JP2003286215A - Bicyclohexane-divinyl ether compound, method for producing the same and photoresist composition containing the compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide (trans, trans)-1,1'-bicyclohexane-4,4'-bivinyl ether compound which has a single structure and is low odorful, low evaporable, low irritative, low toxic, and highly cation-polymerizable. <P>SOLUTION: This (trans, trans)-1,1'-bicyclohexane-4,4'-bivinyl ether compound represented by formula (1), a method for producing the compound, and a photoresist composition containing the compound. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel bicyclohexane-divinyl ether compound, a method for producing the same, and a photoresist composition containing the compound.

[0002]

2. Description of the Related Art Conventionally, vinyl ether compounds have been used as a cationically polymerizable monomer or a radically polymerizable monomer in applications such as photoresists, adhesives and paints. In the case of a phenol derivative, there were problems such as suspicion of action of environmental hormone due to the chemical structure.

On the other hand, in order to overcome these problems,
An attempt to change the phenol skeleton to a cyclohexanol skeleton by reducing the volatility by relatively increasing the molecular weight and reducing the aromatic ring, for example, a method of converting hydrogenated bisphenol A into a vinyl ether is disclosed in JP-A-10-279513. Is disclosed in.

However, the compound obtained by this method has a three-dimensional structure of two cyclohexanol skeletons,
It is a mixture of three types of stereo isomers of trans, trans-form, cis, trans-form and cis, cis-form, and it is known that the isomer composition greatly varies depending on the type of reducing catalyst and reducing conditions. (Japanese Patent Laid-Open No. 53-11
9855, JP-A-64-34935, and JP-A-2000-44503). Therefore, the composition of the divinyl ether compound obtained by these methods is not constant, and the physical properties are not stable.

[0005]

The present invention has low odor, low volatility, low irritation, low toxicity and high cationic polymerizability.
Having a single structure (trans, trans) -1, 1'-
It is intended to provide a bicyclohexane-4,4'-divinyl ether compound.

[0006]

Means for Solving the Problems The present inventor has conducted extensive studies in order to achieve the above object. As a result, a single stereoisomer (trans, trans) -1,1'-bicyclohexane-4,4'-diol has a single structure by divinyl etherification (trans, trans). -1,1'-bicyclohexane-4,4'-divinyl ether compound is obtained, the above-mentioned object can be achieved, and the above-mentioned diol, which is a trans or trans-form which is purified by recrystallization in advance, is divinyl etherified. The desired compound can be preferably obtained, and the above-mentioned diol, which is a trans or trans form, or its cis or trans form.
The present inventors have completed the present invention by finding that the desired compound can be suitably obtained by subjecting the isomer and its cis, cis-isomer stereoisomer mixture to divinyl etherification, followed by recrystallization and purification.

The present invention relates to a divinyl ether compound which is a novel compound having a single structure, a method for producing the compound, and a photoresist composition containing the compound, which are shown below.

1. Formula (1)

[0009]

[Chemical 3] A (trans, trans) -1,1′-bicyclohexane-4,4′-divinyl ether compound represented by:

2. Formula (2)

[0011]

[Chemical 4] The formula (1) is characterized in that (trans, trans) -1,1′-bicyclohexane-4,4′-diol represented by the formula (1) is reacted with acetylene in the presence of an alkali catalyst to form a vinyl ether. A method for producing a (trans, trans) -1,1′-bicyclohexane-4,4′-divinyl ether compound represented by:

3. 3. The method for producing a divinyl ether compound according to item 2, wherein the (trans, trans) -1,1′-bicyclohexane-4,4′-diol represented by the formula (2) is a purified product by recrystallization.

4. The (trans, trans) -1,1′-bicyclohexane-4,4′-diol represented by the formula (2), and its cis, trans-isomer and cis, cis-isomer stereoisomer mixture are treated with an alkali catalyst. In the presence of acetylene for vinyl etherification, and then recrystallization (trans, trans) -1,1′-bicyclohexane-4,4 ′ represented by the formula (1). A method for producing a divinyl ether compound.

5. A photoresist composition comprising a (trans, trans) -1,1'-bicyclohexane-4,4'-divinyl ether compound represented by formula (1).

6. (A) (trans, trans) -1,1′-bicyclohexane-4, represented by the formula (1),
4'-divinyl ether compound, (B) having 0.5 to 10 equivalents of carboxyl group per 1 kg of polymer, and having a number average molecular weight in the range of 3,000 to 100,000 and a glass transition temperature of 0 ° C or higher. (A) having 1 to 10 equivalents of hydroxyphenyl group per 1 kg of the polymer, and having a number average molecular weight in the range of 500 to 100,000 and a glass transition temperature of 0 ° C. or higher ( b) and a glass having 0.2 to 20 equivalents of a hydroxyphenyl group and 0.5 to 10 equivalents of a carboxyl group per 1 kg of a polymer, and having a number average molecular weight in the range of 500 to 100,000 and 0 ° C or higher. At least one polymer selected from polymers (c) having a transition temperature, and (C) a compound capable of generating an acid upon irradiation with active energy rays. The photoresist composition according to claim 5 that.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the following description, 1,1'-
Bicyclohexane-4,4'-diol was added to "4,4 '
-Hydrogenated biphenol ".

