JPS5917548A - Image forming composition - Google Patents

Abstract

PURPOSE:To enhance air-drying properties and alkali solubility, by using an unsatd. polyester resin contg. an adduct of ethylenically unsatd. carboxylic acid and a specified chain diene type compd. CONSTITUTION:The present image forming compsn. consists of a photopolymerizable unsatd. monomer and a photopolymn. initiator; and an unsatd. polyester resin contg. as a constituent, an adduct of a polybasic acid, such as maleic anhydride or fumaric acid, a polyole, such as ethylene glycol or glycerin, an ethylenically unsatd. carboxylic acid, and a chain diene type compd. represented by the general formula: X-(CH=CH)2-Y where X, Y are each carboxy, sulfo, alkyl, aryl, or cycloalkyl. As the adduct, that of maleic anhydride with sorbic acid is the most useful. A printed circuit superior in adhesion is obtained by using this compsn. and forming an image on the copper foil of a print board.

Description

[Detailed description of the invention] Misfire F! A relates to a photocurable image-forming composition useful for purposes such as printed wiring, planographic printing, letterpress printing, and offset printing.

Conventionally, many compositions have been known for such uses, and a typical composition is a combination of a polymer compound and a photopolymerizable monomer.

(7) However, the common problem in both cases is that the polymerization of the photopolymerizable monomer is inhibited by the presence of air, especially oxygen (therefore, the polymerization rate is low and the hardness of the cured film is not sufficient). This is something that can easily happen.

Such curing inhibition may occur, for example, during the production of a photoresist plate, when the l/cyst image is attacked by an etching agent during etching of the substrate, making it difficult to form a precise image, or during the production of a photorelief plate, the image area may be damaged. This poses problems such as being easily worn out and making it impossible to print clearly, so this must be solved before it can be put into practical use.

Yet another problem is that it takes a long time to clean and remove the photocured image area, so it is necessary to shorten this time in order to improve the plate-making efficiency.

However, as a result of extensive research, the present inventors found that (Al polybasic acid, polyhydric alcohol, and ethylenically unsaturated carboxylic acid and the general formula [X←CH=CH can Y (similar to X.

yH Carboxyl group, sulfonic acid group, alkyl group, aryl group, cycloalkane group]] Unsaturated polyester resin whose constituent component is an adduct with a chain diene compound, (B) photopolymerizable Unsaturated monomer, (C
(1) The image-forming composition comprising a photopolymerization initiator has good air-drying properties, and photocuring proceeds easily even in the presence of oxygen to provide an image with sufficient hardness; After discovering new facts such as that when it is necessary to wash or remove the face part, it can be easily dissolved in an extremely short time by washing the face part with an alkaline aqueous solution, and that the plate-making efficiency can be significantly improved. He was able to complete 8A.

As described above, the present invention is characterized in that an unsaturated polynisder resin containing an adduct of an ethylenically unsaturated carboxylic acid and the chain diene compound is used, and in particular, an ethylenically unsaturated dicarboxylic acid and a carboxyl group-containing When an adduct with a diene compound is used, its effect is significantly exhibited.

When using the above adduct, air drying properties and alkali solubility are greatly improved due to the presence of free carboxyl groups and cycloalkene rings formed by Diels-Alder reaction in the unsaturated polyester resin. be. Even if, for example, a large amount of polybasic acid is introduced to increase the amount of free carboxyl groups introduced, although alkaline solubility is imparted, air drying properties are reduced and images with sufficient hardness cannot be obtained.

Further, when only a cycloalkene ring is introduced, although air drying properties are exhibited, alkali solubility is not sufficient.

Examples of polybasic acids which are components of the unsaturated polyester resin of the present invention include maleic anhydride, )-q-lic acid, itaconic acid,
Examples include tetrahydrophthalic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, cepatic acid, and trimellitic acid. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, glycerin, diglinaline, 1.5-7' ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, and pentyl glycol. These include erythritol.

Further, carboxylic acids in the adduct of ethylenically unsaturated carboxylic acid and chain diene thread compound include maleic anhydride, maleic acid, fumaric acid, 〇-carboxycinnamic acid, itaconic acid, glutaconic acid, citraconic acid, Examples include dicarboxylic acids such as tetrahydrophthalic acid (anhydride), 6-methyltetrahydrophthalic acid (anhydride), tetrahydroterephthalic acid, benzalactic acid, benzalmalonic acid, citraconic acid (anhydride), and monocarboxylic acids such as crotonic acid. Ru. On the other hand, as the chain diene compound, butadiene and the like can be used, but dienes containing a carboxyl group in the molecule are useful. Sorbic acid, cinnamylideneacetic acid, β
-2-furyl acrylic acid, dicyclopentadienecarboxylic acid, abietic acid, levopimaric acid, 5,5-jethoxy-1,6-dihydrophthalic anhydride, 4,5-jethoxy-1,2-dihydrophthalic anhydride, 9. I+-octadecadienoic acid, 9, I+, 13-octadecadienoic acid,
α-eleostearic acid, β-eleostearic acid, α
Typical examples include -lycanic acid and β-lycanic acid.

