JPH05230140A - High molecular compound having phenolic hydroxyl group and its production - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as a material for forming patterns on substrates for the production of printed circuit boards, etc., by (co)polymerizing a 1-(3-chloro-4-hydroxybenzenesulfonyl)-6-methacryloyloxyalkane, etc. CONSTITUTION:A 1-(3-chloro-4-hydroxybenzenesulfonyl)-6-methacryloyloxyalkane alone or a mixture of the monomer with (meth)acrylic acid, methyl (meth) acrylate, etc., are (co)polymerized in the presence of dimethyl 2,2-azobis(2- methylpropionate) as a polymerization initiator in a solvent such as isopropyl acetate at a temperature of 80 deg.C with stirring under bubbling nitrogen gas to obtain the objective high-molecular compound having repeating units of formula I (X is H, halogen, alkyl, aryl, etc.; Y is SO2, O, CO, etc.; Z is O, NH; R1 is divalent group; R2 is H, alkyl) or formula II (P is the residual group of the copolymer component; l, m, n are the ratio of the copolymer; l+m+n=100; lnot equal to 0).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polymer compound having a phenolic hydroxyl group, which is useful as a material for forming a pattern on a substrate, and a method for producing the same.

[0002]

2. Description of the Related Art Image formation using a photosensitive resin composition is used in a wide variety of fields such as printed wiring boards, printing boards, IC circuits and color proofs. However, in any case, it is general to include a step of providing a photosensitive resin layer on the substrate, a step of pattern exposure, and a step of developing. Of these processes,
Typical developers used in the developing process are roughly classified into organic solvent type, alkaline aqueous solution or water type, and in recent years, from the viewpoint of working environment, air and water pollution, it is possible to develop with an alkaline aqueous solution or water The transition to resin compositions is progressing. The following are typical references relating to a photosensitive composition that can be developed with an aqueous alkaline solution. JP-B-35-14065 (binder is a polymer containing a side chain acid), JP-B-46-32714 (binder is, for example, methyl methacrylate / methacrylic acid copolymer), JP-B-54-34327. (The binder is, for example, a terpolymer of methyl methacrylate / -2-ethylhexyl methacrylate / methacrylic acid), Japanese Patent Publication No. 55-
38961 (the binder is, for example, a styrene / maleic acid mono-n-butyl ester copolymer), JP-B-56-
No. 33413 (the binder is, for example, a terpolymer of methyl methacrylate / ethyl acrylate / methacrylic acid), JP-B-55-38961 (the binder is, for example, styrene / methyl methacrylate / ethyl acrylate / methacrylic acid). Quaternary copolymer), JP-A-52-9981
No. 0 (the binder is, for example, benzyl methacrylate / methacrylic acid copolymer), JP-B-58-12577 (the binder is, for example, a terpolymer of acrylonitrile / -2-ethylhexyl methacrylate / methacrylic acid). ),
JP-B-55-6210 (The binder is, for example, a terpolymer of methyl methacrylate / ethyl acrylate / acrylic acid and styrene partially esterified with isopropanol /
There are two types of maleic anhydride copolymers), and JP-A-58-1142 (the binder is, for example, methyl methacrylate / methacrylic acid / 2-ethylhexyl acrylate terpolymer or methyl methacrylate / methacrylic acid). Acid / 2-ethylhexyl acrylate / n-butyl methacrylate quaternary copolymer, these alkali-soluble groups are carboxylic acids, while those having a phenolic hydroxyl group as an alkali-soluble group are polyvinyl. Known are phenol and its derivatives, phenol novolac type resins, cresol novolac resins, halogenated phenol novolac resins, etc. Further, as a polymer compound having a phenolic hydroxyl group, JP-A-63-63 is known. Electron-donating colorless dyes and electron-accepting properties shown in Nos. -115783 and 63-141785. Polymer type electron-accepting compound in recording materials using coloring with the compound are also known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer compound useful as a photosensitive resin composition which can be developed with an alkaline aqueous solution, and a method for producing the same.