The compound of the present invention (trans, trans) of the formula (1) which is the compound of the present invention
As 4,4'-hydrogenated biphenol, which is a raw material compound of -1,1'-bicyclohexane-4,4'-divinyl ether compound, 4,4'-hydrogenated biphenol is commercially available as an industrial raw material.
4'-hydrogenated biphenol can be used.

Commercially available 4,4'-hydrogenated biphenol is
Usually, it is a mixture of three stereoisomers of trans, trans-isomer, cis, trans-isomer and cis, cis-isomer, and when the mixture is used after separating the trans and trans-isomers. After divinyl etherification,
The divinyl ether compound of the formula (1) which is the target compound can be obtained without any particular purification. Here, trans, trans-
The method for purifying the body is not particularly limited as long as cis, trans-form and cis, cis-form can be removed, but recrystallization is preferable because the purity of the purified product can be efficiently improved. . As the solvent used for recrystallization,
Alcohols, esters, ketones and the like are preferable, and methanol, ethyl acetate, acetone and the like are particularly preferable. The amount of the solvent used for recrystallization is 0.5 to 10 parts by weight with respect to 1 part by weight of the crude crystal before purification, and may be 1 to 5 parts by weight in consideration of improvement in purity and recovery rate. More preferable.

On the other hand, when 4,4'-hydrogenated biphenol, which is a commercially available stereoisomer mixture, is used as it is for vinyl etherification, only the trans-trans form is purified from the resulting divinyl etherification product. By doing so, the target divinyl ether compound of formula (1) can be obtained.

The compound of the present invention contains 4,4'-hydrogenated biphenol as a mixture of unpurified three stereoisomers of trans, trans-form, cis, trans-form and cis, cis-form. Alternatively, it can be obtained by purifying the mixture as a purified trans or trans-form by introducing acetylene gas in a solvent in the presence of an alkali catalyst to carry out a heating reaction.

The alkali catalyst used in this reaction is not particularly limited, and various known catalysts can be used. Specific examples include alkali metal hydroxides and alkali metal alkoxides. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Examples of the alkali metal alkoxides include sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide and the like. Among these, it is preferable to use a granular alkali metal hydroxide which is inexpensive and has good workability. The amount of alkali catalyst used is 4,4'-
0.1 to 1.0 for 1.0 mol of hydrogenated biphenol
From the viewpoint of reaction rate, it is preferable that the amount is mol.

As the solvent, any solvent can be used without particular limitation as long as it dissolves an unpurified product of 4,4′-hydrogenated biphenol or a trans-trans-form. Specific examples thereof include high-boiling polar solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, sulfolane, and dimethylimidazolidinone. From the viewpoint of workability, the amount of the solvent used is preferably about the same weight to about 3 times the weight of the raw material 4,4′-hydrogenated biphenol.

The vinyl etherification reaction is carried out in the range of 0.10-0.
It can be carried out by blowing acetylene gas or a mixed gas of acetylene and an inert gas into the reaction system at a pressure of 25 MPa while heating and stirring. As the inert gas, for example,
Examples thereof include nitrogen and argon. Reaction temperature is 100-1
The temperature is about 60 ° C., preferably about 120 ° C., and the reaction time is usually about 2 to 24 hours.

The reaction mixture obtained by the vinyl etherification reaction is made into a crude product through the steps of concentrating and distilling, and then removing the alkali content and the high boiling point solvent by washing with water or extraction. The crude product can be purified by appropriately combining separation and purification methods such as distillation under reduced pressure, recrystallization and chromatography. Here, when a trans or trans-form of 4,4′-hydrogenated biphenol is used as a raw material, a substantially pure compound of the present invention can be obtained.

On the other hand, when an unpurified product of 4,4'-hydrogenated biphenol is used as a raw material, at the last stage,
Furthermore, it is necessary to go through a step of removing cis, trans-form and cis, cis-stereoisomer. In this case, the stereoisomer removing step can be used without any particular limitation as long as it can separate trans and trans-forms.
Usually, since the trans and trans-forms have good purity, it is preferable to carry out recrystallization with a solvent such as alcohols, esters and ketones. As the solvent such as alcohols, known solvents can be used without limitation, but it is preferable to use methanol, ethyl acetate, acetone or the like from the viewpoint that the purity can be efficiently improved. The amount of the solvent used for recrystallization is 0.5 to 10 parts by weight with respect to 1 part by weight of the crude crystal, and it is more preferable to set the amount to 1 to 5 parts by weight in consideration of the improvement in purity and the recovery rate. preferable.

Further, the purity can be further improved by performing the solvent extraction before the recrystallization. The solvent used for solvent extraction is preferably a hydrocarbon solvent or the like.

The method for producing the compound of the present invention is not limited to the above-mentioned acetylene method. For example, an exchange reaction with an alkyl vinyl ether using a complex catalyst such as palladium (Japanese Patent Laid-Open No. 9-87224) or vinyl acetate is used. It can also be produced by the exchange reaction of (No. 2001-220364).

The compound of the present invention (trans, trans) -1,1'-bicyclohexane-4 of the formula (1),
The 4′-divinyl ether compound is a single stereoisomer, and is a solid crystal at room temperature and has a melting point of 69 ° C. Also,
The infrared spectrum of the present compound 1, Figure 2 ¹ H-
The NMR spectrum and the ¹³ C-NMR spectrum are shown in FIG. 3, respectively. Therefore, the compound of the present invention can be identified by such means as physicochemical properties.

Photoresist Composition of the Present Invention The photoresist composition of the present invention comprises (A) the above formula (1)
The (trans, trans) -1,1′-bicyclohexane-4,4′-divinyl ether compound represented by
It is a composition characterized by containing.

