JP2003286216A - Hydrogenated bisphenol a-4,4'-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)-hydrogenated bisphenol A-4,4'-bivinyl ether compound which has a single structure and is low in odor, low evaporable, low irritative, low toxic, and highly cation-polymerizable. <P>SOLUTION: This (trans, trans)-hydrogenated bisphenol A-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 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.
It is an object to provide a (trans, trans) -hydrogenated bisphenol A-4,4′-divinyl ether compound having a single structure.

[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) -4,4'-hydrogenated bisphenol A is converted into a divinyl ether to obtain a single stereoisomer (trans, trans)-.
A hydrogenated bisphenol A-4,4′-divinyl ether compound is obtained, the above-mentioned object can be achieved, and the above-mentioned hydrogenated bisphenol A which is a trans or trans-form which is purified by recrystallization is divinyl etherified. The inventors have found that the target compound is preferably obtained and completed the present invention.

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

1. Formula (1):

[0009]

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

2. Formula (2)

[0011]

[Chemical 4] (Trans, trans) -4,4′-hydrogenated bisphenol A is reacted with acetylene in the presence of an alkali catalyst to form a vinyl ether, which is represented by the formula (1) (trans. , Trans) -hydrogenated bisphenol A-4,4'-divinyl ether compound.

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

4. 4. The method for producing a divinyl ether compound according to the above item 2 or 3, which is subjected to a crystallization step after being vinyl etherified.

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

6. (A) (trans, trans) -4,4'-hydrogenated bisphenol A- represented by the formula (1)
4,4'-divinyl ether compound, (B) polymer 1k
A polymer (a) having 0.5 to 10 equivalents of a carboxyl group per g 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,
Polymer (b) having 1 to 10 equivalents of hydroxyphenyl group per 1 kg of 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, and 0 per kg of polymer. A polymer having a hydroxyphenyl group of 2 to 20 equivalents and a carboxyl group of 0.5 to 10 equivalents, 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 6. The photoresist composition as described in the above item 5, which comprises at least one polymer selected from the group (1) and (C) a compound capable of generating an acid upon irradiation with active energy rays.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Inventive Compound (trans, trans) -hydrogenated bisphenol A-4,4'-divinyl ether compound (trans, trans) -4,4'-hydrogen which is a raw material of the compound As the hydrogenated bisphenol A, 4,4′-hydrogenated bisphenol A commercially available as an industrial raw material can be used.

Commercially available 4,4'-hydrogenated bisphenol A
Is usually trans, trans-form, cis, trans-
And a cis-cis-cis mixture of three stereoisomers. The mixture is purified to give trans, trans-
By using after separating the body, after the divinyl etherification, the target compound (trans, trans) -hydrogenated bisphenol A-4,4′-divinyl ether of the formula (1) is not particularly purified. The compound can be conveniently obtained. Here, as a method for purifying a trans or trans-isomer from the above stereoisomer mixture,
There is no particular limitation as long as the cis, trans-form and the 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 solvent used for recrystallization was 0.
It is 5 to 10 parts by weight, and more preferably 1 to 5 parts by weight in consideration of the improvement in purity and the recovery rate.

The compound of the present invention has the formula (2) (trans,
Trans) -4,4′-hydrogenated bisphenol A can be obtained by introducing acetylene gas in a solvent in the presence of an alkali catalyst to cause 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'-
From the viewpoint of reaction rate, it is preferable that the amount of hydrogenated bisphenol A is 0.1 to 1.0 mol per 1.0 mol.

As the solvent, (trans, trans)-
It can be used without particular limitation as long as it dissolves 4,4′-hydrogenated bisphenol A. 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 bisphenol A.

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 after the steps of concentrating and distilling, followed by washing with water or extraction to remove the alkali content and the high boiling point solvent. The crude product can be purified by an appropriate combination of separation and purification methods such as distillation under reduced pressure, recrystallization and chromatography to obtain a compound of the present invention which is almost pure.