[0004]

The present invention provides a polymer compound having a repeating unit represented by the following general formula (I), a general formula (I)

[0005]

[Chemical 3]

[In the formula, X represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group, and Y represents -SO _2- , -NHCO-, -O-, or -CO-.
And Z represents -O- or -NH-. R ₁ represents a divalent group and R ₂ represents a hydrogen atom or an alkyl group. ]

Further, the polymer compound represented by the general formula (I) is a copolymer containing a carboxylic acid represented by the following general formula (II), and a process for producing the same. General formula (II)

[0008]

[Chemical 4]

[In the formula, X, Y, Z, R ₁ and R ₂ are the same as those shown in the general formula (I). P is a residue derived from another copolymerizable component. l, m, and n represent copolymerization ratios, and l + m + n = 100, and l ≠ 0. ]

In the general formula (I), X is preferably a hydrogen atom, a halogen atom (particularly a chlorine atom is preferred) or an alkyl group. In Y, -NHCO- is preferably a bond from the -N side to the benzene ring. R ₁ is preferably an alkylene group having 2 to 20 carbon atoms, an alkoxy group, an aryloxy group,
Substituent such as halogen group and aryl group, or oxygen atom,
It may contain a sulfur atom or a phenylene group. Further, P in the general formula (II) is a residue derived from the general formula (I) and other copolymerizable components which are not the same as the carboxylic acid-containing residue.

The polymer compound of the present invention can be synthesized by various means such as radical polymerization, ionic polymerization, solution polymerization, emulsion polymerization, suspension polymerization and solventless polymerization. For example, radical polymerization can be initiated by a radical initiator. A persulfate-reducing agent, an oily or aqueous azo compound, a peroxide, a metal-based catalyst and the like can be used. The polymerization reaction is preferably carried out in an inert gas atmosphere, and when heated, it is preferably 120 ° C. or lower, particularly 90 ° C. or lower. When a solvent is used, a polar solvent such as water, ester, ether, halide, ketone, amide and alcohol, and a nonpolar solvent such as hydrocarbon and aromatics are used alone or in combination. be able to. Regarding the emulsification method, degassing method, reaction temperature control, metal catalyst handling method, post-treatment method after completion of the polymerization reaction, and purification method of the obtained polymer compound, etc. It is convenient to operate by referring to. For example, for general operating methods, see Sorensen, Polymer Synthesis Experimental Method (Tokyo Kagaku Dojin). The polymer compound of the present invention may be a homopolymer or a copolymer. The copolymerization reaction is a well-known method in the art, and for example, Polymer Ha
Details on ndbook, John Wiley, etc. Copolymerization is useful for controlling properties such as particle size, solubility, dispersibility, tackiness, and Tg. For example, the following can be used.

