KR20140142148A - Photosensitive composition contaning vinyl group-containing compound - Google Patents

Abstract

Provided are a photosensitive composition containing a novel vinyl group containing compound, and a method for forming a pattern using the photosensitive composition. The photosensitive composition relating to the present invention contains a vinyl-containing compound represented by following general formula (1); a compound having a hydroxyl group and/or carboxyl group; and a photo acid generator. In the formula, W1 and W2 are a group represented by following general formula (2) and a group represented by following general formula (4), a hydroxyl group or (meth)acryloyloxy group. Ring Y1 and ring Y2 are aromatic hydrocarbon rings. R is a single bond or specific divalent group. R3a and R3b are cyano group, halogen atom, or monovalent hydrocarbon group. The n1 and n2 are integers from zero to four.

Description

PHOTOSENSITIVE COMPOSITION CONTANNING VINYL GROUP-CONTAINING COMPOUND [0002]

The present invention relates to a photosensitive composition containing a vinyl group-containing compound, and a pattern forming method using the photosensitive composition.

The condensed polycyclic type compound has various excellent functions and is used for various purposes. For example, a compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton or the like), which is a condensed polycyclic aromatic compound, has excellent functions in terms of optical properties such as light transmittance and refractive index, and thermal properties such as heat resistance Is known. Therefore, a compound having a fluorene skeleton is used as a raw material for an optical member such as a lens, a prism, a filter, an image display material, a substrate for an optical disk, an optical fiber, an optical waveguide, a casing material, a film and a coating material. Examples of such a compound having a fluorene skeleton include those disclosed in Patent Document 1.

Japanese Laid-Open Patent Publication No. 2011-201791

The present invention aims to provide a photosensitive composition containing a novel vinyl group-containing compound and a pattern forming method using the photosensitive composition.

The present inventors have conducted intensive studies to solve the above problems. As a result, a photosensitive composition containing a novel vinyl group-containing compound was found and the present invention was completed. Specifically, the present invention provides the following.

A first aspect of the present invention is a photosensitive composition containing a vinyl group-containing compound represented by the following general formula (1), a compound having a hydroxyl group and / or a carboxyl group, and a photoacid generator.

[Chemical Formula 1]

(Wherein W ¹ and W ² independently represent a group represented by the following formula (2), a group represented by the following formula (4), a hydroxyl group or a (meth) acryloyloxy group, provided that W ¹ and W ² are not simultaneously oxygen radicals and are not a group represented by the following general formula (4), the rings Y ¹ and Y ² are the same or different aromatic hydrocarbon rings, R is a single bond, a methylene group which may have a substituent, , An ethylene group which may contain a hetero atom between two carbon atoms, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, and R ^3a and R ^3b independently represent a group represented by Si A halogen atom, or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 to 4)

(2)

(Wherein Ring Z represents an aromatic hydrocarbon ring, X represents a single bond or -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ² represents a monovalent hydrocarbon group, a hydroxyl group, a group represented by group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c represents a group, -SR ^4b represented by -OR ^4a, -N (R ^4d), the group represented by _2, a (meth) acryloyloxy group with an acrylic, a sulfo or a monovalent hydrocarbon group, a group represented by group, -SR ^4b represented by -OR ^4a, an acyl group, an alkoxycarbonyl group, -NHR ^4c by indicating group, or -N (R ^4d) groups are at least part of the hydrogen atoms bonded to a carbon atom monovalent hydrocarbon groups contained indicating _2, groups represented by a hydroxyl group, -OR ^4a, -SR group represented by ^4b, an acyl group , An alkoxycarbonyl group, a halogen atom, a knit Group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, the group represented by -NHR ^4c, -N (R ^4d), the group represented by _2, acryloyloxy group in a (meth) acrylate, mesyl oxy group, or a sulfo group , R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more)

(3)

(Wherein rings Z, X, R ¹ , R ² and m are as defined above)

A second aspect of the present invention is a photosensitive composition comprising a compound having a monovinyl group and a mono (meth) acryloyloxy group represented by the following general formula (10), a compound having a hydroxyl group and / or a carboxyl group, to be.

[Chemical Formula 4]

(Wherein, W ¹¹ and W ¹² which of the one is the represents a group represented by formula (2), the other is to represent a represented by formula (11) or (12), the ring Y ^1, ring Y ^2, R , R ^3a , R ^3b , n1 and n2 are as defined above)

[Chemical Formula 5]

(Wherein R ⁵ represents a hydrogen atom or a methyl group, 1 represents an integer of 1 to 4, and the rings Z, X, R ¹ , R ² and m have the same meanings as defined above)

[Chemical Formula 6]

(Wherein rings Z, X, R ¹ , R ² , R ⁵ and m are as defined above)

A third aspect of the present invention is a photosensitive composition containing a compound having a (meth) acryloyloxy group represented by the following general formula (19), a compound having a hydroxyl group and / or a carboxyl group, and a photoacid generator.

(7)

(Wherein W ¹³ and W ¹⁴ independently represent a group represented by the formula (12), a hydroxyl group or a (meth) acryloyloxy group, provided that at least one of W ¹³ and W ¹⁴ is a group represented by the formula And the ring Y ¹ , the ring Y ² , R, R ^3a , R ^3b , n 1 and n 2 are as defined above)

A fourth aspect of the present invention is a pattern forming method including a coating film forming step of forming a coating film made of the photosensitive composition, an exposure step of selectively exposing the coating film, and a developing step of developing the coating film after exposure .

According to the present invention, it is possible to provide a photosensitive composition containing a novel vinyl group-containing compound and a pattern forming method using the photosensitive composition.

&Quot; Photosensitive composition &

The photosensitive composition according to the present invention is a photosensitive composition comprising a vinyl group-containing compound represented by the general formula (1), a monovinyl group and a mono (meth) acryloyloxy group-containing compound represented by the general formula (10) (Meth) acryloyloxy group-containing compound represented by the general formula (19), a compound having a hydroxyl group and / or a carboxyl group, and a photo acid generator. Hereinafter, each component contained in the composition according to the present invention will be described in detail.

≪ Vinyl group-containing compound represented by general formula (1)

The vinyl group-containing compound contained in the composition according to the present invention is represented by the following general formula (1).

[Chemical Formula 8]

In the general formula (1), W ¹ and W ² independently represent a group represented by the following formula (2), a group represented by the following formula (4), a hydroxyl group or a (meth) acryloyloxy group, , W ¹ and W ² are not simultaneously oxygen radicals and are not represented by the following general formula (4). It is preferable that at least one of W ¹ and W ² is a group represented by the following general formula (2), and it is more preferable that both W ¹ and W ² are groups represented by the following general formula (2). Further, in the present specification, the term "(meth) acryloyl" means both of acryloyl and methacryloyl.

[Chemical Formula 9]

Examples of the ring Z in the general formulas (2) and (4) include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring (e.g., a condensed bicyclic hydrocarbon ring (e.g., a naphthalene ring, etc.) A condensed three-ring aromatic hydrocarbon ring (e.g., an anthracene ring, a phenanthrene ring, etc.) such as a C _{8 -20} condensed bicyclic hydrocarbon ring, preferably a C _{10 -16} condensed bicyclic hydrocarbon ring) To 4-membered aromatic hydrocarbon rings]. The ring Z is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring. When either of W ¹ and W ² is a group represented by the general formula (2), or when one of W ¹ and W ² is a group represented by the general formula (2) and the other is a group represented by the general formula (4) , The ring Z contained in W ¹ and the ring Z included in W ² may be the same or different. For example, one of the rings may be a benzene ring and the other ring may be a naphthalene ring. Particularly preferred is a naphthalene ring. The substitution position of the ring Z which is bonded to the carbon atom to which both W ¹ and W ² are directly bonded via X is not particularly limited. For example, when the ring Z is a naphthalene ring, the group corresponding to the ring Z bonded to the carbon atom may be a 1-naphthyl group, a 2-naphthyl group or the like.

In the general formulas (2) and (4), X represents independently a single bond or a group represented by -S-, and is typically a single bond.

In the general formulas (2) and (4), as R ¹ , for example, a single bond; An alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a propylene group, and a butane-1,2-diyl group; A C _{2 -4} alkylene group (particularly, a C _2-3 alkylene group such as an ethylene group or a propylene group) is preferable, and a single bond is more preferable. When either of W ¹ and W ² is a group represented by the general formula (2), or when one of W ¹ and W ² is a group represented by the general formula (2) and the other is a group represented by the general formula (4) If caused, R ¹ contained in R ¹ and W ² is W ¹ contained in the same or the different.