By using the crystallization method as a method for separating and purifying the crude product, the purity of stereoisomers can be further improved. The solvent used for crystallization is not particularly limited as long as it can dissolve the crude product, but a saturated hydrocarbon compound is preferable. As the saturated hydrocarbon compound, known compounds can be used, but n-pentane, n-hexane, n
-Chain hydrocarbons such as heptane and isohexane, and cyclic hydrocarbons such as cyclohexane and cyclopentane. Among these, chain hydrocarbons are preferably used because the purity can be improved.
The amount of the solvent used for crystallization is 0.5 to 10 parts by weight with respect to 1 part by weight of the crude product, and it is more preferable to set the amount to 1 to 5 parts by weight in consideration of improvement in purity and recovery rate. preferable.

The method for producing the compound of the present invention is not limited to the above-mentioned acetylene method, and for example, an exchange reaction with an alkyl vinyl ether using a complex catalyst such as palladium (JP-A-9-87224), or It can also be produced by an exchange reaction with vinyl acetate (JP 2001-220364 A).

The compound of the present invention, (trans, trans) -hydrogenated bisphenol A-4,4'-of the formula (1)
The divinyl ether compound is a single stereoisomer,
It is liquid at room temperature and has a melting point of 17 ° C. Further, FIG. 1 shows the infrared spectrum of the compound of the present invention, FIG. 2 shows the ¹ H-NMR spectrum, and FIG. 3 shows the ¹³ C-NMR spectrum. 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)
(Trans, trans) -hydrogenated bisphenol A-4,4'-divinyl ether compound represented by

The composition of the present invention is preferably (A) a (trans, trans) -hydrogenated bisphenol A-4,4'-divinyl ether compound represented by the formula (1),
(B) Polymer having 0.5 to 10 equivalents of carboxyl group per 1 kg of polymer, 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 groups per 1 kg of polymer, and 500 to 100,000
Polymer (b) having a number average molecular weight in the range of 0 and a glass transition temperature of 0 ° C. or higher and 0.2 per 1 kg of the polymer.
Having from 20 to 20 equivalents of hydroxyphenyl groups and from 0.5 to 10 equivalents of carboxyl groups, and from 500 to 100,00
At least one polymer selected from the polymers (c) having a number average molecular weight in the range of 0 and a glass transition temperature of 0 ° C. or higher, and (C) a compound that generates an acid upon irradiation with active energy rays (hereinafter, This may be abbreviated as "photoacid generator compound (C)").

[0028] 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) 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 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 polymer (a) preferably has a glass transition temperature (Tg) of 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 and 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 the alkylphenol compound 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 copolymerizable other monomer as the above-mentioned 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 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 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 in the polymer (c) is less than 0.2 equivalent / kg, the degree of crosslinking during 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 used as photoacid generator compounds (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 or the like may be added to the resist film 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 modifier 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 applied directly to a substrate (for example, a printed circuit board) on which an image such as a resist pattern is formed, or the polyethylene terephthalate film surface is coated with the composition, 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.
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.

[0066]

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 industrial chemical (manufactured by Shin Nippon Rika Co., Ltd.) 4,4'-
Hydrogenated bisphenol A (area% by gas chromatography (hereinafter abbreviated as "GC") is cis, cis-
Body: 7.1%; cis, trans-body: 38.4%; trans, trans-body: 50.3%), and recrystallized from methanol to give a melting point of 194 ° C. (trans, trans)-
4,4'-hydrogenated bisphenol A was obtained (GC area%
And trans-trans-forms were 99.9% or more; both cis-cis-forms and cis-trans-forms were 0.0%).