Carboxylic acids such as acrylic acid and methacrylic acid, acrylamide, methacrylamide, acrylanilide, diacetone acrylamide, acrylamide propane sulfonic acid soda, amides such as 1,6-bisacrylaminohexane, and (meth) acryl. Acid esters, for example, methacrylic acid methyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid-2-ethylhexyl ester, (meth) acrylic acid cyclohexyl ester, (meth) acrylic acid octadecyl ester, (meth) acrylic acid benzyl ester , (Meth) acrylic acid cellosolve ester, phenoxethyl (meth) acrylate, allyl (meth) acrylate, cinnamoyloxyethyl (meth) acrylate, diethylene glycol (meth) acrylate , Tri ethylene glycol - Ruechirue - ether (meth) acrylate - DOO, phenoxypropyl (meth) acrylate - DOO, phenyl (meth) acrylate -
, Vinyl styrene, vinyltoluene, divinylbenzene, vinylbenzenesulfonate, vinylphenol, vinylbenzoic acid, vinylpyrudine, vinylmethylpyridine, vinylmethyl-N-methylpyridinium bromide and other vinyl aromatics, or acrylonitrile, vinylacetate. , Vinylcarbazol, chloromethylvinylether, diallyl phthalate, vinyldioxolane, maleic anhydride, epichlorohydrin and the like. In the present invention, copolymerization with a carboxylic acid such as acrylic acid or methacrylic acid is preferable, and terpolymer or quaternary copolymer containing the above-mentioned other copolymerization monomers is also preferable. Furthermore, you may contain multiple types of general formula (I). In this case, the carboxylic acid part is preferably 5 parts by weight to 60 parts by weight, and particularly preferably 10 parts by weight to 50 parts by weight with respect to the total parts by weight. If it is less than 5 parts by weight, the photosensitivity and the image strength are low, and if it exceeds 60 parts by weight, the tackiness becomes a problem, which is not preferable. Further, in the case of copolymerization containing no carboxylic acid such as acrylic acid or methacrylic acid, the phenol in the present invention can be used.
30 parts by weight to 100 parts by weight, and particularly 40 parts by weight to 100 parts by weight are preferable. The molecular weight of these copolymers is preferably 5,000 to 1,000,000, more preferably 5,000 to 800,000. The polymer compounds relating to the present invention include the following.

1) 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane homopolymer, 2) 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane / Acrylic acid copolymer, 3) 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane / acrylic acid / methyl methacrylate copolymer, 4) 1- (3-chloro-4 -Hydroxybenzenesulfonyl) -6-methacryloyloxyhexane / methyl methacrylate copolymer, 5) 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane / acrylic acid / ethyl acrylate copolymer Polymer, 6) 1- (3-chloro-4-hydroxybenzenesulfon ) -8-methacryloyloxyoctane homopolymer, 7) 1- (3-chloro-4-hydroxybenzenesulfonyl) -8-methacryloyloxyoctane / methacrylic acid copolymer, 8) 1- (3-chloro-4 -Hydroxybenzenesulfonyl) -8-methacryloyloxyoctane / acrylic acid copolymer, 9) 1- (3-chloro-4-hydroxybenzenesulfonyl) -8-methacryloyloxyoctane / 2-ethylhexyl methacrylate copolymer , 10) 1- (3-chloro-4-hydroxybenzenesulfonyl) -8-acryloyloxyoctane / methacrylic acid / phenoxyethyl methacrylate copolymer, 11) 1- (3-chloro-4-hydroxybenzenesulfonyl) ) -3-methacryloyloxypropane homopolymer, 1 2) 1- (3-chloro-4-hydroxybenzenesulfonyl) -3-methacryloyloxypropane / methacrylic acid / methyl methacrylate copolymer, 13) 1- (4-hydroxybenzenesulfonyl) -6
-Methacryloyloxyhexane homopolymer, 14) 1- (4-hydroxybenzenesulfonyl) -6
-Methacryloyloxyhexane / butoxyethyl acrylate / acrylic acid copolymer, 15) 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane / 1-
(3-chloro-4-hydroxybenzenesulfonyl)-
8-methacryloyloxyoctane / methacrylic acid copolymer, 16) 4- (6-methacryloyloxyhexyl) oxyphenol homopolymer, 17) 4- (6-methacryloyloxyhexyl) oxyphenol / acrylic acid / butyl Methacrylate copolymer, 18) 4- (3-acryloyloxypropyl) oxyphenol homopolymer, 19) 4- (3-acryloyloxypropyl) oxyphenol / 2-ethylhexyl acrylate copolymer Combined, 20) 4- (3-methacryloyloxypropyl) oxyphenol homopolymer, 21) 4- (3-methacryloyloxypropyl) oxyphenol / acrylic acid copolymer, 22) 1- (3-chloro- 4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane / 4 −
(3-methacryloyloxypropyl) oxypheno-
23 / 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacrylamide hexane / acrylic acid / methyl methacrylate copolymer, 24) 1- (3-chloro -4-Hydroxybenzenesulfonyl) -6-acrylamide hexane / methyl methacrylate copolymer, and the like.