The composition of the present invention is preferably (A) represented by the formula (1) (trans, trans) -1,1 '.
-Bicyclohexane-4,4'-divinyl ether compound, (B) having 0.5 to 10 equivalents of carboxyl group per 1 kg of polymer, and having a number average molecular weight in the range of 3,000 to 100,000 and 0. Polymer (a) having a glass transition temperature of ℃ or more, having 1 to 10 equivalents of hydroxyphenyl group per 1 kg of the polymer, and 500 to 100,
Polymer (b) having a number average molecular weight in the range of 000 and a glass transition temperature of 0 ° C. or higher and 0.2 to 20 equivalents of hydroxyphenyl groups and 0.5 to 1 kg of the polymer.
Having 10 equivalents of carboxyl groups and 500 to 10
At least one polymer selected from the polymers (c) having a number average molecular weight in the range of 10,000 and a glass transition temperature of 0 ° C. or higher, and (C) a compound capable of generating an acid upon irradiation with active energy rays ( Hereinafter, this may be simply abbreviated as “photoacid generator compound (C)”.

[0031] Polymer (B) Polymer (B) component, the polymer (a), it is at least one polymer selected from the polymer (b) and the polymer (c).

Carboxyl group-containing polymer (a) is a film-forming polymer having at least one carboxyl group in one molecule, for example, a homopolymer of a polymerizable unsaturated monomer containing a carboxyl group; Copolymers of the carboxyl group-containing monomer with other copolymerizable monomers; polyester-based, polyurethane-based, polyamide-based, etc. resins having a carboxyl group in the molecular chain or at the molecular end thereof.

Examples of the above-mentioned polymerizable unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid and the like. Further, as the other monomer copolymerizable with the carboxyl group-containing monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
(Meth) acrylic acid such as butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, and decyl (meth) acrylate. C ₁ ~
C ₁₂ alkyl ester; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
3-hydroxypropyl (meth) acrylate, (meth)
C ₂ -C ₆ hydroxyalkyl esters of (meth) acrylic acid such as hydroxyethyl acrylate-butyl; styrene, alpha-
Vinyl aromatic compounds such as methylstyrene and p-tert-butylstyrene; vinyl acetate, (meth) acrylonitrile, (meth) acrylamide, vinylpyrrolidone and the like. Particularly, as the other monomer, styrene, α-
The use of vinyl aromatic compounds such as methyl styrene and C ₁ -C ₆ alkyl-substituted styrene (for example, p-tert-butyl styrene) is advantageous in terms of accuracy of the image pattern to be formed, etching resistance and the like. It is suitable. These monomers may be used alone or in combination of two or more kinds.

The polymer (a) is about 3,000 to about 10.
It is preferred to have a number average molecular weight in the range of 10,000, especially in the range of about 5,000 to about 30,000, and
The content of the carboxyl group is preferably in the range of generally 0.5 to 10 equivalents, especially 0.5 to 5.0 equivalents per 1 kg of the polymer. When the content of the carboxyl group is less than 0.5 equivalent / kg, the degree of crosslinking of the film formed by heating before irradiation with active energy rays is not sufficient, and the solubility of the exposed portion in an alkaline developing solution is low and development is low. However, if it exceeds 10 equivalents / kg,
The storage stability of the composition tends to decrease.

The glass transition temperature (Tg) of the polymer (a) is preferably 0 ° C. or higher, particularly 5 to 70 ° C. If the Tg is less than 0 ° C., the coating film becomes tacky, and dust and dirt are likely to adhere to it, which tends to make it difficult to handle.

Hydroxyphenyl group-containing polymer (b) The polymer (b) is a polymer having at least one hydroxyphenyl group in one molecule, and is, for example, a monofunctional or polyfunctional phenol compound, an alkylphenol compound or Condensates of their mixtures with carbonyl compounds such as formaldehyde and acetone; homopolymers of vinyl aromatic compounds containing hydroxy groups such as p-hydroxystyrene; vinyl aromatic compounds containing hydroxyl groups and other copolymers. Examples thereof include copolymers with possible monomers.

Examples of the monofunctional or polyfunctional phenol compound include phenol, o-cresol, m
-Cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, 2,4-xylenol, catechol, resorcin, pyrogallol, bisphenol A, etc., a compound having 1 to 3 hydroxyl groups on the benzene ring Can be mentioned.

Examples of alkylphenol compounds include p-isopropylphenol and p-ter.
Examples thereof include alkylphenol compounds having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl moiety such as t-butylphenol, p-tert-amylphenol, and p-tert-octylphenol.

The condensation reaction of these compounds with a carbonyl compound such as formaldehyde or acetone can be carried out by a method known per se. Generally, when the condensation reaction is carried out with an alkali catalyst, it becomes insoluble and infusible as the condensation progresses. And a soluble and fusible novolak type is obtained by condensation with an acid catalyst.

The molecular weight of the novolac type phenol resin usually increases as the condensation proceeds, but the molecular weight obtained by condensing in the reaction time of 1 to 3 hours is 500 to
Those within the range of 2,000 are preferable.

As the other monomer copolymerizable with the hydroxy group-containing vinyl aromatic compound, the same other copolymerizable monomer as the above-mentioned other monomer copolymerizable with the carboxyl group-containing monomer can be used. Can be used.