In the general formula (2) and (4), R ² roneun, for example, an alkyl group (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group of the C _{1 -12} alkyl group, preferably It is a C _{1 -8} alkyl group, more preferably C _{1 -6} alkyl group, etc.), such as a cycloalkyl group (a cyclohexyl group C _{5 -10} cycloalkyl group, preferably a C _{5 -8} cycloalkyl group, preferably C ₅ than _-6 cycloalkyl group, etc.), an aryl group (e.g., C _6-14 aryl groups such as phenyl group, tolyl group, xylylene group, a naphthyl group, preferably a C _{6 -10} aryl group, more preferably C _{6 - 8,} an aryl group, etc.), a monovalent hydrocarbon group such as an aralkyl group (benzyl group, phenethyl group, etc. C _{6 -10} aryl -C _{1 -4} alkyl group, and the like); A hydroxyl group; An alkoxy group (a C _{1 -12} alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group, preferably a C _{1 -8} alkoxy group, more preferably a C _{1 -6} alkoxy group), a cycloalkoxy group (a cyclohexyl group, such as C _{5 -10} -1,3 cycloalkoxy group or the like), C ₆ aryloxy, such as (C _6-10 aryloxy group such as phenoxy group), an aralkyl oxy group (e.g., benzyloxy group _-10 aryl -C _{1 -4} alkyl group) group represented by -OR ^4a, such as [wherein, R ^4a is 1 represents a hydrocarbon group (the one of the above-exemplified hydrocarbon group or the like).]; Alkylthio (methyl thio group, ethyl thio group, propyl thio, and butyl thio group, such as the coming of the C _{1 -12} alkyl group, preferably a C _{1 -8} alkylthio group, more preferably C _{1 -6} alkylthio Get, etc.), cyclo alkylthio group (such as cyclohexyl silti import of C _{5 -10} cycloalkyl alkylthio, etc.), arylthio (phenyl C _{6 -10} arylthio group), an aralkyl thio group such as a get tea (e.g. for example, benzyl, C _{6 -10} aryl -C _{1 -4} alkylthio group, such as coming T) of the group wherein a represents -SR ^4b, such as, R ^4b is a monovalent hydrocarbon group (the one of the above-exemplified hydrocarbon groups such as ); An acyl group (such as a C _{1 -6} acyl group such as an acetyl group); Alkoxycarbonyl group (methoxycarbonyl group, such as a C _{1 -4} alkoxy-carbonyl group, etc.); A halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.); A nitro group; Cyano; A mercapto group; A carboxyl group; An amino group; Carbamoyl group; An alkylamino group (a C _{1 -12} alkylamino group such as a methylamino group, an ethylamino group, a propylamino group or a butylamino group, preferably a C _{1 -8} alkylamino group, more preferably a C _{1 -6} alkylamino group), a cycloalkylamino group amino groups such as cyclohexyl, C _{5 -10} cycloalkyl group and the like), aryl group (phenyl group, such as C _{6 -10} aryl group), such as an aralkyl group (e.g., benzyl group C _{6 -10} aryl -C _{1 -4} group represented by -NHR ^4c, such as an alkyl group) [in the formula, R ^4c is 1 represents a hydrocarbon group (such as the one of the above-exemplified hydrocarbon group)]; A dialkylamino group (di (C _1-12 alkyl) amino group such as dimethylamino group, diethylamino group, dipropylamino group or dibutylamino group, preferably di (C _1-8 alkyl) amino group, more preferably di _1-6 alkyl) amino group, etc.), dicyclohexyl alkylamino group (dicyclohexyl-amino group such as di (di (C _6-10 aryl) such as C _5-10 cycloalkyl) amino group, etc.), diarylamino groups (diphenylamino group A group represented by -N (R ^4d ) ₂ such as a di (C _6-10 aryl-C _1-4 alkyl) amino group such as a dibenzylamino group) ^4d independently represents a monovalent hydrocarbon group (for example, the monovalent hydrocarbon group in the above example); (Meth) acryloyloxy group; Sulfo group; A group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a group represented by -NHR ^4c , or a group represented by -N (R ^4d ) ₂ in the above-described monovalent hydrocarbon group, At least a part of the hydrogen atoms to which at least one of the bonded hydrogen atoms are bonded is selected from the group consisting of the monovalent hydrocarbon groups, hydroxyl groups, -OR ^4a , -SR ^4b , acyl, alkoxycarbonyl, halogen, nitro, cyano, , an amino group, a carbamoyl group, a group substituted with a group, a (meth) acryloyloxy group of acrylic, mesyl oxy group, or a sulfo group represented by the group, -N (R ^4d) ₂ represented by -NHR ^4c [e.g., alkoxy aryl group (e. g., such as, methoxy, phenyl C _{1 -4} alkoxy C _{6 -10} aryl group), alkoxycarbonyl aryl group (e.g., methoxy carbonyl group, ethoxy carbonyl C ₁ such as a carbonyl group _-4 alkoxy-carbonyl and the like can be mentioned C _{6 -10} aryl group, etc.)].

Among them, R ² represents a group represented by a monovalent hydrocarbon group, a group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group or -NHR ^4c , -N (R ^4d ) _2, and the like.

Roneun preferred R ^2, 1 is a hydrocarbon group [e.g., an alkyl group (e.g., C _{1 -6} alkyl group), cycloalkyl groups (e.g., C _{5 -8} cycloalkyl group), an aryl group (e.g., C _6-10 aryl group), aralkyl group (for example there may be mentioned C ₆ -C ₁ aryl _{-8 -2} alkyl group like), alkoxy groups (C _{1 -4} alkoxy group and the like). In particular, R ^2a and R ^2b is a group [C _{1 -4} alkyl group (particularly methyl group), etc.], an aryl group, e.g., C _{6 -10} aryl group (especially, phenyl group), etc.], such as monovalent hydrocarbon groups of ( Particularly an alkyl group).

When m is an integer of 2 or more, R ² may be the same or different. When either of W ¹ and W ² is a group represented by the general formula (2), or when one of W ¹ and W ² is a group represented by the general formula (2) and the other is a group represented by the general formula (4) If caused, R ² contained in R ² and W ² W ¹ contained in the May be the same or different.

In the general formulas (2) and (4), the number m of R ² can be selected depending on the kind of the ring Z and is, for example, 0 to 4, preferably 0 to 3, more preferably 0 It may be ~ 2. When either of W ¹ and W ² is a group represented by the general formula (2), or one of W ¹ and W ² is a group represented by the general formula (2) and the other is a group represented by the general formula (4) M, m in W ¹ and m in W ² may be the same or different.

Examples of the ring Y ¹ and the ring Y ^{2 in} the general formula (1) include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring (for example, a condensed bicyclic hydrocarbon ring (for example, naphthalene ring for C _{8 -20} fused 2 fused, such as cyclic hydrocarbon ring, preferably a C _{10 -16} condensed cyclic hydrocarbon ring 2), for the condensation of 3-cyclic aromatic hydrocarbon ring (e.g., anthracene ring, phenanthrene ring, and the like) 2 to 4-ring aromatic hydrocarbon rings] and the like. The ring Y ¹ and the ring Y ² are preferably a benzene ring or a naphthalene ring. The ring Y ¹ and the ring Y ² may be the same or different. For example, one ring may be a benzene ring and the other ring may be a naphthalene ring.

In the general formula (1), R represents a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent, an ethylene group which may contain a hetero atom between two carbon atoms, a group represented by -O-, -NH- or a group represented by -S-, and is typically a single bond. Examples of the substituent include a cyano group, a halogen atom (such as a fluorine atom, a chlorine atom and a bromine atom), a monovalent hydrocarbon group (e.g., an alkyl group (such as a methyl group, an ethyl group, a propyl group, C _{6 -10} aryl group), etc.] and the like, hetero atoms, such as butyl, t- butyl group of the C _1-6 alkyl group), aryl group (phenyl group, for example, an oxygen atom, a nitrogen atom , A sulfur atom, and a silicon atom.

Examples of the R ^3a and R ^{3b in} the general formula (1) include a non-reactive substituent such as a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a monovalent hydrocarbon group for example, an alkyl group, an aryl group and the like (C _{6 -10} aryl groups such as phenyl, etc.), etc.], preferably a cyano group or an alkyl group, particularly preferably an alkyl group. Examples of the alkyl group include C _{1 -6} alkyl groups (e.g., C _{1 -4} alkyl groups, particularly methyl groups) such as methyl, ethyl, propyl, isopropyl, butyl and t- When n1 is an integer of 2 or more, R < ^3a > may be the same or different. When n ² is an integer of 2 or more, R ^3b may be the same or different. R ^3a and R ^3b may be the same or different. The rings Y ¹ and Y ² (Substituted position) of R < ^3a > and R < ^3b > Preferred substitution numbers n1 and n2 are 0 or 1, especially 0. N1 and n2 may be the same or different from each other.

The vinyl group-containing compound represented by the general formula (1) has high reactivity because it has a vinyloxy group and / or a (meth) acryloyloxy group while maintaining excellent optical and thermal properties. In particular, the rings Y ¹ and Y ² Is a benzene ring and R is a single bond, the vinyl group-containing compound represented by the general formula (1) has a fluorene skeleton and is more excellent in optical characteristics and thermal characteristics. Since the vinyl group-containing compound represented by the above general formula (1) can be polymerized, it functions as a polymerizable monomer. In particular, W ¹ and W ² Is a group represented by the general formula (2), the compound represented by the general formula (1) functions as a cationically polymerizable monomer because it can undergo cationic polymerization. On the other hand, when W ¹ and W ² are both (meth) acryloyloxy groups, the compound represented by the general formula (1) functions as a radical polymerizable monomer since it can be subjected to radical polymerization. The vinyl group-containing compound represented by the above general formula (1) is preferably a vinyloxy group and / or a (meth) acryloyloxy group when W ¹ and W ² are independently a group represented by the above general formula (2) Since two vinyl groups contained in the form of a (meth) acryloyloxy group can react with each molecule, they can be preferably used as a crosslinking agent. The vinyl group-containing compound represented by the above general formula (1) is preferably used as a base component in the composition by giving a cured product having a high hardness. In addition, when the photosensitive composition contains the vinyl group-containing compound represented by the general formula (1), good patterning characteristics can be obtained. The photosensitive composition may be a positive type or a negative type. The vinyl group-containing compound represented by the general formula (1) may be used in various applications, for example, an alignment film and a planarization film (for example, an alignment film and a planarization film used for a liquid crystal display or an organic EL display); A resist underlayer film such as an antireflection film, an interlayer insulating film, or a carbon hard mask; Spacers and partition walls such as a liquid crystal display or an organic EL display; A pixel or black matrix of a color filter of a liquid crystal display; A display device such as a liquid crystal display or an organic EL display; Optical members such as lenses (e.g., microlenses), optical fibers, optical waveguides, prism sheets, holograms, high-refraction films, and retroreflective films; A low moisture permeable membrane (for example, a low moisture permeable membrane used as a water vapor barrier layer); Optical material; It can be used for semiconductor materials.

In particular, the vinyl group-containing compound has ^two vinyloxy groups when W ¹ and W ² are both the groups represented by the general formula (2), and corresponds to a divinyl ether compound.