Among the above, adducts of ethylenically unsaturated dicarboxylic acids and carboxyl group-containing diene compounds are preferably used, particularly Diels-Alder reaction adducts of maleic anhydride and sorbic acid, i.e., 6-methylcyclohexane-1,
2,5) dicarboxylic acids are the most useful.

The above adducts are present in the unsaturated polyester resin with 2.5 to 5
Preferably, it is present in a proportion of 0 mol%.

The adduct may be present either at the end of the molecule or in the molecular chain.

By further introducing a polyhydric alcohol allyl ether component into the unsaturated polyester resin of the present invention, a higher degree of air-drying property can be exhibited, so its use is advantageous. Allyl ethers of polyhydric alcohols, such as glycerin,
Mono- or diallyl ethers such as trimethylolpropane and trimethylolethane, mono-, di- or triallyl ethers of pentaerythritol, allylglycidyl ether, allyloxydicyclopentadiene, partially allyl etherified products of phenol-formaldehyde initial condensates, etc. In addition to the above, oils such as tung oil, linseed oil, dehydrated castor oil, soybean oil, etc. are also used as modifiers when preparing unsaturated polyester resins. fatty acids or polyhydric alcohol fatty acid esters are used as appropriate.

Unsaturated polyester resins are prepared by any method.

For example, by condensing a polybasic acid, a polyhydric alcohol, an ethylenically unsaturated carboxylic acid, and, if necessary, a modifier, according to a conventional method, a chain is formed on the double bond of the ethylenically unsaturated carboxylic acid in the obtained prepolymer. A method of causing a Diels-Alder reaction of a diene compound, in which an ethylenically unsaturated carboxylic acid and a chain diene compound are reacted in advance to prepare an adduct, and this is reacted with a polybasic acid, a polyhydric alcohol, and if necessary a denaturing agent. Methods such as condensing are carried out.

The resulting unsaturated polyester resin is a viscous liquid or solid. The molecular weight of the resin is not particularly limited, but it usually has an average molecular weight of 500 to 5000 and an acid value (KOH, q/da) of 5.
0 to 400, preferably 100 to 500, is suitably used. If the acid value is less than 5D, it is difficult to obtain sufficient alkaline cleaning properties, while if it is more than 400, it is likely to be affected by chemicals in the etching liquid phase, making it impossible to obtain a clear image or causing noticeable stickiness in the image area.

Next, the photopolymerizable unsaturated monomer used in the present invention is not particularly limited, and any compound capable of radical polymerization can be used. A preferred monomer is an ethylenically unsaturated monomer (vinyl monomer) and a compound containing a functional group such as a hydroxyl group or a carboxyl group. Examples of functional groups include epoxy groups in addition to those mentioned above. Of course, ethylenically unsaturated monomers that do not contain functional groups can also be used, and these can be used to impart elasticity to the image forming film or to adjust the hardness (7. For this purpose, it is used as an auxiliary agent in combination with ethylenically unsaturated monomers containing functional groups.

The compounds will be specifically explained below, but the present invention is not limited thereto.

Monomers containing hydroxyl groups include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,4-butylene glycol monoacrylate, pentaerythritol mono-, di-, or triacrylate;
Examples include ethylene glycol monoacrylate, diethylene glycol monoacrylate, propylene glycol monoacrylate, dipropylene glycol monoacrylate, mono- or diacrylate of glycerin, N-methylol acrylamide, and N-methylol methacrylamide.

In addition, as a monomer containing a carboxyl group, (meth)acryloyl group-containing polybasic acid ester represented by
C=an integer of 2 to 4, R' represents an alkylene group, a phenylene group, a phenylene group replaced with a carboxyl group, etc. ). The ester is obtained by a partial esterification reaction between hydroxy (meth)acrylate and a polybasic acid.

The compound includes mono(2-acryloxyethyl) phthalate.
Ester succinic acid mono(2-acryloxyethyl) ester 0
0 111 (CH2=CH-C-0-CH2-CH, O-C-CH
2-CH2-COOH: ), mono(2-acryloxyethyl) maleate, mono(5-acryloxyethyl) hexahydrophthalate, mono(2-acryloxyethyl) tetrahydrophthalate
Ester trimellitic acid mono(2-acryloxyethyl) ester methyltetrahydrotrimellitic acid mono(2-acryloxyethyl) ester pyromellitic acid mono(2-acryloxyethyl) ester and the above acryloyl group replaced with a methacryloyl group Examples include various esters.