Such hydroxyphenyl group-containing polymer (b) is generally about 500 to about 100,000, especially about 6
It is preferred to have a number average molecular weight within the range of 00 to about 30,000.

The content of the hydroxyphenyl group in the polymer (b) is generally 0.5 to 10 per 1 kg of the polymer.
It is convenient for it to be in the range of equivalents, especially 2.0 to 10.0 equivalents. If the hydroxyphenyl group content is less than 0.5 equivalent / kg, the degree of crosslinking of the film formed by heating before irradiation with active energy rays tends to be insufficient, and if it exceeds 10 equivalent / kg, the resist film is formed. Tend to be brittle.

The polymer (b) is also the same as the polymer (a).
Its glass transition temperature (Tg) is 0 ° C. or higher, especially 5 to 70.
It is preferably in the range of ° C. If the Tg is less than 0 ° C., the coating film becomes tacky, and dust and dirt are likely to adhere to it, which tends to make it difficult to handle.

Carboxyl group and hydroxyphenyl group
Content polymer (c) The polymer (c) is a film-forming polymer containing at least one carboxyl group and hydroxyphenyl group in one molecule, and for example, hydroxystyrene such as p-hydroxystyrene, Examples thereof include copolymers with a polymerizable unsaturated monomer containing a carboxyl group; hydroxystyrene and copolymers of the carboxyl group-containing monomer with another copolymerizable monomer.

Examples of the above-mentioned polymerizable unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid and the like. Examples of the other copolymerizable monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylate, nonyl (meth) C ₁ -C ₁₂ alkyl esters of (meth) acrylic acid such as decyl acrylate; (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxypropyl, (meth) acrylate, 3-hydroxypropyl, (meth) C ₂ -C ₆ hydroxyalkyl esters of (meth) acrylic acid such as hydroxyethyl acrylate-butyl; styrene, alpha-methyl styrene, p
Vinyl aromatic compounds such as -tert-butylstyrene;
Examples thereof include vinyl acetate, (meth) acrylonitrile, (meth) acrylamide, vinylpyrrolidone and the like. These monomers may be used alone or in combination of two or more kinds.

Further, as the polymer (c), phenolcarboxylic acids such as hydroxybenzoic acid, gallic acid and resorcinic acid, or phenols, mono- or di-alkylphenols having 1 to 18 carbon atoms or naphthols, resorcin, A polymer obtained by condensing a mixture of one or more phenols selected from catechol and the like with formaldehyde can also be used.

The polymer (c) is generally about 500 to about 1.
It is preferred to have a number average molecular weight in the range of 0,000, especially about 650 to about 30,000.

In the polymer (c), the content of carboxyl group in the polymer is generally 0.5 per 1 kg of the polymer.
In the range of 10 to 10 equivalents, especially 0.5 to 5.0 equivalents,
The hydroxyphenyl group of the polymer is preferably at least 1.0 equivalent, and particularly preferably 2.0 to 8.0 equivalents per kg of the polymer.

When the content of the carboxyl group of the polymer (c) is less than 0.5 equivalent / kg, the degree of crosslinking of the film formed by heating before actinic ray irradiation is not sufficient, and
The solubility of the exposed part in an alkaline developing solution is low and the developability tends to be low, while when it exceeds 10 equivalents / kg, the storage stability of the composition tends to be low, which is not preferable.

When the content of the hydroxyphenyl group of the polymer (c) is less than 0.2 equivalent / kg, the degree of crosslinking at the time of crosslinking becomes insufficient, while when it exceeds 20 equivalent / kg, unreacted substances increase. It is not preferable because the pattern resolution becomes poor.

The glass transition temperature (Tg) of the polymer (c) is preferably 0 ° C. or higher, particularly 5 to 70 ° C. If the Tg is less than 0 ° C., the coating film becomes tacky, and dust and dirt are likely to adhere to it, which tends to make it difficult to handle.

Photo-acid generator compound (C) The photo-acid generator compound (C) is decomposed by irradiation with the following active energy rays to produce a bond between the polymer (B) and the divinyl ether compound (A). It is a compound that generates an acid having a sufficient strength to cleave the formed crosslinked structure, and conventionally known compounds can be used.

Examples of compounds and mixtures which can be used as the photoacid generator compound (C) are diazonium, phosphonium, sulfonium and iodonium salts: halogen compounds: organometallic / organohalogen combinations: strong acids, for example benzoin of toluenesulfonic acid. And o-nitrobenzyl esters: and N-hydroxyamides and N-hydroxyimide sulfonates described in US Pat. No. 4,371,605. Also included are arylnaphthoquinonediazide-4-sulfonates. Suitable photosolubilizers are diaryliodonium or triarylsulfonium salts.