The divinyl ether compound has two vinyloxy groups, and since these vinyloxy groups can react with the respective molecules, they are used as crosslinking agents. For example, JP-A-2012-103723, JP-A-4313611 and JP-A-3206989 disclose photosensitive compositions containing a divinyl ether compound, a polymer having a hydroxyl group and / or a carboxyl group, and a photoacid generator In this photosensitive composition, a divinyl ether compound is used as a crosslinking agent. However, the inventors of the present invention have found that conventional photosensitive compositions containing a divinyl ether compound have a problem of poor storage stability and patterning properties.

On the other hand, the photosensitive composition containing the vinyl group-containing compound represented by the general formula (1) has excellent storage stability and patterning properties.

The vinyl group-containing compounds represented by the above general formula (1) may be used alone or in combination of two or more. Among the vinyl group-containing compounds represented by the general formula (1), particularly preferred specific examples include the compounds represented by the following formulas.

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

The content of the vinyl group-containing compound represented by the general formula (1) is preferably from 1 to 90% by mass, more preferably from 20 to 80% by mass, more preferably from 40 to 70% by mass based on the solid content of the photosensitive composition related to the present invention. More preferably, it is in mass%. Within the above range, the storage stability and patterning characteristics of the photosensitive composition tend to be improved.

[Production method of vinyl group-containing compound represented by formula (1a)] [

Among the vinyl group-containing compounds represented by the above general formula (1), those represented by the following general formula (1a) can be produced, for example, by the following Production Methods 1 to 3.

[Chemical Formula 14]

(Wherein W ^1a and W ^2a independently represent a group represented by the general formula (2), a group represented by the general formula (4), a hydroxyl group or a (meth) acryloyloxy group, provided that W ^1a and W ^2a are not simultaneously oxygen radicals and are not a (meth) acryloyloxy group other than the above-described general formula (4) and the ring Y ¹ , the ring Y ² , R, R ^3a , R ^3b , n 1 and n 2 are as described above )

ㆍ Manufacturing Method 1

The vinyl group-containing compound represented by the above-mentioned general formula (1a) can be produced, for example, by the following general formula (13) in the presence of a transition element compound catalyst and an inorganic base in accordance with the production method described in JP- Can be synthesized by reacting a vinyl ester compound represented by the following general formula (3) with a hydroxyl group-containing compound represented by the following general formula (3). The inorganic base is preferably a solid inorganic base containing 10 wt% or more of particles having a particle diameter of less than 150 mu m. Specifically, the vinyl group-containing compound represented by the general formula (1a) can be synthesized as in Synthesis Example 1 described later.

^{R 6 -CO-O-CH =} CH 2 (13)

(Wherein R ⁶ represents a hydrogen atom or an organic group)

[Chemical Formula 15]

Wherein W ³ and W ⁴ independently represent a group represented by the above-mentioned formula (4) or a hydroxyl group, provided that W ³ and W ⁴ are not a hydroxyl group at the same time, and a ring Y ¹ , a ring Y ² , ^3a , ^R3b , n1 and n2 are as described above)

The compound represented by the above general formula (3) can be produced, for example, by reacting a compound represented by the following general formula (14) and / or a compound represented by the following general formula (15) 16). ≪ / RTI > The desired hydroxyl group-containing compound represented by the above general formula (3) can be obtained by appropriately adjusting the combination method and the addition amount of the compound represented by the following general formula (14) and the compound represented by the following general formula (15) After the reaction, the intended hydroxyl group-containing compound may be separated by a known separation method such as, for example, silica gel column chromatography.

[Chemical Formula 16]

(In the formulas (14), (15) and (16), the ring Y ¹ , the ring Y ² , the rings Z, R, R ¹ , R ² , R ^3a , R ^3b , m, As shown in FIG.

Examples of the acid catalyst, reaction conditions, and the like used in the synthesis of the compound represented by the general formula (3) include, for example, in Patent Document 1 or Japanese Patent Application Laid-Open No. 2002-255929, And those described as being usable for the production method of the compound.

ㆍ Manufacturing Method 2

The compound represented by the general formula (1a) can be produced, for example, from the hydroxyl group-containing compound represented by the general formula (3) via the leaving group-containing compound represented by the following general formula (5) To obtain a vinyl group-containing compound represented by the following general formula (1).

[Chemical Formula 17]

(Wherein W ⁵ and W ⁶ independently represent a group represented by the following formula (6) or a hydroxyl group, with the proviso that W ⁵ and W ⁶ are not a hydroxyl group at the same time, and a ring Y ¹ , a ring Y ² , ^3a , ^R3b , n1 and n2 are as described above)

[Chemical Formula 18]

(Wherein E represents an alkyloxy group having 1 to 4 carbon atoms substituted with a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a paratoluenesulfonyloxy group or a benzenesulfonyloxy group, , Rings Z, X, R ¹ , R ² and m are as defined above)

The leaving group-containing compound represented by the general formula (5) can be synthesized, for example, by reacting the hydroxyl group-containing compound represented by the general formula (3) with a leaving group-containing compound. Examples of the silyl group-containing compound include thionyl chloride, a compound represented by the following formula, and the like. The reaction temperature is, for example, -20 to 150 占 폚, preferably -10 to 140 占 폚, and more preferably 30 to 130 占 폚.

[Chemical Formula 19]

The vinyl group-containing compound represented by the general formula (1a) can be synthesized, for example, by reacting a silyl group-containing compound represented by the general formula (5) with a vinylating agent. Examples of the vinylating agent include sodium hydroxide, triethylamine, diisopropylethylamine, 1,4-diazabicyclo [2.2.2] octane, diazabicyclo undecene, sodium methoxide, sodium ethoxide Sodium ethoxide, potassium-t-butoxide, and the like, preferably diazabicyclo undecene, sodium ethoxide, potassium t-butoxide and the like, more preferably potassium- t-butoxide. The reaction temperature is, for example, -20 to 150 占 폚, preferably -10 to 100 占 폚, and more preferably 0 to 60 占 폚.

Manufacturing Method 3

The compound represented by the general formula (1a) can be obtained, for example, from a hydroxyalkyloxy group-containing compound represented by the following general formula (7) via a leaving group-containing compound represented by the general formula (5) May be synthesized by a production method comprising obtaining a vinyl group-containing compound represented by the formula (1a).

[Chemical Formula 20]

(Wherein W ⁷ and W ⁸ independently represent a group represented by the following formula (8) or a hydroxyl group, provided that W ⁷ and W ⁸ are not simultaneously a hydroxyl group, and a ring Y ¹ , a ring Y ² , ^3a , ^R3b , n1 and n2 are as described above)

[Chemical Formula 21]

(Wherein, 1 represents an integer of 1 to 4, and the rings Z, X, R ¹ , R ² and m are as defined above)

The hydroxyalkyloxy group-containing compound represented by the above general formula (7) can be produced, for example, by reacting a compound represented by the following general formula (17) and / or a compound represented by the following general formula (18) Can be synthesized by reacting the compound represented by the above general formula (16). The desired hydroxyalkyloxy group-containing compound represented by the above general formula (7) can be obtained by appropriately adjusting the combination method and the addition amount of the compound represented by the following general formula (17) and the compound represented by the following general formula (18) After the reaction, the intended hydroxyalkyloxy group-containing compound may be separated by a known separation method such as, for example, silica gel column chromatography or the like. Examples of the acid catalyst and the reaction conditions used in the synthesis of the compound represented by the general formula (7) include those exemplified in the description of the synthesis method of the compound represented by the general formula (3).

[Chemical Formula 22]

(In the formulas (17) and (18), ring Z, R ¹ , R ² and m are as defined above)

The leaving group-containing compound represented by the general formula (5) can be synthesized, for example, by reacting a hydroxyalkyloxy group-containing compound represented by the general formula (7) with a compound containing a leaving group. Examples of the compound containing a silyl group and the reaction temperature include those exemplified above for the production method 2.

The vinyl group-containing compound represented by the general formula (1a) can be synthesized, for example, by reacting a silyl group-containing compound represented by the general formula (5) with a vinylating agent. Examples of the vinylating agent and the reaction temperature include those exemplified above for the production method 2.

From the hydroxyalkyloxy group-containing compound represented by the above general formula (7), the compound represented by the above general formula (1a) can be obtained in a high yield by the production method 3. According to the production method 3, the load in the purification step of the compound represented by the general formula (1a) can be lowered. Further, in the production method 3, the reaction can be carried out at normal pressure, so that a special reaction facility such as a heat-resistant container is unnecessary, and a more simple apparatus can be used. Further, in the production method 3, since a combustible gas such as acetylene gas is not used, the compound represented by the general formula (1a) can be produced more safely.

<Purification method>

The vinyl group-containing compound represented by the above general formula (1) may be purified after synthesis. The purification method is not particularly limited and known methods such as silica gel column chromatography and the like can be mentioned. By the purification, the purity of the vinyl group-containing compound represented by the general formula (1) is improved and the content of the metal component is reduced. The purified vinyl group-containing compound is likely to have improved reactivity and effectively inhibit coloring during reaction.

- The elimination group-containing compound represented by the general formula (5)

The leaving group-containing compound represented by the general formula (5) is useful as an intermediate for producing the vinyl group-containing compound represented by the general formula (1). The leaving group-containing compound represented by the above general formula (5) can be synthesized, for example, by the method described in Production Method 2 or 3 above.

- Monovinyl group-containing compounds represented by the general formula (9) and production methods thereof

The monovinyl group-containing compound represented by the following general formula (9) is useful as an intermediate for producing the vinyl group-containing compound represented by the general formula (1a).