Other usable monomers include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 1-vinyl-5,4-epoxycyclohexayu,
, trimethylolpropane triacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexene glycol diacrylate,
Examples include N-vinylpyrrolidone, styrene, methyl methacrylate, tetrahydrofuran acrylate, butoxy acrylate, cyclohexyl acrylate, phenoxyethyl acrylate, and inbonnel acrylate.

In the present invention, it is advantageous to use various monomers such as those described in 1177 in combination, especially (meth)acryloxy group-containing polybasic acid partial esters, and phosphoric acid monomers as described below. That is, when the composition of the present invention is used as a resist ink for printed wiring, the combination of monomers allows the ink to exhibit good adhesion to substrates such as copper plates, and the alkaline cleaning after image formation is much shorter. This is because it is done effectively and on time.

Mixing ratio of phosphoric acid monomer and the polymerizable monomer: 5/1
oo~50/+00 is preferable.

Specific examples include phosphoric acid monomers.

The (meth)acryloxy group-containing phosphate ester shown (
where R; hydrogen or methyl group; A; alkylene group or hydroxyl-substituted alkylene group; a; an integer of 1 to 3; b;
(an integer of 1 to 2).

The ester is obtained by reacting a hydroxyalkyl (meth)acrylate with phosphoryl chloride, phosphorus pentoxide, orthophosphoric acid, or the like. The compounds include mono(2-acryloxyethyl) phosphate ester di(2-acryloxyethyl) phosphate ester mono(2-methacryloxyethyl) phosphate ester.

Other examples include phosphoric acid tri(2-acrylonitrile) ester and phosphoric acid tri(2-methacryloxyethyl) ester.

As a photopolymerization initiator, C is a benzoin alkyl ether such as benzoin methyl needle, benzoin ethyl ether, and penzoin isoglobyl ether, an organic iodine compound such as digityl sulfide, benzyl sulfide, and decylphenyl sulfide, diazonicum salt, and tetrazonicum salt. Or a complex salt of these and zinc chloride or its 11#
4 compounds, azobisisobutyronitrile, dyes such as methylene blue, or combinations thereof with p-toluenesulfonate ions, organic peroxides, hydrogen peroxide, virilicum salts or thiapyrylium salts, acetophenone, benzophenone, benzyl, phenanthrene , thioxanthone,
Dichloropropylphenyl ketone, acitraquinone, 2
-chloroanthraquinone, 2-bromoanthraquinone,
Anthraquinone β-sulfonate, 1,5-dinitroanthraquinone, 1,2-benzonthraquinone, phenanthrenginone, 5-benzoylacenaphthene, 5-
Nitroacenaphthene, 1,4-naphthoquinone, 1,8-
Examples include phthaloylnaphthalene, 2-nitrofluorene, p-nitroaniline, and biclamide, and these may be used alone or in combination of two or more.

It is not limited to those listed above, and any substance that promotes photopolymerization can be used. Among these, benzoin alkyl ether gives particularly good results in terms of price and sensitivity.

In the composition of the present invention, the photopolymerizable but unsaturated monomer is used in a proportion of 20 to 500% by weight based on the unsaturated polyester resin.

In addition, the photopolymerization initiator Iri is 1 to 10% by weight based on the resin.
Mixed use within the range.

Since the photopolymerizable unsaturated monomer also serves as a solvent, the composition can be applied to the substrate as it is, but if necessary, organic solvents such as volatile saturated fatty acid esters, ketones, aromatic hydrocarbons, etc. For example, ethyl acetate, methyl ethyl! Reketone,
It can also be used after being diluted with toluene or Ikexylene 7.

Further, auxiliary agents such as dyes, pigments, and thermal polymerization inhibitors can be used in combination as required. ``When forming an image using the composition, a zinc plate,
When the composition is applied to a base material such as an aluminum plate, copper plate, or steel plate, and UV rays are irradiated through the negative, only the exposed areas will be cured, so the unexposed areas can be washed away with alkaline to form an image, or screen printing is performed. After an image is formed on a substrate by a method, the image can be cured by irradiating it with ultraviolet rays.

The former is suitable for producing resist plates and relief plates, and the latter is suitable for purposes such as printed wiring.

For resist plates, printed wiring, etc., the base material obtained as described above is etched, the exposed metal parts are corroded, and the remaining photosensitive parts are cleaned with alkali and removed. Only the first one is used in the offset version. In alkaline cleaning, an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate is usually used as an aqueous solution of about 0.1 to 5%. Any method such as a spray method or a dipping method can be used for the cleaning operation.

The alkali contact time is 5 seconds to 20 seconds, and the temperature at the time of contact is 2
A temperature of about 5 to 50°C is practical.