(2) A 100 ml four-necked flask equipped with a stirrer, a thermometer, an acetylene gas introduction tube and a reflux condenser with a pressure equalizing tube was purified in the above (1) (trans, trans)-
4,4'-hydrogenated bisphenol A 12.0 g (50 mmol), potassium hydroxide 1.65 g (25 mmol)
And 25 g of dimethyl sulfoxide were charged, and nitrogen gas was introduced at normal pressure from an acetylene gas introduction pipe 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 at the same temperature for 16 hours under acetylene gas atmosphere at normal pressure. Then, the vinyl etherification reaction was carried out. After confirming that the reaction was almost complete by GC (GC area% was starting material diol body: 0.0%; monovinyl ether body: 7.1%; divinyl ether body: 91.2%), The reaction solution was extracted twice with 50 ml of n-heptane. The extracts were collected and concentrated under reduced pressure to obtain 12.46 g of an oily crude product (GC area%: raw material diol body: 0.0%; monovinyl ether body: 3.
5%; divinyl ether form: 93.0%) was obtained.

The oily crude product was dissolved in n-heptane, cooled to -30 ° C. and crystallized to have a GC area% of 99.6%.
4.38 g of colorless crystals having a melting point of 17 ° C. were obtained. This crystal is (trans, trans) -hydrogenated bisphenol A
It was identified to be -4,4'-divinyl ether by ¹ H- and ¹³ C-NMR analysis methods (solvent is deuterated chloroform) and infrared spectroscopy (IR) (Neat, NaCl plate). The IR spectrum is shown in FIG.
In the ¹ H- spectrum in FIG. 2, the attribution in Table 2, ¹³
The C spectrum is shown in FIG. 3 and the attribution is shown in Table 3, respectively.

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

[Table 3] Synthesis Example 2 In a 100 ml four-necked flask equipped with a stirrer, a thermometer, an acetylene gas introduction tube, and a reflux condenser with a pressure equalizing tube, a commercially available industrial chemical (manufactured by Shin Nippon Rika Co., Ltd.) 4,4′-hydrogenated bisphenol A was used. (Area% by cis in cis, cis-form: 7.
1%; cis, trans-form: 38.4%; trans, trans-form: 50.3%) 12.0 g (50 mmol), potassium hydroxide 1.65 g (25 mmol) and dimethyl sulfoxide 25 g were charged. Then, nitrogen gas was introduced through the acetylene gas introduction pipe 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 at the same temperature for 16 hours under acetylene gas atmosphere at normal pressure. Then, the vinyl etherification reaction was carried out.

After confirming disappearance of the raw material diol by GC, the reaction solution was cooled and extracted with 50 ml of n-heptane three times.
The extracts were collected and concentrated under reduced pressure to obtain 13.20 g of oily crude product.
Got This oily substance was purified with a silica gel column,
4.96 g of purified oil (GC area%: raw material diol body: 0.0%; monovinyl ether body: 0.0%; divinyl ether body: 98.4%). Body: 1.5%; cis, trans-
Body: 39.4%; trans, trans-body: 57.5
%) Was obtained. This oil is hydrogenated bisphenol A-
That it is 4,4'-divinyl ether (mixture),
¹ H- and ¹³ C-NMR analysis methods (solvent is deuterated chloroform) and infrared spectroscopy (IR) (Neat, NaCl)
Plate).

Synthetic Example 3 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.

Synthesis Example 4 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 5 Synthesis of Polymer (c) Containing Carboxyl Group and Hydroxyphenyl Group 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 3 and 53 mmol / (trans, trans) -hydrogenated bisphenol A-4,4'-divinyl ether obtained in Synthesis Example 1
A mixture of 100 g of the polymer and 2 parts of "UVAC1591" (manufactured by Daicel UCB Co., Ltd., trade name, photoacid generator compound, having the same meaning below) was dissolved in cyclohexanone to prepare a 30% by weight solution. . Thus, the photoresist composition of the present invention was obtained.

Example 2 Hydroxyphenyl group-containing polymer 100 obtained in Synthesis Example 4
Part, (trans, trans) -hydrogenated bisphenol A-4,4′-divinyl ether 53 mm obtained in Synthesis Example 1
A mixture of 100 g of ol / polymer and 2 parts of "UVAC1591" was dissolved in cyclohexanone to prepare a 30 wt% solution. Thus, the photoresist composition of the present invention was obtained.