(23)

(Wherein, W ⁹ and W ¹⁰ of either the above represents a group represented by formula (2), the other is the monovalent represented by the following formula (6), the ring Y ^1, ring Y ^2, R, R ^3a, R ^3b , n1 and n2 are as defined above)

The monovinyl group-containing compound represented by the above-mentioned general formula (9) is obtained by a production method comprising obtaining a monovinyl group-containing compound represented by the above general formula (9) from a leaving group-containing compound represented by the following general formula (5a) It is possible to synthesize. That is, the monovinyl group-containing compound represented by the general formula (9) can be synthesized, for example, by reacting a silyl group-containing compound represented by the following general formula (5a) with a vinylating agent. Examples of the vinylating agent and the reaction temperature include those exemplified above for the production method 2. The amount of the vinylating agent to be used is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, still more preferably 0.8 to 2 mol, per mol of the eliminator in the eliminator-containing compound represented by the following general formula (5a) to be.

&Lt; EMI ID =

(Wherein W ^5a and W ^6a each represent a group represented by the general formula (6), and the ring Y ¹ , the ring Y ² , R, R ^3a , R ^3b , n1 and n2 are as defined above)

<Monovinyl group and mono (meth) acryloyloxy group-containing compound represented by general formula (10)>

The monovinyl group and the mono (meth) acryloyloxy group-containing compound contained in the composition according to the present invention are represented by the following general formula (10). The monovinyl group and the mono (meth) acryloyloxy group-containing compound may be used alone or in combination of two or more. This compound has high reactivity because it has a vinyloxy group and a (meth) acryloyloxy group while maintaining excellent optical and thermal properties. Particularly, when the ring Y ¹ and the ring Y ² are benzene rings and R is a single bond, the compound represented by the following general formula (10) has a fluorene skeleton and is more excellent in optical characteristics and thermal characteristics. The compound represented by the following general formula (10) can function as a polymerizable monomer because it can be polymerized in the same manner as the vinyl group-containing compound represented by the general formula (1), and can be preferably used as a crosslinking agent. Further, the compound represented by the following general formula (10) is preferable as a base component in the composition by giving a cured product having a high hardness. In addition, when the negative photosensitive resin composition contains a compound represented by the following general formula (10), it is possible to obtain good minute patterning characteristics. The compound represented by the following general formula (10) can be used for various uses, for example, those specifically exemplified for the compound represented by the general formula (1).

(25)

(Wherein, W ¹¹ and W ¹² which of the one is the represents a group represented by formula (2), the other is to represent a represented by formula (11) or (12), the ring Y ^1, ring Y ^2, R , R ^3a , R ^3b , n1 and n2 are as defined above)

(26)

(Wherein R ⁵ represents a hydrogen atom or a methyl group, and rings Z, X, R ¹ , R ² , m and 1 are as defined above)

(27)

(Wherein rings Z, X, R ¹ , R ² , R ⁵ and m are as defined above)

The content of the compound represented by the formula (10) is preferably 1 to 90% by mass, more preferably 20 to 80% by mass, and more preferably 40 to 70% by mass with respect to the solid content of the composition according to the present invention desirable. Within the above range, the storage stability and patterning characteristics of the photosensitive composition tend to be improved.

<(Meth) acryloyloxy group-containing compound represented by general formula (19)>

The (meth) acryloyloxy group-containing compound contained in the composition according to the present invention is represented by the following general formula (19). The (meth) acryloyloxy group-containing compounds may be used alone or in combination of two or more. This compound has high reactivity because it has a (meth) acryloyloxy group while maintaining excellent optical and thermal properties. In particular, when the ring Y ¹ and the ring Y ² are benzene rings and R is a single bond, the compound represented by the following general formula (19) has a fluorene skeleton and is more excellent in optical properties and thermal properties. Since the compound represented by the following general formula (19) can be polymerized in the same manner as the vinyl group-containing compound represented by the general formula (1), it functions as a polymerizable monomer and can be preferably used as a crosslinking agent. Further, the compound represented by the following general formula (19) is preferably used as a base component in the composition by giving a cured product having a high hardness. In addition, when the compound represented by the following general formula (19) is contained in the negative-working photosensitive resin composition, it is possible to obtain good fine patterning characteristics. The compound represented by the following general formula (19) can be used for various uses, for example, those specifically exemplified for the compound represented by the general formula (1).

(28)

(Wherein W ¹³ and W ¹⁴ independently represent a group represented by the formula (12), a hydroxyl group or a (meth) acryloyloxy group, provided that at least one of W ¹³ and W ¹⁴ is a group represented by the formula And the ring Y ¹ , the ring Y ² , R, R ^3a , R ^3b , n 1 and n 2 are as defined above)

Among the compounds represented by the above general formula (19), particularly preferred specific examples include the compounds represented by the following formulas.

[Chemical Formula 29]

(30)

(31)

The content of the compound represented by the formula (19) is preferably 1 to 90% by mass, more preferably 20 to 80% by mass, and more preferably 40 to 70% by mass relative to the solid content of the composition according to the present invention desirable. Within the above range, the storage stability and patterning characteristics of the photosensitive composition tend to be improved.

[Process for producing (meth) acryloyloxy group-containing compound represented by general formula (19)] [

The compound represented by the above general formula (19) can be produced, for example, by a process comprising obtaining a (meth) acryloyloxy group containing compound represented by the above general formula (19) from the hydroxyl group containing compound represented by the general formula (3) Method can be used.

The compound represented by the above general formula (19) can be synthesized, for example, by reacting a hydroxyl group-containing compound represented by the above general formula (3) with a (meth) acrylating agent. Examples of the (meth) acrylating agent include (meth) acryloyl halides such as (meth) acryloyl chloride; (Meth) acrylic acid anhydride, and the like, and (meth) acryloyl halide is preferable, and (meth) acryloyl chloride is more preferable. The reaction temperature is, for example, -20 to 150 占 폚, preferably -10 to 100 占 폚, and more preferably 0 to 60 占 폚. In the present specification, the term "(meth) acrylating agent" means both of an acrylating agent and a methacrylating agent, and "(meth) acrylic acid anhydride" means both of acrylic anhydride and methacrylic anhydride.

The compound represented by the above general formula (19) may be purified after synthesis. The purification method is not particularly limited and known methods such as silica gel column chromatography and the like can be mentioned. By the purification, the purity of the compound represented by the general formula (19) is improved and the content of the metal component is reduced. The resultant compound tends to have improved reactivity and effectively inhibit coloring during the reaction.

&Lt; Compounds Having Hydroxyl Group and / or Carboxyl Group &

The compound having a hydroxyl group and / or a carboxyl group in the photosensitive composition according to the present invention is preferably a compound having a hydroxyl group and / or a carboxyl group, which is obtained by heating the vinyl group-containing compound represented by the general formula (1), the monovinyl group represented by the general formula (10) (Meth) acryloyloxy group-containing compound represented by the general formula (19) and / or a (meth) acryloyloxy group-containing compound represented by the general formula (19) Can be used. Examples of the compound having a hydroxyl group and / or a carboxyl group include compounds having a carbon, hydrogen, oxygen, boron, nitrogen, aluminum, phosphorus, silicon, &Lt; / RTI &gt; and combinations comprising more than one species. The number of the hydroxyl group and the carboxyl group contained in the compound having a hydroxyl group and / or carboxyl group is not particularly limited, but in order to form a dense crosslink in the cured product of the photosensitive composition, it is preferable that the number is two or more in total. The compounds having a hydroxyl group and / or a carboxyl group may be used alone or in combination of two or more.

Specific examples of the compound having a hydroxyl group and / or a carboxyl group will be described below.

Specific examples of the compound having a hydroxyl group and / or a carboxyl group include those represented by the following general formula (a-1).

V ¹ -R ^a1 -V ² (a-1)

( ^Wherein R ^a1 is an organic group, and V ¹ and V ² are independently a hydroxyl group or a carboxyl group)

In the general formula (a-1), R ^a1 includes, for example, a divalent hydrocarbon group, a divalent heterocyclic group, and a group formed by bonding them together, and a divalent hydrocarbon group is preferable. The divalent hydrocarbon group and the divalent heterocyclic group may have a substituent. R ^a1 preferably has a cyclic structure.

Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and a group formed by bonding two or more thereof.

Examples of the divalent aliphatic hydrocarbon group include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a s-butylene group, a t-butylene group, a pentylene group, An alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms, such as a dodecylene group; An alkenylene group having 2 to 20, preferably 2 to 10, more preferably 2 to 3 carbon atoms such as a vinylene group, a propenylene group and a 1-butenylene group; An alkynylene group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 3 carbon atoms, such as an ethynylene group and a propynylene group.

Examples of the bivalent alicyclic hydrocarbon group include a cycloalkyl group having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, more preferably 5 to 8 carbon atoms, such as cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, A cycloalkylene group; A cycloalkenylene group having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, and more preferably 5 to 8 carbon atoms, such as a cyclopentenylene group and a cyclohexenylene group; More preferably 6 to 16 carbon atoms such as a perhydronaphthylene group, a perhydronaphthylene group, a norbornylene group, an adamantylene group and a tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecylene group Include a divalent bridged cyclic hydrocarbon group of 7 to 12 carbon atoms.

Examples of the divalent aromatic hydrocarbon group include an arylene group having 6 to 20 carbon atoms, preferably 6 to 13 carbon atoms such as a phenylene group, a naphthylene group and a fluorenylene group.

Examples of the group formed by bonding of the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group include a cycloalkylene-alkylene group such as a cyclopentylene methylene group, a cyclohexylene methylene group, a cyclohexyleneethylene group, For example, C _{3 -20} cycloalkylene-C _{1 -4} alkylene group, etc.).

Group is a divalent aliphatic hydrocarbon group and a divalent group formed by combining an aromatic hydrocarbon, for example, an arylene-alkylene group (e.g., C _{6 -20} arylene -C _{1 -4} alkyl group, etc.), arylene - there may be mentioned an arylene group (e.g., C _{6 -20} arylene -C _{1 -4} alkyl group -C _{6 -20} aryl group, etc.), and the like-alkylene.

Groups is more than 22 that is formed by combining an aromatic hydrocarbon group each other, for example, an arylene-arylene group (e.g., C _{6 -20} arylene -C _{6 -20} aryl group, etc.), arylene - arylene-arylene group, and the like (e.g., C _{6 -10} arylene -C _{6 -13} arylene -C _{6 -10} aryl group, etc.).

