it was confirmed that a 5 μm extraction pattern was resolved on the silicon wafer.
The resolution was evaluated by SEM observation of the obtained pattern.

(Curing shrinkage)
The obtained resin composition was applied onto a silicon wafer and heated in an oven at 110 ° C. for 5 minutes and then at 200 ° C. for 60 minutes to cure the resin. The obtained coating film was peeled off, the specific gravity before and after curing was measured, and the curing shrinkage was calculated by the following formula.
Curing shrinkage: D = (S−S ′) / S × 100
Here, S is the specific gravity before curing, and S ′ is the specific gravity after curing. The specific gravity was measured by B method pycnometer method of JIS K-7112.

(Solvent insolubilization rate)
The obtained resin composition was applied onto a silicon wafer and heated in an oven at 110 ° C. for 5 minutes and at 200 ° C. for 60 minutes to cure the resin. The obtained coating film was peeled off, and the weight was accurately weighed (W ₁ ). This film was placed in a bag-shaped 200 mesh wire net, heated and extracted in THF at 60 ° C. for 1 hour, and then THF was vacuum dried. The weight of the membrane (W ₂ ) was determined. The “solvent insolubilization rate” was determined by the following formula.
[Solvent insolubilization rate (%)] = (W ₂ ) / (W ₁ ) × 100

(Examples 2 to 20, Comparative Examples 1 to 3)
<Preparation of resin composition>
The polymer compound (A-1) in the resin composition in the example described in Example 1 was changed to the polymer compounds (A-2) to (A-7) obtained in Synthesis Example 2 to Synthesis Example 7. A resin composition was prepared in the same manner as in Example 1, except that the benzoxazine compound to be combined and the photoacid activator were changed as shown in Table 1.

(Comparative Example 4)
<Preparation of resin composition>
In the preparation of the resin composition of Example 1, except that benzoxazine compound (B-1) was changed to the weight of HMON-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) in the same manner, the resin compositions of Comparative Obtained.

(Comparative Example 5)
<Preparation of resin composition>
Resulting in the preparation of the resin composition of Example 1, except that benzoxazine compound (B-1) was changed to the weight of NIKALAC N2702 (manufactured by Sanwa Chemical Co., Ltd.) in the same manner, the resin compositions of Comparative It was.

(Comparative Example 6)
In the production of the resin composition of Example 1, the resin was changed in the same manner except that the benzoxazine compound (B-1) was changed to the same weight of KAYARAD DPHA (crosslinking agent represented by the following formula, manufactured by Nippon Kayaku Co., Ltd.). A composition was obtained.

(Comparative Example 7)
In the preparation of the resin composition of Example 1, except that the benzoxazine compound (B-1) of the same weight EHPA-3150 (epoxy crosslinking agent represented by the following formula, manufactured by Daicel Chemical Industries, Ltd.) In the same manner, a resin composition was obtained.

(Comparative Example 8)
A resin composition was prepared in the same manner as in Example 1 except that the polymer compound (A-1) in Example 1 was changed to the comparative polymer (J-1) synthesized as described below. Evaluation was performed.

-Synthesis of comparative polymer (J-1)-
Synthesis was performed according to the method described in Example 5 of JP-A-2004-133088. Under a dry air stream, 155 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (manac Co., Ltd., 0.5 mol), 138 g of 3-hydroxyphenylethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.0 mol) was added to 2000 mL of γ-butyrolactone and 79 g of pyridine (manufactured by Tokyo Chemical Industry Co., Ltd., 1.0 mol), and stirring was continued at 50 ° C. for 6 hours. The solution was cooled to -10 ° C. and added dropwise dicyclohexylcarbodiimide 206 g (manufactured by Tokyo Kasei Kogyo Co., Ltd., 1.0 mol) A solution of the γ- butyrolactone 2000mL as internal temperature does not exceed 0 ℃ It began to. After completion of the dropwise addition, stirring was continued at -10 ° C for 30 minutes, and then the temperature was gradually raised to 20 ° C. At 20 ° C., 51 g of 4,4′-diaminodiphenyl ether (Wakayama Seika Kogyo Co., Ltd., 0.4 mol) and 3,5-diaminobenzoic acid (Tokyo Kasei Co., Ltd., 0.1 mol) were added. . The stirring was continued for 2 hours at 20 ° C. and then for 2 hours at 40 ° C. After the stirring, filtration was performed to remove by-products generated in the reaction, and this solution was poured into 50 L of water to obtain a white precipitate. This precipitate was collected by filtration and further washed with 5 L of water. The white precipitate was dried with a vacuum dryer at 50 ° C. for 48 hours to obtain a polyamic acid ester powder (comparative polymer J-1) as a polyimide precursor.

