JPS5953835A - Water-soluble photohardenable resin composition - Google Patents

Abstract

PURPOSE:To obtain a water-developable photohardenable resin, by using a polymer contg. at least one kind or >=2 kinds of specified unsatd. monomer as repeating units. CONSTITUTION:Maleic or citraconic anhydride of the like represented by genneral formula III is added to a polymer of at least one kind or >=2 kinds of unsatd. monomer, such as diethylene glycol aryl ether represented by general formula II, hydroxyethyl acrylate, di(ethylene glycol) maleate, or di(ethylene glycol) itaconate, or a copolymer of said monomer and a copolymerizable ethylenically unsatd. monomer. Further, alkali metal hydroxide, ammonium, or one of various amines are added to incorporate in the structural components at least one kind or >=2 kinds of unsatd. monomers represented by general formula I in the form of an alkali metal, ammonium, or amine salt as repeating units.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble photocurable resin composition that can be polymerized and cured by actinic light such as ultraviolet light or visible light, and can be developed with water.

Water-soluble polymers, such as natural polymers such as ovalbumin, casein, glue, gelatin, gum arabic, and 7-acrylic, polyvinyl alcohol, poly7-acrylamide,
Photosensitive materials made by mixing polymeric acid salts into an aqueous solution of synthetic polymers such as poly-N-vinyl bifritone are used in the production of printing plates as photoresists used in the photoetching process, as well as in printed heddle boards and color televisions. It is widely used in the field of making shadow masks, fluorescent surfaces for cathode ray tubes, and precision processing of their strips, but these products cannot be stored for long periods of time because they tend to cause dark reactions, and they do not contain dichromates. Because of the use of chromium, it has the disadvantage of requiring pollution treatment for hexavalent chromium in wastewater.

On the other hand, photoresists made by adding cinnamic acid to polyvinyl alcohol or those made by adding an azide compound to cyclized rubber are photoresists with excellent storage stability, but they require the use of large amounts of organic solvents for dissolution and development. 1 has some disadvantages that must be addressed.

Therefore, there has been a strong demand in the art for a photosensitive material that does not have these drawbacks, that is, a water bath photoresist F that does not use dichromate.

For this reason, the inventor of the tree made 9+5:Q: As a result of his research, he found that it does not use nail chromate, has no dark reaction, has excellent long-term durability, and can be made with ordinary water! 1, 1 (gpi1) 5Y-curable FF14 fat composition was invented.

That is, the present invention uses a photocurable polymer containing one or more unsaturated monomers represented by the general formula (1) as a constituent component in the polymer as an active ingredient. The present invention provides a water-soluble photocurable resin composition.

Polymerization of one or more monomeric monomers represented by the formula ([l)] or an ethylenic monomer copolymerizable with the unsaturated monomer represented by the general formula ([l)] Unsaturated IItλ
The following general formula (IN) is added to the polymer obtained by copolymerization with
Obtained by forming an alkali metal salt using an alkali metal hydroxide such as thorium or potassium hydroxide or an alkali metal alkoxide compound such as sodium methoxide, or by forming an ammonium salt or amine salt using ammonia or various amines. be able to. Here, the amines include aliphatic primary amines, aliphatic! Almost all of them can be used, such as 82 amines, aliphatic tertiary amines, alkanolamines, aromatic primary amines, aromatic secondary amines, aromatic tertiary amines, and alicyclic amines.