Among these divalent hydrocarbon groups, and preferably has a ring structure, C _{6 -10} arylene -C _{6 -13} aryl group -C _{6 -10} aryl group, C ₆ -C _{1 -4 -20} arylene alkylene group -C _{6 -20} aryl group, a divalent group crosslinked cyclic hydrocarbon group of a carbon number of 7-12 is particularly preferred.

The divalent hydrocarbon group may have various substituents such as a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group or an acyloxy group) A substituted or unsubstituted carbamoyl group, a cyano group, a nitro group, a substituted or unsubstituted amino group, a sulfo group, a heterocyclic group or the like . The hydroxyl group and the carboxyl group may be protected by a common protecting group in the field of organic synthesis. The ring of the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group may be condensed with an aromatic or nonaromatic heterocyclic ring.

The divalent heterocyclic group is a group formed by removing two hydrogen atoms from a heterocyclic compound. The heterocyclic compound may be an aromatic heterocyclic compound or a non-aromatic heterocyclic compound. Examples of such heterocyclic compounds include heterocyclic compounds containing an oxygen atom as a heteroatom (for example, heterocyclic compounds of a triatomic ring such as oxirane, quateminal rings such as oxetane, A heterocyclic compound of a five-membered ring such as furan, tetrahydrofuran, oxazole or? -Butyrolactone, a heterocyclic compound of a five-membered ring such as 4-oxo-4H-pyran, tetrahydropyran, Heterocyclic compound having a condensed ring such as benzofuran, 4-oxo-4H-chromene and chroman, a heterocyclic compound having 3- ^oxatricyclo [4.3.1.1 ^4,8 ] undecane- A heterocyclic compound having a crosslinking ring such as 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one), a heterocyclic compound containing a sulfur atom as a hetero atom (for example, , Heterocyclic compounds of five-membered rings such as thiophene, thiazole, and thiadiazole, 4-oxo-4H-thiadiazole A heterocyclic compound having a condensed ring such as benzothiophene, etc.), a heterocyclic compound containing a nitrogen atom as a heteroatom (e.g., pyrrole, Heterocyclic compounds of five-membered rings such as pyrrolidine, pyrazole, imidazole and triazole, heterocyclic compounds of six-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, piperidine and piperazine, , Heterocyclic compounds having condensation rings such as indoline, quinoline, acridine, naphthyltin, quinazoline, purine, etc.) and the like. The divalent heterocyclic group may have an alkyl group (for example, a C _{1 -4} alkyl group such as a methyl group or an ethyl group), a cycloalkyl group, an aryl group (for example, a phenyl group, such as a naphthyl group C _{6 -10} or may have a substituent such as an aryl group, etc.).

Specific examples of the compound represented by the general formula (a-1) include compounds represented by the following formulas.

(32)

Specific examples of the compound having a hydroxyl group and / or a carboxyl group include a resin having a hydroxyl group and / or a carboxyl group.

Examples of the resin having a hydroxyl group include a resin having an alcoholic hydroxyl group and an alkali-soluble resin having a phenolic hydroxyl group.

ㆍ Resin with alcoholic hydroxyl group

Examples of the resin having an alcoholic hydroxyl group include an acrylic polymer, a vinyl polymer, an alkylene glycol polymer, a cellulosic polymer, a urea polymer, an epoxy polymer, an amide polymer, a melamine polymer, a polyethylene polymer, As the resin such as a polymer or a sulfonamide resin, those having an alcoholic hydroxyl group in its structure can be used. More specifically, there may be mentioned acrylic acid, methacrylic acid, N-vinylpyrrolidone, vinyl alcohol, N-vinylimidazolidinone, N, N-dimethylacrylamide, N, N-dimethylaminopropylmethacrylamide, Acrylamide, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, A homopolymer and / or a copolymer of at least one monomer selected from the group consisting of N-acryloylmorpholine, N-acryloylmorpholine, and 3-hydroxy-1-adamantyl methacrylate, Can be used.

ㆍ Alkali-soluble resin having phenolic hydroxyl group

As the alkali-soluble resin having a phenolic hydroxyl group, for example, a polyhydroxystyrene-based resin can be used.

The polyhydroxystyrene-based resin has at least a structural unit derived from hydroxystyrene.

Here, "hydroxystyrene" means a compound in which hydrogen atoms bonded to the α-position of hydroxystyrene and hydroxystyrene are substituted with other substituents such as a halogen atom, an alkyl group and a halogenated alkyl group, and hydroxystyrene derivatives (Monomer).

The "hydroxystyrene derivative" refers to a derivative in which at least a benzene ring and a hydroxyl group bonded thereto are held, and for example, a hydrogen atom bonded to the α-position of the hydroxystyrene is substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, , And those obtained by bonding an alkyl group having 1 to 5 carbon atoms to the benzene ring to which the hydroxyl group of the hydroxystyrene is bonded and a benzene ring to which the hydroxyl group is bonded in addition to one or two hydroxyl groups The sum of the number of hydroxyl groups is 2 to 3), and the like

Examples of the halogen atom include a chlorine atom, a fluorine atom and a bromine atom, and a fluorine atom is preferable.

The &quot; position of hydroxystyrene &quot; refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The structural unit derived from the hydroxystyrene is represented by the following formula (a-2), for example.

(33)

In formula (a-2), R ^a2 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, R ^a3 represents an alkyl group having 1 to 5 carbon atoms, p represents an integer of 1 to 3, Represents an integer from 0 to 2.

The alkyl group of R ^a2 preferably has 1 to 5 carbon atoms. The alkyl group is preferably a linear or branched alkyl group, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, And the like. Among them, methyl group is preferable industrially.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

As the halogenated alkyl group, a part or all of hydrogen atoms of the above-described alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Among these, it is preferable that all hydrogen atoms are substituted with fluorine atoms. The fluorinated alkyl group is preferably a linear or branched fluorinated alkyl group, more preferably a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or a nonafluorobutyl group, more preferably a trifluoromethyl group (-CF ₃ ) is most preferable.

As R ^{a2, a} hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

The alkyl group having 1 to 5 carbon atoms for R ^{a3 includes} the same groups as those for R ^a2 .

and q is an integer of 0 to 2. Of these, 0 or 1 is preferable, and an industrial aspect is particularly preferably 0.

The substitution position of R ^a3 may be an ortho, meta, or para position when q is 1, and arbitrary substitution positions may be combined when q is 2.

p is an integer of 1 to 3, preferably 1.

The substitution position of the hydroxyl group may be any of ortho, meta, and para positions when p is 1, but it is preferably para to the point that it is readily available and the price is low. When p is 2 or 3, arbitrary substitution positions can be combined.

The structural unit represented by the above formula (a-2) may be used alone, or two or more kinds may be used in combination.

The proportion of the structural unit derived from hydroxystyrene in the polyhydroxystyrene-based resin is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, based on the total structural units constituting the polyhydroxystyrene-based resin , And still more preferably 80 to 100 mol%. Within the above range, the alkali solubility of the photosensitive composition can be made appropriate.

The polyhydroxystyrene-based resin preferably has a structural unit derived from styrene.

Herein, the "structural unit derived from styrene" is meant to include a constitutional unit formed by cleavage of an ethylenic double bond of styrene and a styrene derivative (but not hydroxystyrene).

The "styrene derivative" is a compound in which a hydrogen atom bonded to the α-position of styrene is substituted with another substituent such as a halogen atom, an alkyl group, a halogenated alkyl group or the like, and a hydrogen atom of a phenyl group of styrene is substituted with a substituent such as an alkyl group having 1 to 5 carbon atoms And the like.

Examples of the halogen atom include a chlorine atom, a fluorine atom and a bromine atom, and a fluorine atom is preferable.

The &quot; position of styrene &quot; refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The constituent unit derived from this styrene is represented by the following formula (a-3), for example. In the formula, R ^a2 , R ^a3 and q have the same meanings as in the formula (a-2).

(34)

R ^a2 and R ^a3, the of the formula (a2) R ^a2 and R ^a3 Respectively.

and q is an integer of 0 to 2. Of these, 0 or 1 is preferable, and an industrial aspect is particularly preferably 0.

The substitution position of R ^a3 may be an ortho, meta, or para position when q is 1, and arbitrary substitution positions may be combined when q is 2.

The structural unit represented by the above formula (a-3) may be used alone, or two or more kinds may be used in combination.

The proportion of the structural unit derived from styrene in the polyhydroxystyrene-based resin is preferably 40 mol% or less, more preferably 30 mol% or less, and most preferably 20 mol% or less based on the total structural units constituting the polyhydroxystyrene- Mol% or less. By setting the amount within the above range, the alkali solubility of the photosensitive composition can be made suitable, and the balance with other constituent units can be improved.

The polyhydroxystyrene-based resin may have a constitutional unit derived from hydroxystyrene or a constitutional unit derived from styrene. More preferably, the polyhydroxystyrene-based resin is a polymer comprising only a constituent unit derived from hydroxystyrene, or a copolymer comprising a constituent unit derived from hydroxystyrene and a constituent unit derived from styrene.

The mass average molecular weight of the polyhydroxystyrene-based resin is not particularly limited, but is preferably 1,500 to 40,000, and more preferably 2,000 to 8,000.

As the alkali-soluble resin having a phenolic hydroxyl group, a novolak resin may also be used. This novolak resin can be obtained by subjecting phenols and aldehydes to addition condensation in the presence of an acid catalyst.

The phenols include phenol; cresols such as o-cresol, m-cresol and p-cresol; Such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5- Ylenol; butylphenol, p-butylphenol, p-methylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, monoalkyl phenols such as tert-butyl phenol; Trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; Polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and fluoroglycinol; Alkyl-substituted phenols such as alkyl resorcin, alkyl catechol and alkyl hydroquinone (all alkyl groups having 1 to 4 carbon atoms); and polycyclic phenols such as? -naphthol,? -naphthol, hydroxydiphenyl and bisphenol A. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, various properties such as the sensitivity of the resulting photosensitive composition can be adjusted by adjusting the blending ratio of both.