They are generally present in the form of salts of complex metal halide ions, such as tetrafluoroborate, hexafluoroantimonate, hexafluoroarsenate and hexafluorophosphate. Another useful group of photolabile acid generators includes oligomers and polymers to which anionic groups having an aromatic onium acid generator as the positive counterion are attached. Examples of the above polymers include US Pat.
1,429, column 9, lines 1-68 and column 10, lines 1-
Included are the polymers described in line 14. It is desirable to add a sensitizer to this system in order to adjust the spectral sensitivity to the available wavelengths of actinic radiation. This need depends on the requirements of the system and the particular photosensitive compound used. For example, in the case of iodonium and sulfonium salts that respond only to wavelengths below 300 nm, benzophenone and its derivatives, polycyclic aromatic hydrocarbons such as perylene, pyrene and anthracene, and their derivatives can be used to obtain longer Can be wavelength sensitive. Decomposition of diaryliodonium and triarylsulfonium salts is also
Bis- (p-N, N-dimethylaminobenzylidene)-
Photosensitivity can be provided with acetone. Sulfonium salts linked to anthracene having a chain length of 3 to 4 atoms are effective photosolubilizers. MG.Tilley PhD Thesis, North Dakota State University, Fargo, ND (1988)
[Diss.Abstr.lnt.B, 49, 8791 (1989): Chem. Abstr., 11
The compounds described in [1,39942u] are a suitable class of photosolubilizers. Other suitable acid generators are ATASS,
That is, 3- (9-anthracenyl) probiyldiphenylsulfonium hexafluoroantimonate. In this compound, the anthracene and sulfonium salt are linked by a chain of 3 carbons.

Photoacid generator compound (C) usable here
Additional examples of are diphenyliodonium tosylate, benzoin tosylate, and triarylsulfonium hexafluoroantimonate. In addition to the above, for example, iron-allene complexes, ruthenium allene complexes, silanol-metal chelate complexes, triazine compounds, diazidonaphthoquinone compounds, sulfonic acid esters, sulfonic acid imide esters, halogen-based compounds. Compounds and the like can be used. Further, JP-A-7-14
The acid generators described in Japanese Patent No. 6552 and Japanese Patent Application No. 9-289218 can also be used.

The photoresist composition of the present invention is used as an organic solvent-based or water-based type in which the above components are dispersed or dissolved in an organic solvent (if a pigment is used as a coloring agent, the pigment is further finely dispersed). can do.

The blending ratio of the photoresist composition can be varied over a wide range depending on the use of the composition, etc., but the divinyl ether compound (A) is added to 100 parts by weight of the polymer (B). On the other hand, it is preferably used in the range of about 5 to 150 parts by weight, particularly 10 to 100 parts by weight.
The photoacid generator compound (C) is about 0.1 to 40 parts by weight, particularly 0.2 to 20 parts by weight, based on 100 parts by weight of the total amount of the polymer (B) and the divinyl ether compound (A). It is suitable to use within the range.

A sensitizing dye may be added to the photoresist composition of the present invention if necessary. Examples of sensitizing dyes that can be used include phenothiazine-based, anthracene-based, coronene-based, benzanthracene-based, perylene-based,
Examples include dyes of pyrene type, merocyanine type, ketocoumarin type, and the like.

The blending amount of these sensitizing dyes is such that the polymer (B)
A suitable range is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, relative to 100 parts by weight.

A colorant may be added to the photoresist composition of the present invention if necessary, and as the colorant which can be used, for example, a combination of a leuco dye and a halogen compound is well known. Examples of the leuco dye include tris (4-dimethylaminophenyl) methane hydrochloride “leuco crystal violet” and bis (4-dimethylaminophenyl) methane hydrochloride “leucomalachite green”. On the other hand, as the halogen compound, amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzoyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p
-Chlorophenyl) ethane, hexachloroethane and the like. Coloring agents other than those shown here may be contained.

In the photoresist composition of the present invention, a plasticizer such as a phthalate ester, a polyester resin, an acrylic resin, etc. may be added in order to impart appropriate flexibility and non-adhesiveness to the resist film, if necessary. May be added. Usually, the addition amount thereof is preferably 50 parts by weight or less based on 100 parts by weight of the total amount of the divinyl ether compound (A) and the polymer (B).

If necessary, a fluidity regulator may be added to the photoresist composition of the present invention.

The photoresist composition of the present invention can be prepared by mixing the above-mentioned components as they are or in a solvent if necessary. The solvent that can be used in that case is not particularly limited as long as it can dissolve each component of the composition, and examples thereof include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; methyl acetate, ethyl acetate, acetic acid. Esters such as butyl; aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol; alcohols containing an aromatic group such as benzyl alcohol; glycols such as ethylene glycol and propylene glycol; these glycols and methanol , Glycol ethers such as mono- or diethers with ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, etc. or esters of the monoethers; cyclic ethers such as dioxane, tetrahydrofuran; Ji Ren carbonate, cyclic carbonates such as propylene carbonate, aliphatic and aromatic hydrocarbons, and the like. These solvents may be used alone or in combination of two or more, if necessary.

The photoresist composition of the present invention is coated with the composition directly on a substrate (for example, a printed circuit board) on which an image such as a resist pattern is formed, or on the surface of a polyethylene terephthalate film, followed by drying and baking. The photoresist dry film thus obtained can be applied to the same substrate as described above to form a photoresist film on the substrate.

As the above-mentioned coating method, for example, a roller, roll coater, spin coater, curtain roll coater, spray, electrostatic coating, dip coating, silk printing, spin coating or the like can be used for coating.
Further, the formed resist coating film is set according to need and then baked as necessary (about 50 to 130).
A resist film can be obtained by carrying out (° C.).

The photoresist coating is directly exposed to light so that a desired resist coating (image) can be obtained, and the coating on the exposed portion is developed with a conventionally known developing solution (alkali development, acid development, water development). Development, organic solvent development, etc.)
Can be removed.