Example 3 100 parts of the carboxyl group- and hydroxyphenyl group-containing polymer obtained in Synthesis Example 5, (trans, trans) -hydrogenated bisphenol A-4,4'-divinyl ether 53 mmol / obtained in Synthesis Example 1 Polymer 100g, "UVAC
1591 "dissolved in 2 parts of cyclohexanone,
A 30% by weight solution was prepared. 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 53 mmol of hydrogenated bisphenol A-4,4'-divinyl ether (mixture) obtained in Synthesis Example 2 / polymer 100
g, a mixture of 2 parts of "UVAC1591" was dissolved in cyclohexanone to obtain a 30 wt% solution. Thus, a photoresist composition for comparison was obtained.

Comparative Example 2 Hydroxyphenyl group-containing polymer 100 obtained in Synthesis Example 4
Part, hydrogenated bisphenol A-4,4 ′ obtained in Synthesis Example 2
-Divinyl ether (mixture) 53 mmol / polymer 1
A mixture of 00 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 3 100 parts of the carboxyl group- and hydroxyphenyl group-containing polymer obtained in Synthesis Example 5 and hydrogenated bisphenol A-4,4'-divinyl ether (mixture) 53 obtained in Synthesis Example 2
A mixture of mmol / 100 g of polymer and 2 parts of "UVAC1591" was dissolved in cyclohexanone to obtain a 30 wt% solution. Thus, a photoresist composition for comparison was obtained.

Test Example 1 As described below, a resist film was formed using the photoresist compositions of Examples and Comparative Examples, and the performance thereof was evaluated.

Each of the compositions obtained in Examples 1 to 3 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.

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

After exposure to the optimum exposure dose of each photoresist composition of Examples and Comparative Examples and leaving it at room temperature for 10 minutes, 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.

[0087]

[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.

[0088]

The novel compound of the present invention (trans,
The trans) -hydrogenated bisphenol A-4,4'-divinyl ether compound is a compound having low odor, low volatility, low irritation and low toxicity, high cationic polymerizability and a mixture of stereoisomers. It has characteristics such as excellent reactivity due to a single steric structure with high symmetry compared to known divinyl ether compounds, and is an additive such as a monomer base for photoresists, adhesives, paints, crosslinking agents, etc. It is also useful as

[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) 4H006 AA01 AA02 AB46 AC43 AD15                       BA02 BA29 BA32 BD60 GN22                       GP02                 4H039 CA61 CD10 CF20

Claims (6)

[Claims] 1. Formula (1): A (trans, trans) -hydrogenated bisphenol A-4,4′-divinyl ether compound represented by: 2. Formula (2): (Trans, trans) -4,4′-hydrogenated bisphenol A is reacted with acetylene in the presence of an alkali catalyst to form a vinyl ether, which is represented by formula (1) (trans , Trans) -hydrogenated bisphenol A-4,4'-divinyl ether compound. 3. The method for producing a divinyl ether compound according to claim 2, wherein the (trans, trans) -4,4′-hydrogenated bisphenol A represented by the formula (2) is a purified product by recrystallization. 4. The method for producing a divinyl ether compound according to claim 2 or 3, which comprises a crystallization step after the vinyl etherification. 5. A photoresist composition containing a (trans, trans) -hydrogenated bisphenol A-4,4′-divinyl ether compound represented by the formula (1). 6. (A) Formula (1) (transformer,
Trans) -4,4'-hydrogenated bisphenol A-4,
4'-divinyl ether compound, (B) polymer having 0.5 to 10 equivalents of carboxyl group per kg, and having a number average molecular weight in the range of 3,000 to 100,000 and a glass transition of 0 ° C or higher. Polymer (a) having a temperature, a polymer having 1 to 10 equivalents of a hydroxyphenyl 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. (B) and a polymer having 0.2 to 20 equivalents of hydroxyphenyl groups and 0.5 to 10 equivalents of carboxyl groups 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 glass transition temperature, and (C) a compound capable of generating an acid upon irradiation with active energy rays. The photoresist composition of claim 5 that.