[0014]

EXAMPLES Examples will be shown below, but the present invention is not limited thereto. In the examples, unless otherwise specified, weight% is indicated. Example 1 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane 100 g
Place in a three-necked L flask and add isopropyl acetate 3
00 ml was added. This three-necked flask is set outside 80 ℃
In an oil bath and stirred under nitrogen bubbling, and dimethyl 2,2-azobis (2-methylpropione-
G) 1 g of a solution of 10 g of acetic acid isopropyl ester was added and stirred for 1 hour, and a solution of 1 g of dimethyl 2,2-azobis (2-methylpropionate) dissolved in 10 ml of acetic acid isopropyl ester was added and stirred for 1 hour. After that, set the temperature to 100 ° C and continue stirring for 2 hours.
-(3-chloro-4-hydroxybenzenesulfonyl)
A homopolymer of -6-methacryloyloxyhexane was obtained. The molecular weight of this polymer is (Pst (polystyrene)
MW = 53,000 (in terms of conversion).

Example 2 30 g of 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane
The mixture was placed in a 0 ml three-necked flask and 90 ml of isopropyl acetate was added. This three-necked flask is set outside 80
The mixture was placed in an oil bath at ℃ and stirred under nitrogen bubbling, and a solution prepared by dissolving 0.3 g of 2,2′-azobis (2,4-dimethylvaleronitrile) in 2 ml of isopropyl acetate was added as an initiator and stirred for 1 hour. 2 g of 2,2'-azobis (2,4-dimethylvaleronitrile)
After adding 1 liter of a solution of acetic acid isopropyl ester and stirring for 1 hour, the external temperature was set to 100 ° C. and stirring was continued for 2 hours to obtain 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane alone. Got united. The molecular weight of this polymer (in Pst conversion)
MW = 23,000.

Example 3 27 g of 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane and 3 g of methyl methacrylate were placed in a 500 ml three-necked flask and 90 ml of isopropyl acetate was added. This three-necked flask was placed in an oil bath set at an external temperature of 80 ° C., stirred under nitrogen bubbling, and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) 0.3 g was used as an initiator.
The solution dissolved in acetic acid isopropyl ester of was added and stirred for 1 hour, and a solution of 0.3 g of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 2 ml of acetic acid isopropyl ester was added and stirred for 1 hour. After that, the temperature was set to 100 ° C outside and stirring was continued for 2 hours.
4-Hydroxybenzenesulfonyl) -6-methacryloyloxyhexane / methyl methacrylate copolymer was obtained. The molecular weight of this polymer is MW (in Pst conversion).
= 125,000.

Example 4 60 g of 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane, 20 g of acrylic acid and 20 g of methyl methacrylate were added to 500 m.
1 L of tetrahydrofuran was added to a 3-necked flask. This three-necked flask was placed in an oil bath with an external setting of 80 ° C., stirred under nitrogen bubbling, and a solution prepared by dissolving 1 g of dimethyl 2,2-azobis (2-methylpropionate) as an initiator in 10 ml of tetrahydrofuran was placed for 1 hour. After stirring and further adding a solution of 1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 10 ml of tetrahydrofuran and stirring for 1 hour, the external setting 100
Stirring was continued at 2 ° C for 2 hours to obtain 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane / methacrylic acid / methyl methacrylate copolymer. The molecular weight of this polymer was MW = 75,600 (in terms of Pst).