The light source used for exposure is not particularly limited.
Without, for example, ultra high pressure, high pressure, medium pressure, low pressure mercury lamp,
Chemical lamp, carbon arc lamp, xenon lamp,
Talhalide lamp, Tungsten lamp, Argon laser
(488 nm), YAG-SHG laser (532n
m), oscillating line to UV laser (351 to 364 nm)
You can also use your own laser. The dose is usually 0.
5-2000 mJ / cm ², Preferably 1 to 1000 m
J / cm²The range of is preferable.

[0069]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, Examples, Comparative Examples and Test Examples. In each example, “%” and “part” are, as a general rule, on a weight basis.

Synthesis Example 1 (1) Commercially available reagent (manufactured by Tokyo Chemical Industry Co., Ltd.) 4,4′-hydrogenated biphenol (gas chromatography (hereinafter referred to as “G”
Abbreviated as “C”) is% cis, cis-form: 2.
3%; cis, trans-form: 11.5%; trans, trans-form: 86.2%) was recrystallized from methanol to give a melting point of 215 ° C. (trans, trans)-
1,1′-bicyclohexane-4,4′-diol was obtained (GC area% is cis, cis-form: 0.0%; cis, trans-form: 0.9%; trans, trans-form: 9
It was 9.1%).

(2) A 100 ml four-necked flask equipped with a stirrer, a thermometer, an acetylene gas inlet tube and a reflux condenser with a pressure equalizing tube was purified in the above (1) (trans, trans)-
1,1'-bicyclohexane-4,4'-diol 9.
92 g (50 mmol), potassium hydroxide 1.65 g
(25 mmol) and dimethyl sulfoxide (24 g) were charged, and nitrogen gas was introduced through the acetylene gas introduction tube at normal pressure to replace the inside of the system with nitrogen. After stirring and heating to 100 ° C. to dissolve the diol, acetylene gas is introduced at normal pressure, nitrogen gas is replaced with acetylene gas, the temperature is raised to 120 ° C., and acetylene gas atmosphere at normal pressure for 16 hours is maintained. The vinyl etherification reaction was carried out by keeping it underneath.
After confirming that the reaction was almost completed by GC (GC area% was raw diol body: 0.8%; monovinyl ether body: 8.5%; divinyl ether body: 87.7%), After cooling, the reaction solution was extracted 5 times with 50 ml of n-heptane. The extract was collected, concentrated under reduced pressure, and cooled to crystallize 10.25 g of a crude product (GC area%: raw material diol: 0.0%; monovinyl ether: 2.8).
%; Divinyl ether form: 93.8%) was obtained.

The above crude product was recrystallized from methanol,
5.75 g of colorless needle crystals having a GC area% of 99.8% or more and a melting point of 69 ° C. were obtained. The fact that this crystal is (trans, trans) -1,1'-bicyclohexane-4,4'-divinyl ether means that ¹ H- and ¹³ C-NMR analysis methods (solvent is heavy chloroform) and infrared spectroscopic analysis. Law (IR)
(KBr method). The IR spectrum is shown in Figure 1.
Its characteristic absorption value is shown in Table 1, ¹ H-NMR spectrum is shown in FIG. 2, its attribution is shown in Table 2, ¹³ C-spectrum is shown in FIG.
The attribution is shown in Table 3, respectively.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3] Synthesis Example 2 (1) 50.0 g of 4,4'-biphenol (manufactured by Honshu Chemical Industry Co., Ltd.), which is a commercial industrial chemical, was placed in a 1,000 ml autoclave and 500 ml of tetrahydrofuran, 5% Pd-C.
Charged with 2.5 g, hydrogen pressure 10 MPa, reaction temperature 2
Nuclear hydrogenation was carried out at 00 ° C. for 16 hours. The obtained reaction product was cooled, filtered, concentrated, and recrystallized from methanol to obtain 4,4′-hydrogenated biphenol having a melting point of 179 ° C. (GC area% is cis, cis-form: 8. 8%; cis, trans-form: 47.6%; trans, trans-form: 4
It was 3.7%).

(2) As the hydrogenated biphenol as the raw material, 4,4′-hydrogenated biphenol synthesized in the above (1) 9.9
A vinyl etherification reaction was carried out in the same manner as in Synthesis Example 1 (2) except that 2 g was used. After confirming that the reaction was almost completed by GC, the reaction solution was cooled and extracted with 50 ml of n-heptane three times. The extract was collected, concentrated under reduced pressure, and cooled to separate into two layers of a crystallizing portion and a liquid portion, and then filtered to obtain 3.06 g of a crystal component mainly composed of a trans-trans-form. 7.43 g of a liquid component that is a mixture of three isomers was obtained. The crystal component was recrystallized from methanol to obtain 1.13 g of colorless needle crystals having a GC area% of 99.8% or more and a melting point of 69 ° C. Since the IR spectrum and ¹ H- and ¹³ C-NMR spectrum of this crystal are the same as those of Synthesis Example 1, (trans, trans) -1,1′-bicyclohexane-4,
It was confirmed to be 4'-divinyl ether.

Synthetic Example 3 A vinyl etherification reaction was carried out in the same manner as in Synthetic Example 2 (2), and the concentrated liquid after extraction was purified by a silica gel column to obtain 7.64 g of an oily product (GC area% was the starting diol). Body: 0.0%; monovinyl ether body: 0.0%; divinyl ether body: 99.8%, and cis, cis-body: 4.7% of divinyl ether body; cis, trans-
Body: 45.3%; trans, trans-body: 49.8
%) Was obtained. The fact that this oily substance was 1,1′-bicyclohexane-4,4′-divinyl ether (mixture) means that ¹ H- and ¹³ C-NMR spectra (solvent is heavy chloroform) and IR spectra (Neat, NaCl plate). )
More identified.