Examples of the aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; Organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfuric acid and para-toluenesulfonic acid; And metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

Specific examples of the novolak resin thus obtained include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolac resin, phenol-naphthol / formaldehyde condensed novolac resin, and the like.

The mass average molecular weight of the novolak resin is not particularly limited, but is preferably from 1,000 to 30,000, and more preferably from 3,000 to 25,000.

As the alkali-soluble resin having a phenolic hydroxyl group, a phenol-xylylene glycol condensation resin, a cresol-xylylene glycol condensation resin, a phenol-dicyclopentadiene condensation resin, or the like may be used.

Examples of the resin having a carboxyl group include a homopolymer or a copolymer containing a constituent unit derived from a polymerizable compound having a carboxyl group.

Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; A carboxyl group such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid, Compound; And the like. The polymerizable compound having a carboxyl group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

The mass average molecular weight of the resin having a carboxyl group is not particularly limited, but is preferably 50000 to 800000.

Specific examples of the compound having a hydroxyl group and / or a carboxyl group include polysilsesquioxane having a hydroxyl group and / or a carboxyl group, polysiloxane having a hydroxyl group and / or a carboxyl group, tetrahydroxytitanium, 2,4-pentanedione di Dioxime compounds such as oxime.

The content of the compound having a hydroxyl group and / or a carboxyl group can be appropriately selected in accordance with the content of the vinyl group-containing compound represented by the general formula (1), the monovinyl group and the mono (meth) acryloyloxy group-containing compound represented by the general formula (10) Is preferably 20 to 200 parts by mass, more preferably 50 to 150 parts by mass based on 100 parts by mass of the (meth) acryloyloxy group-containing compound represented by the general formula (19) or a combination of at least two of them. Within the above range, the patterning property of the photosensitive composition tends to be good.

&Lt;

The photoacid generator in the photosensitive composition according to the present invention is not particularly limited and conventionally known photoacid generators may be used. The photoacid generators may be used alone or in combination of two or more.

Specific examples of the photoacid generator include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, halogen-containing triazine compounds, diazomethane acid generators, nitrobenzylsulfonate acids Generators (nitrobenzyl derivatives), iminosulfonate acid generators, and disulfone acid generators.

A preferable sulfonium salt-based acid generator is, for example, a compound represented by the following formula (t-1).

(35)

In the formula (t-1), R ^t1 and R ^t2 each independently represent a hydrocarbon group which may have a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent and R ^t3 represents a halogen R ^t4 represents a hydrocarbon group which may have a hydrogen atom, an oxygen atom or a halogen atom, a benzoyl group which may have a substituent, or a polyphenyl group which may have a substituent , And A ^- represents a counter ion of an onium ion.

Specific examples of A ^- include SbF ₆ ^- , PF ₆ ^- , AsF ₆ ^- , BF ₄ ^- , SbCl ₆ ^- , ClO ₄ ^- , CF ₃ SO ₃ ^- , CH ₃ SO ₃ ^- , FSO ₃ ^- , F ₂ PO ₂ ^- , p-toluenesulfonate, nonafluorobutanesulfonate, adamantanecarboxylate, tetraarylborate and fluorinated alkyl fluoro phosphoric anions represented by the following formula (t-2).

(36)

In the formula (t-2), Rf represents an alkyl group in which at least 80% of hydrogen atoms have been substituted with fluorine atoms. g is the number, and represents an integer of 1 to 5. g Rf may be the same or different.

Examples of the photoacid generator represented by the above formula (t-1) include 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4- chlorophenyl) sulfonium hexafluoroantimonate, (4- (2-chloro-4-benzoylphenylthio) phenylbis (4-methylphenyl) sulfonium hexafluoroantimonate, 4- 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- 4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-fluoro-4- Sulfonium hexafluoroantimonate , 4- (2-methyl-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,3,5,6-tetramethyl- (2,6-dichloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis 4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4 (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-fluoro-4-benzoylphenylthio) phenylbis Sulfonium hexafluoroantimonate, 4- (2-methyl-4-benzoylphenylthio (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3,5,6-tetramethyl-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,6-dimethyl-4-benzoyl) Phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2,3-dimethyl-4-benzoylphenylthio) phenylbis 4-acetylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methylbenzoyl) phenylthio) phenyldiphenylsulfonium 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2- Methoxybenzoyl) phenylthio) phenyldiphenylsulfonium hexafluoroanti (2-chloro-4-dodecanoylphenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-acetylphenylthio) phenylbis Phenyl) sulfonium hexafluoroantimonate, 4- (4-methylbenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4- (4-methoxybenzoyl) phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis 4- (2-chloro-4-acetylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- Thio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimo 4- (2-chloro-4- (4-fluorobenzoyl) phenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (4-chlorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-dodecanoylphenylthio) phenylbis (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- (2-chloro-4- benzoylphenylthio) phenyldiphenylsulfonium tetrafluoro Borate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium perchlorate, 4- (2-chloro-4- benzoylphenylthio) phenyldiphenylsulfonium trifluoromethanesulfonate, 4- 4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4- Tetrafluoro (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium perchlorate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium p-toluenesulfonate, 4- 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium nonafluorobutanesulfonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-chlorophenyl) sulfonium perchlorate, 4- Sulfonium trifluoro Methanesulfonate, diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethylphosphite, diphenyl [4- (p-terphenylthio) phenyl] sulfonium hexafluoroantimonate , Diphenyl [4- (p-terphenylthio) phenyl] sulfonium trifluorotris pentafluoroethyl phosphite, and the like.

Examples of other onium salt-based acid generators include the cationic moiety of the above formula (t-1), for example, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, Butoxyphenyl) phenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) (3,4-ditert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, diphenyl Butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, Dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfone (4-tert-butylphenyl) iodonium such as diphenyliodonium, bis (4-tert-butylphenyl) iodonium, -Butoxyphenyl) phenyliodonium, and (4-methoxyphenyl) phenyliodonium, and other aryl iodonium cation.

Examples of the oxime sulfonate-based acid generators include [2- (propylsulfonyloxyimino) -2,3-dihydrothiophen-3-ylidene] (o-tolyl) acetonitrile, (Benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile,? - (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, 2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, and? - (ethylsulfonyloxyimino) -1-cyclopentenyl acetonitrile.

In addition to the above, a compound represented by the following formula (t-3) may be mentioned.

(37)

In the formula (t-3), R ^t5 is a monovalent, divalent, or represents a trivalent organic, R ^t6 represents a substituted or saturated unsubstituted hydrocarbon group, unsaturated hydrocarbon group or an aromatic compound, h is 1 and 6 &lt; / RTI &gt;

R ^t5 is particularly preferably an aromatic compound group. Examples of such an aromatic compound group include aromatic hydrocarbon groups such as phenyl group and naphthyl group, and heterocyclic groups such as furyl group and thienyl group. They may have one or more substituents suitable on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, and a nitro group. R ^t6 is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. Also, h is preferably an integer of 1 to 3, more preferably 1 or 2.

Examples of the photoacid generator represented by the formula (t-3) include a compound wherein R ^t5 is a phenyl group, a methylphenyl group, or a methoxyphenyl group when h = 1, and R ^t6 is a methyl group. More specifically, as the photoacid generator represented by the above formula (t-3), α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) Methylphenyl) acetonitrile and? - (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile.

Examples of the photoacid generator represented by the general formula (t-3) include a photoacid generator represented by the following formula when h = 2.

(38)

Examples of halogen-containing triazine compounds include 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (Trichloromethyl) -6- [2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis -Tetrahydro] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5- dimethoxyphenyl) ethenyl] (Trichloromethyl) -6- [2- (3,5-diethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- -triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] L-methylethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] - (trichloromethyl) -6- (3,4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- 4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- Trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis- 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4 (Trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) Triazine, 2- 2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) - dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4- dimethoxyphenyl) ethenyl] Bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6- (Trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1 , Halogen-containing triazine compounds such as 3,5-triazine, and halogen-containing triazine compounds represented by the following formula (t-4) such as tris (2,3-dibromopropyl) isocyanurate have.

[Chemical Formula 39]

In the formula (t-4), ^Rt7 , ^Rt8 , ^Rt9 Each independently represent a halogenated alkyl group having 1 to 6 carbon atoms.

Examples of other photoacid generators include bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1- Bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (4-ethylphenylsulfonyl) diazomethane, bis (4-methoxyphenylsulfonyl) diazomethane, bis Bis sulfonyl diazomethanes such as bis (4-fluorophenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane and bis (4-tert-butylphenylsulfonyl) diazomethane ; Methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (p- toluenesulfonyl) propane, 2- Methylthio) propiophenone, and 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one; 1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarbamyl Diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (1,1-dimethylethylsulfonyl) Dimethyl-2-butanone, 1-acetyl-1- (1-methylethylsulfonyl) diazomethane, 1-diazo-1- (p- toluenesulfonyl) -3,3- , 1-diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (p- toluenesulfonyl) 2-diazo-2-benzenesulfonylacetic acid isopropyl, 2-diazo-2-methanesulfonyl acetoacetate, Sulfonylcarbonyldiazomethanes such as cyclohexyl 2-benzenesulfonylacetate and -tert-butyl 2-diazo-2- (p-toluenesulfonyl) acetic acid; nitrobenzyl derivatives of p-toluenesulfonic acid-2-nitrobenzyl, p-toluenesulfonic acid-2,6-dinitrobenzyl, p-trifluoromethylbenzenesulfonic acid-2,4-dinitrobenzyl and the like; Methanesulfonic acid esters of pyrogallol, benzenesulfonic acid esters of pyrogallol, p-toluenesulfonic acid esters of pyrogallol, p-methoxybenzenesulfonic acid esters of pyrogallol, mesylenesulfonic acid esters of pyrogallol, benzylsulfonic acid esters of pyrogallol, Methanesulfonic acid ester of alkyl, methanesulfonic acid ester of alkylsulfate, p-toluenesulfonic acid ester of alkylsulfuric acid, p-methoxybenzenesulfonic acid ester of alkyl (having alkyl group of 1 to 15 carbon atoms) ester, Esters of polyhydroxy compounds such as benzylsulfonic acid esters of alkyl allyl and aliphatic or aromatic sulfonic acids; And the like.