<Characteristic evaluation>
The obtained resin composition was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Table 1 shows the following.
-After apply | coating on the board | substrate, the resin composition of this invention was able to form a favorable pattern at the temperature of 125 degreeC, and the cured relief pattern of the sufficiently high solvent insolubilization rate was formed by the heat processing of 200 degreeC. Therefore, it is excellent in pattern formability and has sufficient low-temperature curability.
Furthermore, the resin compositions prepared using the polymer compound of the present invention all have the advantages of good resolution and the ability to form small patterns, and low cure shrinkage and small dimensional changes.
On the other hand, the resin compositions of Comparative Examples 1 to 3 and 8 have poor pattern formability and resolution, and in particular, the resin compositions of Comparative Examples 2 and 3 have a high cure shrinkage rate. The resin compositions of Comparative Examples 4 to 7 had a low solvent insolubilization rate when cured at 200 ° C. for 60 minutes.

  The resin composition of the present invention has sufficient solubility in a general-purpose coating solvent in the field of electronic device production, and the resin composition of the present invention is uniform and free from precipitation of insoluble matter, and can be obtained by the resin composition. The pattern has advantages of excellent alkali dissolution rate, pattern formability, resolution, heat resistance and insulation, and includes a surface protection film for semiconductor devices, an interlayer insulation film, a planarization film for display devices, and an interlayer insulation film. Can be suitably used.

Claims (13)

Resin composition containing a polymer compound having a repeating unit represented by the following general formula (1A) or (1B) and a benzoxazine compound:

(In the formula, Ar ₁ , Ar ₂ , and Ar ₄ each independently represent a trivalent to hexavalent organic group having 6 to 30 carbon atoms, and the organic group may be substituted with a substituent. Ar ₃ Represents a divalent to hexavalent organic group having 6 to 30 carbon atoms, and the organic group may be substituted with a substituent, and Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently an acidic group. Alternatively, it represents an acidic group protected with an acid-decomposable group, Z represents a linking group, and may form a ring with at least one of Ar ₁ and Ar _2. a, b, and f are each independently 1-4. C represents an integer of 0 to 4. n1 and n2 are the number of repetitions, and 2 to 3000). The resin composition according to claim 1, wherein the benzoxazine compound is represented by the following general formula (5):

(In the formula, R ₉ and R ₁₀ represent an organic group having 1 to ₁₀ carbon atoms, R ₁₁ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Y represents a single bond, —C (CH ₃ ) _2. - group, -CO- group, -O -, - S -, - SO ₂ - group, -CH ₂ - group, -C _{(CF 3) 2} - group, or a group represented by the following general formula (6) Represents;);

(Wherein R ₁₂ represents an organic group having 1 to 10 carbon atoms, R ₁₃ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ₁₄ represents a methylene group or a p-xylylene group. M represents 1 to 10). Indicates an integer). The resin composition according to claim 1, wherein the benzoxazine compound is represented by the following general formula (7):

(Wherein R ₁₅ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ₁₆ represents an alkyl group having 1 to 6 carbon atoms, a cyclohexyl group, a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group. ). In said general formula (1A) or (1B), the acidic group protected by the said acidic group or acid-decomposable group is group represented by the following general formula (y1), Any one of Claims 1-3 Item 1. The resin composition according to item 1:

(In the formula, A, .B .P _g is representing a hydrogen atom or an acid-decomposable group represents a single bond or a (t + 1) -valent linking group is part showing acidity is protected by an acid decomposable group P _g And t represents an integer of 1 to 5.)
  The resin composition according to claim 4, wherein the acidic group is a COOH group or an OH group.   The resin composition according to any one of claims 1 to 5, wherein the acid value is 100 mgKOH / g or more.   The resin composition according to any one of claims 1 to 6, wherein 20 mol% to 80 mol% of the acidic groups are protected with an acid-decomposable group. The polymer represented by the general formula (1A) or (1B) is a monomer represented by the following general formula (2A) or (2B) and a monomer represented by the general formula (3), respectively. The resin composition according to any one of claims 1 to 7, which is obtained by condensation polymerization with:

(In the formula, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Z, a, b, c, and f are those in the general formula (1A) or (1B). R ₁ and R ₂ each independently represents a hydrogen atom or a silyl group, and X ₁ and X ₂ each independently represent a leaving group. The linking group represented by Z is a single bond, an alkylene group having 1 to 20 carbon atoms, —O—, —S—, —SO ₂ — group, —CO— group, —N (R ₁₁ ) — group (R ₁₁ 9 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms), or a group formed by combining these, 9. Resin composition.   Furthermore, the resin composition of any one of Claims 1-9 containing a photosensitizer.   The resin composition according to claim 10, wherein the photosensitive agent is a photoacid generator.   The resin composition according to any one of claims 1 to 11, comprising a crosslinking agent.   A cured relief pattern comprising a step of applying the resin composition according to any one of claims 10 to 12 onto a substrate and drying, a step of exposing, and a step of developing using an aqueous alkali solution or an organic solvent. Forming method.