Synthesis Example 4 Synthesis of Carboxyl Group-Containing Polymer (a) 7.8 parts of acrylic acid, 50 parts of methyl methacrylate, 12.2 parts of ethyl acrylate, 30 parts of phenoxyethylene glycol acrylate, tertiary butylper as a polymerization initiator Obtained by polymerizing a mixture consisting of 1 part oxy-2-ethylhexanoate. The obtained carboxyl group-containing polymer had a number average molecular weight of 4,500 and a carboxyl group content of 1 equivalent / kg.

Synthetic Example 5 Synthesis of hydroxyphenyl group-containing polymer (b) o-cresol 1,490 parts, 30% formalin 1,
145 parts, 130 parts of deionized water and 6.5 parts of oxalic acid were placed in a flask and refluxed for 60 minutes. Then add 15% hydrochloric acid to 1
After adding 3.5 parts and refluxing for 40 minutes, 400 parts of about 15 ° C
Deionized water was added to keep the contents at about 75 ° C to allow the resin to settle. Then, a 35% sodium hydroxide solution was added to neutralize, the aqueous layer was removed, and the same washing operation was repeated twice, followed by drying at about 120 ° C. under reduced pressure to obtain a novolac phenol resin. The resulting novolac phenol resin (hydroxyphenyl group-containing polymer) has a number average molecular weight of 6
00, hydroxyphenyl group content is 10 equivalents / kg
It was a polymer.

Synthesis Example 6 Synthesis of carboxyl group- and hydroxyphenyl group-containing polymer (c) 600 parts of o-hydroxybenzoic acid, 90 parts of o-cresol
0 parts, 30% formalin 1,145 parts, deionized water 1
30 parts and 6.5 parts of oxalic acid were placed in a flask and refluxed for 60 minutes. Then, 13.5 parts of 15% hydrochloric acid was added and refluxed for 40 minutes, then 400 parts of deionized water of about 15 ° C. was added to keep the content at about 50 ° C. to precipitate the resin. After further adding 400 parts of deionized water to wash the resin at 50 ° C., the water layer was removed, and the same washing operation was repeated 3 times, followed by drying under reduced pressure at about 120 ° C. to obtain a novolac phenol resin. It was
The resulting novolac phenol resin (polymer containing carboxyl group and hydroxyphenyl group) has a number average molecular weight of about 650 and a carboxyl group content of 2.8 mol / kg.
Polymer, hydroxyl phenyl group content is 5.4 mol /
It was a kg polymer.

Example 1 100 parts of the carboxyl group-containing polymer obtained in Synthesis Example 4, (trans, trans) -1,1 'synthesized in Synthesis Example 1
-Bicyclohexane-4,4'-divinyl ether 53
mmol / polymer 100 g, "UVAC1591" (manufactured by Daicel UCB Co., Ltd., trade name, photoacid generator compound, the same meaning below) 2 parts of a mixture was dissolved in cyclohexanone to prepare a 30 wt% solution. And Thus, the photoresist composition of the present invention was obtained.

Example 2 100 parts of the carboxyl group-containing polymer obtained in Synthesis Example 4 and (trans, trans) -1,1 'synthesized in Synthesis Example 2
-Bicyclohexane-4,4'-divinyl ether 53
A mixture of mmol / 100 g of polymer and 2 parts of "UVAC1591" was dissolved in cyclohexanone to obtain a 30 wt% solution. Thus, the photoresist composition of the present invention was obtained.

Example 3 Hydroxyphenyl group-containing polymer 100 obtained in Synthesis Example 5
Part, synthesized in Synthesis Example 1 (trans, trans)-
1,1'-bicyclohexane-4,4'-divinyl ether
Teru 53 mmol / 100 g of polymer, "UVAC159
A mixture of 1 part and 2 parts was dissolved in cyclohexanone to form a 30 wt% solution. Thus, the photoresist composition of the present invention was obtained.

Example 4 100 parts of the carboxyl group- and hydroxyphenyl group-containing polymer obtained in Synthesis Example 6, (trans, trans) -1,1'-bicyclohexane-4, synthesized in Synthesis Example 1
4'-divinyl ether 53 mmol / polymer 100
g, a mixture of 2 parts of "UVAC1591" was dissolved in cyclohexanone to obtain a 30 wt% solution. Thus, the photoresist composition of the present invention was obtained.

Comparative Example 1 100 parts of the carboxyl group-containing polymer obtained in Synthesis Example 3 and 1,1'-bicyclohexane-4,4'- obtained in Synthesis Example 3
Divinyl ether (mixture) 53 mmol / polymer 10
A mixture of 0 g and 2 parts of "UVAC1591" was dissolved in cyclohexanone to give a 30 wt% solution. Thus,
A photoresist composition for comparison was obtained.

Comparative Example 2 Hydroxyphenyl group-containing polymer 100 obtained in Synthesis Example 5
Part, 1,1′-bicyclohexane-4 obtained in Synthesis Example 3,
A mixture of 53 mmol of 4'-divinyl ether (mixture) / 100 g of the polymer and 2 parts of "UVAC1591" was dissolved in cyclohexanone to prepare a 30 wt% solution. Thus, a photoresist composition for comparison was obtained.