The content of the photoacid generator is not particularly limited so long as the content of the vinyl group-containing compound represented by the general formula (1), the monovinyl group and the mono (meth) acryloyloxy group-containing compound represented by the general formula (10) Is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 10 parts by mass based on 100 parts by mass of the (meth) acryloyloxy group-containing compound represented by the general formula (1) or a combination of at least two of them. Within the above range, the patterning property of the photosensitive composition tends to be good.

&Lt; Other components &gt;

The photosensitive composition according to the present invention may contain a photopolymerization initiator, a photopolymerizable monomer, an acid-crosslinking substance, a photobase generator, a colorant, a dispersant, a sensitizer, a adhesion enhancer, do.

«Pattern formation method»

The pattern forming method according to the present invention includes a coating film forming step of forming a coating film comprising the photosensitive composition according to the present invention, an exposure step of selectively exposing the coating film, and a developing step of developing the coating film after exposure will be. Hereinafter, each process will be described.

&Lt; Coating film forming step &

In the coating film forming step, the photosensitive composition is applied to the surface of the photoreceptor to form a coating film comprising the photosensitive composition. Examples of the application method include a dipping method, a spraying method, a bar coating method, a roll coating method, a spin coating method, and a curtain coating method. The thickness of the coating film is not particularly limited. Typically, the thickness of the coating film is preferably 2 to 100 mu m, more preferably 3 to 50 mu m. The thickness of the coating film can be appropriately controlled by adjusting the coating method and the solid content concentration and viscosity of the photosensitive composition.

After the formation of the coating film, the coating film may be heated for the purpose of removing the solvent in the coating film before proceeding to the exposure step. The heating temperature and the heating time are not particularly limited as long as thermal degradation or thermal decomposition does not occur in the components contained in the photosensitive composition. When the boiling point of the solvent in the coating film is high, the coating film may be heated under reduced pressure.

<Exposure Step>

In the exposure step, the coating film obtained in the coating film forming step is selectively exposed in a predetermined pattern. The selective exposure is typically performed using a mask of a predetermined pattern. Examples of the radiation used for exposure include ultraviolet rays, electron beams, and laser beams emitted from a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a g-line stepper, and an i-line stepper. The exposure dose is usually from 1 to 1000 mJ / cm 2, preferably from 10 to 500 mJ / cm 2 although it varies depending on the light source used or the film thickness of the coating film.

<Development Process>

In the developing step, the exposed portion or the unexposed portion is removed from a coated film selectively exposed in a predetermined pattern in the exposure step to develop the coated film. The exposed portion or the unexposed portion is usually removed by dissolving in an alkaline developer. Examples of the developing method include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. As the alkali developing solution, an aqueous solution containing at least one alkaline compound selected from an inorganic alkaline compound and an organic alkaline compound can be used. The concentration of the alkaline compound in the developing solution is not particularly limited as long as it can develop a coated film after exposure. Typically, the concentration of the alkaline compound in the developer is preferably 1 to 10% by mass.

Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium dihydrogenphosphate, dipotassium hydrogenphosphate, disodium hydrogenphosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, sodium borate , Potassium borate and ammonia. Examples of the organic alkali compound include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, There may be mentioned triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine and triethanolamine.

A water-soluble organic solvent such as methanol, ethanol, propanol or ethylene glycol, a surfactant, a storage stabilizer, and a resin dissolution inhibitor may be added to the developer in an appropriate amount, if necessary.

&Lt; Difference between Positive Patterning and Negative Patterning &gt;

After formation of the coating film in the coating film forming step, it is also possible to perform positive patterning according to the temperature at which the coating film is processed before the transition to the exposure step, and it is also possible to perform negative patterning.

In the case of the positive patterning, first, the vinyl group-containing compound represented by the general formula (1), the monovinyl group and the mono (meth) acryloyloxy group-containing compound represented by the general formula (10) The crosslinking is caused by heating the coating film at a temperature at which crosslinking occurs between the (meth) acryloyloxy group-containing compound represented by the formula (19) and a compound having a hydroxyl group and / or a carboxyl group, and the coating film becomes a cured film insoluble in developer . When the coating film is selectively exposed in the exposure step, the crosslinking is dissociated by the acid generated from the photoacid generator, and the exposed part becomes soluble in the developer. In the developing process, this exposed portion is removed by the developer.

On the other hand, in the case of the negative patterning, during the period from the coating film formation step to the exposure step, the coating film is formed by coating the vinyl group-containing compound represented by the general formula (1), the monovinyl group represented by the general formula (10) (Meth) acryloyloxy group-containing compound represented by the general formula (19) and a compound having a hydroxyl group and / or a carboxyl group is generated at a temperature lower than the temperature at which the crosslinking occurs. This coating film has no crosslinking and is soluble in a developing solution. When the coating film is selectively exposed in the exposure step, the crosslinking occurs due to the acid generated from the photoacid generator, and the exposed part is insoluble in the developer. On the other hand, the unexposed portion is still available for the developer. In the developing process, the unexposed portion is removed by the developer.

(Meth) acryloyloxy group-containing compound represented by the general formula (1), the monovinyl group and the mono (meth) acryloyloxy group-containing compound represented by the general formula (10) The temperature at which the crosslinking between the acryloyloxy group-containing compound and the compound having a hydroxyl group and / or the carboxyl group is generated may vary depending on the combination of components in the photosensitive composition, but is typically 70 ° C or higher. As described above, the temperature at which crosslinking occurs may vary depending on the combination of components in the photosensitive composition. Therefore, when the temperature is, for example, higher than 80 ° C, the temperature is preferably 80 ° C or lower, more preferably 70 ° C or lower Negative patterning is possible.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

«Materials»

The materials used in Examples and Comparative Examples are as follows.

&Lt; Vinyl ether compound (compound represented by formula (1) and comparative compound) &gt;

As the compound represented by the above general formula (1), Compound 1 represented by the following formula was prepared. For comparison, Comparative Compounds 1 to 3 represented by the following formulas were prepared.

(40)

(41)

The synthesis method of Compound 1 is shown below (Synthesis Example 1). The materials used in the synthesis examples are as follows.

[Inorganic base]

(1) Sodium carbonate

Particle diameter distribution: 250 占 퐉 or more; 3 wt%

                150 占 퐉 or more and less than 250 占 퐉; 15 wt%

                75 占 퐉 or more and less than 150 占 퐉; 50 wt%

                Less than 75 탆; 32 wt%

The above particle diameter distribution was divided by using a sieve of 60 mesh (250 탆), 100 mesh (150 탆) and 200 mesh (75 탆), and then the weight of each of the sieved component .

[Transition element compound catalyst]

(1) Di-μ-chlorobis (1,5-cyclooctadiene) is an iridium (I): [Ir (cod) Cl] ₂

[Hydroxy compound]

(1) 9,9'-bis (6-hydroxy-2-naphthyl) fluorene

(2) 9,9'-bis (4-hydroxyphenyl) fluorene

[Vinyl ester compound]

(1) Vinyl propionate

[Synthesis Example 1] Synthesis of Compound 1

(1,5-cyclooctadiene) was dissolved in a 1000 ml reaction vessel equipped with a decanter for separating the organic layer from the reaction tube, the cooling tube, and the condensate to return the organic layer to the reaction vessel and discharging the aqueous layer out of the system, ) [Ir (cod) Cl] ₂ (839 mg, 1.25 mmol), sodium carbonate (12.7 g, 0.12 mol), 9,9'-bis (6-hydroxy- 0.5 mol), vinyl propionate (125 g, 1.25 mol) and toluene (300 ml) were charged, the number of revolutions was set to 250 rpm using a stirring blade having a surface area of 10 cm 2, . The reaction was allowed to proceed for 5 hours under reflux while the by-product water was removed with a decanter. The reaction solution was analyzed by gas chromatography to find that the conversion rate of 9,9'-bis (6-hydroxy-2-naphthyl) fluorene was 100%, and 9,9'-bis (6- (6-vinyloxy-2-naphthyl) fluorene (Compound 1) was 81%, and bis 6-naphthol fluorene monovinyl ether was 4% Yield. &Lt; / RTI &gt;

_{^{1 H-NMR (CDCl 3)}} : 4.47 (dd, 2H, J = 1.5 ㎐, 5.0 ㎐), 4.81 (dd, 2H, J = 3.5 ㎐, 12.0 ㎐), 6.71 (dd, 2H, J = 6.0 ㎐) , 7.12-7.82 (m, 20H)

&Lt; Compounds Having Hydroxyl Group and / or Carboxyl Group &

As the compound having a hydroxyl group and / or a carboxyl group, the following compounds 2 to 8 were used.

(42)

Compound 3: hydroxyl group-containing polysilsesquioxane (mass average molecular weight: 10,000)

(43)

Compound 8: Cresol novolak resin (trade name: GTR-B9, manufactured by KANEI Chemical Co., Ltd.)

R in compound 4 and s in compound 5 represent a positive number. The mass average molecular weight of Compound 4 is 10,000, and the mass average molecular weight of Compound 5 is 12,000.

&Lt;

(44)

<Adhesion Enhancer>

Adhesion enhancer 1: KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.)