Example 5 500 ml of 60 g of 1- (3-chloro-4-hydroxybenzenesulfonyl) -8-methacryloyloxyoctane, 20 g of acrylic acid and 20 g of butyl acrylate.
1 L of tetrahydrofuran was added to the three-necked flask. This three-necked flask was placed in an oil bath with an external setting of 80 ° C., stirred under nitrogen bubbling, and a solution prepared by dissolving 1 g of dimethyl 2,2-azobis (2-methylpropionate) as an initiator in 10 ml of tetrahydrofuran was placed for 1 hour. After stirring and further adding a solution of 1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 10 ml of tetrahydrofuran and stirring for 1 hour, the external setting 100
Stirring was continued for 2 hours at ℃ to obtain 1- (3-chloro-4-hydroxybenzenesulfonyl) -8-methacryloyloxyoctane / acrylic acid / butyl acrylate copolymer. The molecular weight of this polymer (in Pst conversion)
The MW was 112,000.

Example 6 30 g of 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane and 1-
(3-chloro-4-hydroxybenzenesulfonyl)-
20 g of 8-methacryloyloxyoctane and 20 g of acrylic acid were placed in a 500 ml three-necked flask, and 1 L of tetrahydrofuran was added. This three-necked flask is set outside 8
The mixture was placed in an oil bath at 0 ° C. and stirred under nitrogen bubbling. A solution of 1 g of dimethyl 2,2-azobis (2-methylpropionate) as an initiator in 10 ml of tetrahydrofuran was added and the mixture was stirred for 1 hour. A solution prepared by dissolving 1 g of 2'-azobis (2,4-dimethylvaleronitrile) in 10 ml of tetrahydrofuran was added, and the mixture was stirred for 1 hour.
(3-chloro-4-hydroxybenzenesulfonyl)-
6-methacryloyloxyhexane / 1- (3-chloro-4-hydroxybenzenesulfonyl) -8-methacryloyloxyoctane / acrylic acid copolymer was obtained. The molecular weight of this polymer is MW = 15 (in terms of Pst).
It was 4,000.

Example 7 40 of 1- (3-chloro-4-hydroxybenzenesulfonyl) -6-methacryloyloxyhexane / methacrylic acid / methyl methacrylate copolymer obtained in Example 4
1% by weight solution (solvent is propylene glycol monomethyl ether and residual solvent tetrahydrofuran) 1965 parts, dipentaerythritol hexaacrylate 314 parts, benzyl dimethyl ketal 30 parts, Megafask F-17
7P 7.56 parts, hydroquinone monomethyl ether 1
5 kinds of the above mixture were prepared, coated on 100 μm polyethylene terephthalate using a bar coater, dried, and then superposed on a photomask and exposed with a 2 Kw ultra-high pressure mercury lamp from a distance of 50 cm. After that, 0.1% N
When developed with an aOH aqueous solution at 30 ° C. for 1 minute and 30 seconds,
An image faithful to the photo mask was obtained.

[0021]

INDUSTRIAL APPLICABILITY The polymer compound having a phenolic hydroxyl group according to the present invention is useful as a raw material for an image forming material which can be developed with an aqueous alkaline solution.

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Claims (3)

[Claims] 1. A polymer compound having a phenolic hydroxyl group, which has a repeating unit represented by the following general formula (I). General formula (I): [In the formula, X represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and Y represents -SO _2- ,
-NHCO-, -O-, or -CO-, and Z is -O.
Represents-, or -NH-. R ₁ is a divalent group, R ₂
Represents a hydrogen atom or an alkyl group. ] 2. The phenol according to claim 2, wherein the polymer compound represented by the general formula (I) is a copolymer containing a carboxylic acid represented by the following general formula (II). Polymer compound having a reactive hydroxyl group. General formula (II): [In the formula, X, Y, Z, R ₁ and R ₂ are the same as those in the general formula (I). P is a residue derived from another copolymerizable component. l, m, n are copolymerization ratios, and l + m +
When n = 100, l ≠ 0. ] 3. A method for producing a polymer compound having a phenolic hydroxyl group represented by the general formula (II) according to claim 2.