Comparative Example 3 100 parts of the carboxyl group- and hydroxyphenyl group-containing polymer obtained in Synthesis Example 6, 1,1'-bicyclohexane-4,4'-divinyl ether (mixture) obtained in Synthesis Example 3
53 mmol / 100 g of polymer, "UVAC1591"
30 parts by weight of a mixture of 2 parts dissolved in cyclohexanone
Solution. Thus, a photoresist composition for comparison was obtained.

Test Example 1 As described below, a resist film was formed using the photoresist composition of each Example and Comparative Example, and its performance was evaluated.

Each composition obtained in Examples 1 to 4 and Comparative Examples 1 to 3 was coated on a copper foil with a bar coater to a dry film thickness of 10 μm and dried at 100 ° C. for 10 minutes to obtain a carboxyl group or A hydroxyphenyl group and a vinyl ether group were subjected to an addition reaction to form a resist film.

Then, the substrate was irradiated with 365 nm ultraviolet light through a step tablet (21 step, manufactured by Hitachi Chemical Co., Ltd.), allowed to stand at room temperature for 10 minutes, and developed with a 0.75% sodium carbonate aqueous solution at 25 ° C. The sensitivity was measured.

Further, the photoresist was exposed to the optimum exposure dose of each of the photoresist compositions of Examples and Comparative Examples, and was left at room temperature for 10 minutes, then 25
The resist pattern was formed by developing using a 0.75% sodium carbonate aqueous solution at ℃. Table 4 shows the results of evaluating the photosensitivity, resolution, and pattern shape of each resist.

[0092]

[Table 4] In the evaluation of the pattern shape, “good” means that the edge portion of the pattern is clear, and “bad” means that the edge portion of the pattern is not clear.

[0093]

The novel compound of the present invention (trans,
Trans) -1,1'-bicyclohexane-4,4'-
The divinyl ether compound is a compound with low odor, low volatility, low irritation and low toxicity, high cationic polymerizability,
Compared to the conventionally known divinyl ether compound, which is a mixture of stereoisomers, it has characteristics such as excellent reactivity due to a single steric structure with high symmetry, and is a monomer group for photoresists, adhesives, paints, etc. It is also useful as an additive for agents and cross-linking agents.

[Brief description of drawings]

FIG. 1 shows an infrared spectrum of the compound of the present invention.

FIG. 2 is a chart showing ¹ H-NMR spectrum of the compound of the present invention.

FIG. 3 is a diagram showing a ¹³ C-NMR spectrum of the compound of the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Genji Imai             Seki, 4-17-1, Higashi-Hachiman, Hiratsuka City, Kanagawa Prefecture             West Paint Co., Ltd. (72) Inventor Takaaki Sone             1-9 Tsurumi, Tsurumi-ku, Osaka-shi, Osaka             Kawa Chemical Industry Co., Ltd. (72) Inventor Jiro Mizuya             1-9 Tsurumi, Tsurumi-ku, Osaka-shi, Osaka             Kawa Chemical Industry Co., Ltd. F-term (reference) 2H025 AA01 AD01 BC23 BC42                 4H006 AA01 AA02 AA03 AB92 AC43                       AD15 BA02 BA29 BB11 BB14                       BB22 GN22 GP02                 4H039 CA21 CA61 CF20

Claims (6)

[Claims] 1. A formula (1): A (trans, trans) -1,1′-bicyclohexane-4,4′-divinyl ether compound represented by: 2. Formula (2): The formula (1) is characterized in that (trans, trans) -1,1′-bicyclohexane-4,4′-diol represented by the formula (1) is reacted with acetylene in the presence of an alkali catalyst to form a vinyl ether. A method for producing a (trans, trans) -1,1′-bicyclohexane-4,4′-divinyl ether compound represented by: 3. The divinyl ether according to claim 2, wherein the (trans, trans) -1,1′-bicyclohexane-4,4′-diol represented by the formula (2) is a purified product by recrystallization. Method of manufacturing compound. 4. Stereoisomerism of (trans, trans) -1,1'-bicyclohexane-4,4'-diol represented by the formula (2), its cis, trans-form and its cis, cis-form. The body mixture is reacted with acetylene in the presence of an alkali catalyst to be vinyl etherified, and then recrystallized, which is represented by the formula (1) (trans, trans) -1,1'-bi. Process for producing cyclohexane-4,4'-divinyl ether compound. 5. A photoresist composition containing a (trans, trans) -1,1′-bicyclohexane-4,4′-divinyl ether compound represented by the formula (1). 6. (A) Formula (1) (transformer,
Trans) -1,1'-bicyclohexane-4,4'-
Divinyl ether compound, having 0.5 to 10 equivalents of carboxyl group per 1 kg of the polymer (B), and 3,0
Number average molecular weight in the range of 00 to 100,000 and 0 ° C
Polymer (a), Polymer 1 having the above glass transition temperature
Polymer (b) having 1 to 10 equivalents of hydroxyphenyl group per kg and having a number average molecular weight in the range of 500 to 100,000 and a glass transition temperature of 0 ° C or higher.
And a polymer having 0.2 to 20 equivalents of a hydroxyphenyl group and 0.5 to 10 equivalents of a carboxyl group per 1 kg of a polymer, and having a number average molecular weight in the range of 500 to 100,000 and a glass transition temperature of 0 ° C or higher. (C) having
6. The photoresist composition according to claim 5, which comprises at least one polymer selected from the following, and (C) a compound capable of generating an acid upon irradiation with active energy rays.