In the present invention, unsaturated monomers represented by the general formula (where A part of Ill is a 7lyloxy group and its lower alkyl, aryl or) rogene substituted product include diethylene glycol allyl ether, triethylene glycol allyl ether, propylene There are glycol allyl ether, propylene-diethylene glycol allyl ether, tetraethylene glycol allyl ether, diethylene glycol crotyl ether, hexaethylene glycol allyl ether, nonaethylene glycol allyl ether, pentadecaethylene glycol allyl ether, etc. A of the general formula (■) Unsaturated monomers in which the moiety is 1 chloroyloxy group and its lower alkyl, aryl or Hagen equivalents include hydroxyethyl acrylate, diethylene glycol acrylate, two-traethylene glycol acrylate, f
Caethylene glycol acrylate, hexadecaethylene glycol acrylate-11 tetracontaethylene glycol 7 acrylate, hydro-1-cyethyl methacrylate, diethylene glycol methacrylate, triethylene glycol methacrylate, tetraethylene glycol methacrylate, hexaethylene glycol methacrylate, nonaethylene glycol methacrylate, Pentadecaethylene glycol methacrylate, tricosaethylene glycol methacrylate, diethylene glycol cinnamate, etc., where part A of the general formula (■) is a maleoyloxy group or a fumaroyloxy group and their lower alkyl, aryl, or hapogen substituted product. The unsaturated basis weight is di(ethylene glycol).
Malate, di(triethylene glycol) malate, di(tetraethylene glycol) malate, di(hexaethylene glycol) malate, di(nonaethylene glycol) malate, di(pentadecaethylene glycol)
There are malate, di(tricosaethylene glycol) malate, fumarate corresponding to the above, and the general formula (I
Examples of unsaturated monomers in which part A of I) is an itaconoyloxy group or an isomer thereof include di(ethylene glycol) itaconate, di(diethylene glycol) itaconate, di(tetraethylene glycol) itaconate, and di(decaethylene glycol) itaconate. Glycol) Itaconate must be it.

In addition, as ethylenically unsaturated monomers (hereinafter referred to as ethylenically unsaturated monomers) that can be co-fabricated with the general formula (Ill), 2 esters,
Methacrylic acid ester, crotonic acid ester, maleic acid ester, Nisder fumarate, Nistil itaconate,
Examples include acryl 7mide, acrylonitrile, ethylene, vinyl chloride, vinyl acetate, vinylidene chloride, methyl vinyl ether, methyl vinyl ketone, styrene, and vinyl toluene.

Furthermore, examples of the acid anhydride represented by the general formula (IN) include maleic anhydride and citraconic anhydride.

The chemical and physical properties of the photocurable nail base used in the present invention are as follows.
It mainly depends on the type and copolymerization ratio of the ethylenically unsaturated monophosphor. Therefore, by appropriately selecting the unsaturated monomer and the ethylenically unsaturated monomer represented by the -JQ formula (TI) and appropriately changing the copolymerization ratio, chemical and physical properties can be varied. It is possible to obtain a photocurable polymer having the following properties.

Polymerization or copolymerization methods for the unsaturated mono-Ij heptad represented by the general formula (IIJ) include polymerization methods such as solution, emulsification, suspension, and bulk polymerization in the presence of a radical polymerization catalyst, as well as ionic nail platform, etc. Almost all methods are applicable.

The average molecular weight (M Sakaki average) of the polymer is determined by water solubility and curing ratio;
It is related to the strong D of
The range is from o' to 100,000.

In order to add (=J) anhydride (hereinafter referred to as acid anhydride) represented by the general formula value) to the polymer obtained in this way, the obtained m polymer must already be 6 If it is a liquid, use it as is, or if it is a simple polymer, use an appropriate solvent such as pyridine, dimethylform, dimethyl sulfoxide, hexamethylposphoramide, benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl. Dissolve in ketone, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, etc. to make a 1'+'i' L solution, and then add acid anhydride to 1 mole of hydroxyl groups in the polymer at 05%
It is sufficient to add the compound in an amount of up to 2 moles and heat the reaction. For this ll'j, a conventional esterification catalyst may be used if necessary.

By adding an aqueous or alcoholic solution of an alkali metal hydroxide, ammonia, or various amines to the polymer solution in which the acid anhydride has been separated in this way to form a salt, a water-soluble photocurable polymer can be produced. is l'J.

In addition, by adding the above-mentioned acid anhydride to the monotetrahydric monomer represented by the general formula (phantom) in advance, and then polymerizing or copolymerizing this to form an alkali metal salt or ammonium salt. A water-soluble photocurable polymer can also be obtained.

In the present invention, this photocurable polymer is used as it is if it is in solution, or if it is isolated, it is dissolved in water, a weak alkaline aqueous solution, etc. ).

Examples of photosensitizers include common benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dibutyl sulfide, benzyl sulfide, thiuram disulfide, anthraquinone, anthraquinone-β-
Sodium sulfonate, 5-2) p-acenaphthene, thioxanthone, and further organic peroxides are used. The proportion of the photosensitizer used is preferably 0.1 to 30% of the total amount of the photosensitive solution. Further, as the photocrosslinking agent, water-soluble azide compounds such as diazonium salts, acrylates, acrylamide carbon 1, etc. can be used.

The light solution of the present invention is used as described below and has a length of 4 degrees.