&Lt; Preparation of photosensitive composition &gt;

5 g of the vinyl ether compound shown in Table 1 and 2 g of the compound having hydroxyl group and / or carboxyl group shown in Table 1 (in the case of the compound 6) or 5 g (in other cases) and 10.5 g of the photo acid generator And 10.015 g of the enhancer were mixed and dissolved in 58 g of propylene glycol monomethyl ether acetate to obtain a solution. The obtained solution was filtered using a polyethylene filter having a pore size of 0.10 占 퐉 and a polyethylene filter having a pore size of 0.05 占 퐉 to prepare a photosensitive composition.

«Evaluation»

<Storage stability>

The obtained photosensitive composition was allowed to stand at 20 占 폚 or 30 占 폚 for 2 weeks, and the presence or absence of a precipitate was visually observed. When the precipitate was observed even at a temperature of 20 占 폚 or 30 占 폚, it was judged that the storage stability was poor (占). When the precipitate was confirmed only at 30 占 폚, the storage stability was slightly poor , And it was judged that the storage stability was good (?) In the case where no precipitate was observed even at the temperature of 20 占 폚 or 30 占 폚. The results are shown in Table 1.

<Patterning characteristics 1>

The obtained photosensitive composition was allowed to stand at 25 占 폚 for 3 days, and the photosensitive composition after being left to stand was coated on a glass substrate with a coater. And then heated (prebaking) on a hot plate at 100 DEG C for 2 minutes to obtain a cured film. This cured film was exposed with broadband light. After heating (PEB) at 100 占 폚 for 2 minutes on a hot plate, development was performed with a 2.38 mass% TMAH aqueous solution to perform positive patterning.

In the same manner, the photosensitive composition was coated on a substrate and heated (prebaked) at 70 캜 for 2 minutes on a hot plate. The coated film after heating was exposed with broadband light. After heating (PEB) on a hot plate at 70 캜 for 2 minutes, development was performed with a 2.38 mass% TMAH aqueous solution, and negative patterning was performed.

It was confirmed by a microscope whether a pattern was formed. When the pattern is formed in either the positive or negative patterning, it is determined that the patterning characteristic is good (?), And when the pattern is formed only in the positive patterning, it is determined that the patterning characteristic is slightly bad (?) , And when the pattern is not formed in either the positive or negative patterning, it is determined that the patterning characteristic is bad (X). The results are shown in Table 1.

<Patterning characteristics 2>

The obtained photosensitive composition was allowed to stand at 25 占 폚 for 3 days, and the photosensitive composition after being left to stand was coated on a glass substrate with a coater. (Prebaking) was performed on a hot plate at 80 DEG C for 2 minutes. The coated film after heating was exposed with broadband light. After heating (PEB) on a hot plate at 70 캜 for 2 minutes, development was performed with a 2.38 mass% TMAH aqueous solution, and negative patterning was performed.

It was confirmed by a microscope whether a pattern was formed. When the pattern is formed, it is determined that the patterning characteristic is good (O), and when the pattern is not formed, it is determined that the patterning characteristic is bad (X). The results are shown in Table 1.

As can be seen from Table 1, the photosensitive composition containing Compound 1 was excellent in storage stability and patterning property. On the other hand, the photosensitive composition containing any of Comparative Compounds 1 to 3 was inferior in storage stability and patterning characteristics as compared with the photosensitive composition containing Compound 1.

Claims (10)

A photosensitive composition comprising a vinyl group-containing compound represented by the following general formula (1), a compound having a hydroxyl group and / or a carboxyl group, and a photoacid generator.
[Chemical Formula 1]

(Wherein W ¹ and W ² independently represent a group represented by the following formula (2), a group represented by the following formula (4), a hydroxyl group or a (meth) acryloyloxy group, provided that W ¹ and W ² are not simultaneously oxygen radicals and are not a group represented by the following general formula (4), the rings Y ¹ and Y ² are the same or different aromatic hydrocarbon rings, R is a single bond, a methylene group which may have a substituent, , An ethylene group which may contain a hetero atom between two carbon atoms, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, and R ^3a and R ^3b independently represent a group represented by Si A halogen atom, or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 to 4)
(2)

(Wherein Ring Z represents an aromatic hydrocarbon ring, X represents a single bond or -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ² represents a monovalent hydrocarbon group, a hydroxyl group, a group represented by group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c represents a group, -SR ^4b represented by -OR ^4a, -N (R ^4d), the group represented by _2, a (meth) acryloyloxy group with an acrylic, a sulfo or a monovalent hydrocarbon group, a group represented by group, -SR ^4b represented by -OR ^4a, an acyl group, an alkoxycarbonyl group, -NHR ^4c by indicating group, or -N (R ^4d) groups are at least part of the hydrogen atoms bonded to a carbon atom monovalent hydrocarbon groups contained indicating _2, groups represented by a hydroxyl group, -OR ^4a, -SR group represented by ^4b, an acyl group , An alkoxycarbonyl group, a halogen atom, a knit Group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, the group represented by -NHR ^4c, -N (R ^4d), the group represented by _2, acryloyloxy group in a (meth) acrylate, mesyl oxy group, or a sulfo group , R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more)
(3)

(Wherein rings Z, X, R ¹ , R ² and m are as defined above) The method according to claim 1,
And the ring Z is a benzene ring or a naphthalene ring. The method according to claim 1,
Wherein R &lt; ^{1 &gt;} is a single bond. A photosensitive composition comprising a compound having a monovinyl group and a mono (meth) acryloyloxy group represented by the following general formula (10), a compound having a hydroxyl group and / or a carboxyl group, and a photoacid generator.
[Chemical Formula 4]

(Wherein one of W ¹¹ and W ¹² represents a group represented by the following general formula (2) and the other represents a group represented by the following general formula (11) or (12), and the ring Y ¹ and the ring Y ² are the same R represents a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent, an ethylene group which may contain a hetero atom between two carbon atoms, a group represented by -O-, -NH- or -S-, R ^3a and R ^3b independently represent a cyano group, a halogen atom or a monovalent hydrocarbon group, and n 1 and n 2 independently represent an integer of 0 to 4)
[Chemical Formula 5]

(Wherein Ring Z represents an aromatic hydrocarbon ring, X represents a single bond or -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ² represents a monovalent hydrocarbon group, a hydroxyl group, a group represented by group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c represents a group, -SR ^4b represented by -OR ^4a, -N (R ^4d), the group represented by _2, a (meth) acryloyloxy group with an acrylic, a sulfo or a monovalent hydrocarbon group, a group represented by group, -SR ^4b represented by -OR ^4a, an acyl group, an alkoxycarbonyl group, -NHR ^4c by indicating group, or -N (R ^4d) groups are at least part of the hydrogen atoms bonded to a carbon atom monovalent hydrocarbon groups contained indicating _2, groups represented by a hydroxyl group, -OR ^4a, -SR group represented by ^4b, an acyl group , An alkoxycarbonyl group, a halogen atom, a knit Group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, the group represented by -NHR ^4c, -N (R ^4d), the group represented by _2, acryloyloxy group in a (meth) acrylate, mesyl oxy group, or a sulfo group , R ^4a to R ^4d independently represent a monovalent hydrocarbon group, and m represents an integer of 0 or more)
[Chemical Formula 6]

(Wherein R ⁵ represents a hydrogen atom or a methyl group, 1 represents an integer of 1 to 4, and the rings Z, X, R ¹ , R ² and m have the same meanings as defined above)
(7)

(Wherein rings Z, X, R ¹ , R ² , R ⁵ and m are as defined above) 5. The method of claim 4,
Wherein ring Z is a benzene ring or a naphthalene ring. 5. The method of claim 4,
Wherein R &lt; ^{1 &gt;} is a single bond. A photosensitive composition comprising a (meth) acryloyloxy group-containing compound represented by the following general formula (19), a compound having a hydroxyl group and / or a carboxyl group, and a photoacid generator.
[Chemical Formula 8]

(Wherein W ¹³ and W ¹⁴ independently represent a group represented by the following formula (12), a hydroxyl group or a (meth) acryloyloxy group, provided that at least one of W ¹³ and W ¹⁴ is a group represented by the following formula , The ring Y ¹ and the ring Y ² may be the same or different and represent an aromatic hydrocarbon ring, R may be a single bond, a methylene group which may have a substituent, a substituent, or a heteroatom between two carbon atoms An ethyl group which may contain an atom, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, R ^3a and R ^3b independently represent a cyano group, a halogen atom or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 to 4)
[Chemical Formula 9]

(Wherein Ring Z represents an aromatic hydrocarbon ring, X represents a single bond or -S-, R ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ² represents a monovalent hydrocarbon group, a hydroxyl group, a group represented by group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, -NHR ^4c represents a group, -SR ^4b represented by -OR ^4a, -N (R ^4d), the group represented by _2, a (meth) acryloyloxy group with an acrylic, a sulfo or a monovalent hydrocarbon group, a group represented by group, -SR ^4b represented by -OR ^4a, an acyl group, an alkoxycarbonyl group, -NHR ^4c , A group represented by -OR ^4a , a group represented by -SR ^4b , an acyl group (for example, a group represented by -SR ^4b) , or a group represented by -SR ^4b in which at least a part of the hydrogen atoms bonded to the carbon atom contained in the group represented by -N (R ^4d ) ₂ is a monovalent hydrocarbon group, , An alkoxycarbonyl group, a halogen atom, a knit Group, a cyano group, a mercapto group, a carboxyl group, an amino group, a carbamoyl group, the group represented by -NHR ^4c, -N (R ^4d), the group represented by _2, acryloyloxy group in a (meth) acrylate, mesyl oxy group, or a sulfo group , R ^4a to R ^4d independently represent a monovalent hydrocarbon group, R ⁵ represents a hydrogen atom or a methyl group, and m represents an integer of 0 or more) 8. The method of claim 7,
Wherein ring Z is a benzene ring or a naphthalene ring. 8. The method of claim 7,
Wherein R &lt; ^{1 &gt;} is a single bond. A process for producing a photosensitive film, comprising the steps of: forming a coating film comprising the photosensitive composition according to any one of claims 1 to 9;
An exposure step of selectively exposing the coating film,
And a developing step of developing the coating film after exposure.