First, this photosensitive liquid is applied onto a metal plate or other type plate and dried (IY) to form a photosensitive film. This photosensitive film is
By exposing the photosensitive film to ultraviolet light or visible light through a predetermined pattern, the exposed portion of the photoresist film is polymerized and crosslinked and cured.

Since the unexposed area is water-soluble, the unexposed area can be created by washing with water after exposure. Light sources include low pressure, high pressure,
Ultra-high pressure mercury lamps, metal halide lamps, xenon lamps,
Chemical lamps and various laser lamps are required once a month. This cured film has good acid resistance and forms a strong resist layer, so it is suitable for making printing plates and printed wiring boards, and can also be used for various fine cutting processes.

Next, the present invention will be explained in detail using an actual example.

The present invention is not limited to the following authorities. In addition, the middle part of the example shows the hoe (Tt part), the part shows the tsume huchi part, and the molecular weight shows the average molecular fbe.

The real power side! (Pour 780 parts of Geogiza into a flask equipped with fE stirrer, raise the temperature to 100C while blowing nitrogen, and add triethylene glycol methacrine to 4fJ while stirring.) 30
．． 6ms styrene 10.8 parts, ethyl methacrylate 7.
2 parts, notyl acrylate 1.41i5 tertiary butyl peroxy (2-ethylhex"j-/ate) 0.
A mixed solution of 7 parts of dioxane and 50 parts of dioxane was added dropwise over 2 hours.

After the completion of the dropwise addition, the reaction was continued for 2 hours at the same temperature Iy, and then cooled butyl peroxy(2-ethylhexanony)
) and 710 parts of dioxa were added thereto, and the mixture was further stirred at the same temperature for 2 hours.

Next? , Blow H1 [Hime, maleic anhydride 9]
A solution prepared by dissolving 8 parts of dioxane in 10 parts of dioxane was added thereto, and the reaction was carried out at the same temperature for 6 hours, then the temperature was lowered to room temperature and 20
20 parts of an aqueous sodium dihydroxide solution was added dropwise over 30 minutes to obtain a precipitate of a water-soluble photocurable polymer. The molecular weight of the polymer was 32,000.

Dissolve 10 parts of the precipitate after separation and drying in 90 parts of water, add 02 parts of sodium anthraquinone-β-sulfonate,
It was made into a photosensitive liquid. Next, this photosensitive solution was applied onto a grained aluminum plate using a spinner, dried, and exposed for 7 seconds using a 400V/high-pressure mercury lamp through a 1o5+ pattern. Noji f'i 11 ga 1 work ``1st edition IK company υ's nephew times hard 1 shiba 壓 and put it on the aluminum plate qri p+'f11+7
The resist pattern is 1-10 J1.

Male phase 1 row 2 Stirring 4;, nonaethyleneglyfur methacrylate V-) in a flask with island 38.64"157.1-1/7
2 parts of El, 32 parts of methoxy hexaedylene glycol methacrylate, 177,200 parts of oxy, and 08 parts of azobisisobutyronitrile were added (5 It at 9op while blowing in 7 elements).The reaction was continued by stirring. After that, 110C and shoulder table 171! Start blowing N, add molten anhydrous maleic (H + 27.8 parts), and
The reaction was carried out for 6 hours, and after completion of 1 or 1, the mixture was poured into a 10 times warmer oil needle and the polymer was precipitated. After filtering and drying this, it was dissolved in methanol and 20q6
Add 16 parts of sodium hydroxide/aqueous solution dropwise over 20 minutes, and water-soluble light 1+1! ! 1')
Ta. The molecule 1λ of the aggregate was 3700 (in I).

10 parts of the sediment after drying was dissolved in 90 parts of water,
A good resist pattern similar to that of Example 1 was obtained by applying it onto a plate using a spinner, exposing it to light for 1 minute through the pattern using Chemika and Relamp, and washing with water.

Example 3 100 parts of dimethylformamide was placed in a flask equipped with a stirrer, and the temperature was raised to 1ooC while blowing in 9 parts, and while stirring, 256 parts of decaethylene glycol acrylate was added.
A mixture of 138 parts of tetraethylene glycol methacrylate, 5.2 parts of methyl methacrylate, 54 parts of acrylamide, and 0.5 parts of penzoyl peroxide was added dropwise over an hour or so, and the reaction was carried out at the same temperature for 5 hours. After the polymerization reaction was completed, nitrogen blowing was stopped, 11.2 parts of molten citraconic anhydride was added, and the reaction was carried out at the same temperature for 6 hours, then the temperature was lowered to room temperature, and 28 parts of a 20% potassium hydroxide aqueous solution was added in the shade for 15 minutes. was added dropwise to obtain a precipitate of a water-soluble photocurable polymer. The molecular weight of the polymer was 28,000.

Sedimentation after separation and drying t9. A photosensitive solution was prepared from the product in the same manner as in Example 1, and exposure and development were performed in the same manner as in Example 111 (1:1), and a good resist pattern was obtained.

Example 4 Di(triethylene glycol) in a flask with stirring tower
12 parts of malate, 7 parts of di(hexaethylene glycol) malate, 6 parts of vinegar l'it<vinyl, 14 parts of styrene,
Add 05 parts of tertiary butyl peroxydipenzoate and 150 parts of butyl acetate, and heat to 90C while blowing nitrogen.
After the polymerization reaction was carried out for 6 hours, the aggregate was precipitated by pressurizing it into normal hexane; 1. generated. After drying (d-1), 20 parts of the polymer was dissolved in 770 parts of dioxa, and a solution of 4.2 parts of maleic anhydride dissolved in 5 parts of dioxane was added, followed by reaction at 95C for 4 hours. After the reaction, the polymer solution No. 11 was poured into petroleum ether to precipitate it, and then filtered and dried. Further, 15 parts of this aggregate was dissolved in 40 parts of methanol, and 3 parts of a 30% sodium hydroxide aqueous solution was added dropwise over 10 minutes to obtain a precipitate fqt of a water-soluble photocurable polymer. The molecular weight of the polymer is 3
It was 0000.

The precipitate after separation and drying was made into a photosensitive solution by the same method as in Example 2, and then exposed and imaged in the same manner as in Example 2, and a good resist pattern was obtained.

Example 5 In a flask equipped with a stirrer, 15 parts of di(tetraethylene glycol) itaconate, 12 parts of hexaethylene glycol allyl ether, 10 parts of styrene, 7 parts of dimethyl phthalate, 3 parts of ethyl methacrylate, and tert-butyl peroxy(2-ethyl hexanoate) 0.8 parts, dimethylpolamide 120
The temperature was raised to 1,000 ℃ while blowing nitrogen,
After carrying out the polymerization reaction for 5 hours, nitrogen blowing was stopped, 7.2 parts of molten maleic anhydride was added, and the reaction was carried out at the same temperature for 4 hours, then the polymer was pressurized into a large amount of n-hexane. A precipitate was formed. After drying, 20 parts of the polymer was dissolved in 50 parts of methanol, and 6 parts of aqueous sodium 20 thihydroxide was added dropwise for 15 minutes or once, to obtain a water-soluble photocurable polymer, T42. . η+=ii4o of the polymer.

It was 00.

The precipitate after drying was heated as in Example 1.
A photosensitive solution was prepared by the process, and when exposure and Sj imaging were performed in the same manner as in Example 1, a good resist pattern 1') was obtained.

74A 'IAfil 6 In a flask equipped with a stirrer, add 35 parts of hexaethyleneglyfur methacrylate, 10 parts of styrene, and 5 parts of acrylamide.
part, abbisisobutyronitrile 06 parts, dioxane 1 part
00 parts was charged, the temperature was raised to 100 C while blowing nitrogen, and polymerization reaction 111 was carried out at the same temperature for 6 hours. Thereafter, the nitrogen blowing was stopped, and 98 parts of dissolved maninic anhydride was added, and the reaction was carried out at the same temperature for 5 hours. This polymer solution was cooled to room temperature, and at the same temperature, solution 11k, which was prepared by dissolving 61 parts of ethanolamine in 200 parts of water, was added dropwise over 30 minutes, and the reaction was further carried out for 1 hour (・Water-soluble light (i'r
! A solution of polymer (molecular weight: 42,000) is ().

1. Expose 80 parts of water to 15 parts of this water-bathable photocurable polymer solution in the same manner as in AND1. When IJ imaging was performed, a good resist pattern was obtained.

Example 7

Claims (1)

[Claims] A water-soluble photocurable resin composition comprising, as an active ingredient, a photocurable polymer containing one or more unsaturated monomers represented by the formula (A) 2 or more as the fj1 component in the polymer.