In addition, the base material is not limited to the above-mentioned metal plate, but also cotton, rayon, wool, polyester, boria 3F, etc.
Images can be formed on the surface of woven or non-woven fabrics made from synthetic fibers such as polyvinyl alcohol and polyacrylonitrile through a screen, then cured by irradiation with ultraviolet rays, and dyed as appropriate to create patterns on the fabric. It is possible.

In addition, paper, synthetic resin sheets, etc. may be used as the base material.

Light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps,
Carbon arc lamps, xenon lamps, etc. are used.

Hereinafter, the composition of non-explosion No. 1 will be explained in more detail by giving an example.

Example 1 9739 parts of phthalic anhydride, 9.8 parts of isophthalic acid 11], 172.9 parts of maleic anhydride, 9 parts of ethylene glycol
9.6 parts of propylene glycol and 122.1 parts of propylene glycol were condensed in a nitrogen atmosphere at 220°C for 4 hours to obtain an acid value of 4.
A prepolymer of 8 (KOHwlit) was obtained.

Next, this prepolymer was cooled to 100°C, 97.7 parts of sorbic acid was added, and the reaction was carried out at 150°C for 1.5 hours to prepare a liquid unsaturated polyester resin with an acid value of 166 [KOIIwvg]. 100 parts of this resin. , 50 parts of 2-hydroxypropyl acrylate, 15 parts of di(2-acryloxyethyl) phosphate, 40 parts of barium sulfate, 6 parts of Aerosil, 0.5 part of phthalocyanine blue, and Irgacure 651.
(Manufactured by Ciba Geigy, acetophenone-directed photopolymerization initiator)
Mix 2 parts and mix thoroughly with a Miki roll to reach a viscosity of +550.
An image forming composition of 0CI' (measured using a B-type viscometer, t5 Q rpm, and 20°C) was obtained.

Next, using this composition, an image was formed on a copper foil of a printed circuit board by a screen printing method, and immediately 80 W/c1n
Irradiation was performed for 1 second using a UV lamp with an output of .

The hardness of the image coating film was a pencil hardness of 2H, and the adhesion to the substrate was 1°0/1oo, indicating good adhesion.

Next, this sample was etched with an aqueous ferric chloride solution at 40° C. for 50 minutes. The image showed sufficient chemical resistance. Furthermore, when a 6% sodium hydroxide aqueous solution at 40 DEG C. was sprayed, the image area dissolved after 8 seconds.1-7Excellent alkaline cleaning properties were obtained, and2 a precise printed wiring circuit image was obtained.

Comparative Example 1 The same experiment as in Example 1 was conducted except that unsaturated polyester was used, omitting the use of turvicic acid.

The hardness of the image coating film was F.

Also, some difficulties were observed in chemical resistance.

Control Example The same experiment as in Example 1 was conducted except that an unsaturated polyester resin was used, omitting the use of maleic anhydride. Alkaline cleaning required a long time of 40 seconds.

Examples 2 to 7 Images were formed according to Example 1 using the compositions shown in Table 1 (only the unsaturated polyester resin polymerizable monomer was changed). The results are shown in Table 1.

No. 1 Representing a Detective★ Italian Patent Applicant Nippon Gosei Kagaku Kogyo Co., Ltd. Procedural Amendment (Self-control, Incident Display Composition 3, Relationship with the case of the person making the amendment Patent applicant address: No. 6 @ 9 Nozaki-cho, Kita-ku, Osaka 4, subject of amendment 5, content of amendment 1, page 7, line 18 of the specification , for example, change ``10.'' to ``
For example, 10. ” he corrected.

2.Page 8, line 6 “-Thylated substances are also 01.”
-Tylated products are mentioned. In addition, 1. ] Correct.

3. On page 8, line 10, insert ``1'' next to ``stell''.

4, page 14, line 7 "+1; 1-2 11."[b; 1-3 01.] I am corrected.

5, page 17, line 17, 110. suitable for the purpose of ”
After that, insert "It can also be used to fill holes in through-hole type printed wiring boards."

that's all 2- 271

Claims (1)

[Claims] +, (A) polybasic acid, polyhydric alcohol, and ethylenically unsaturated carboxylic acid with the general formula [: X('-CH=CH
-)2Y (similar to X, Y represents carboxyl group, sulfonic acid group, alkyl group, aryl group, cycloalkane group)
] An image-forming composition comprising an unsaturated polyester resin containing an adduct with a chain diene compound represented by (131), a photopolymerizable unsaturated monomer, and (C) a photopolymerization initiator. 2. The image-forming composition according to claim 1, wherein the adduct of an ethylenically unsaturated carboxylic acid and a diene compound is a cycloalkene containing at least two carboxyl groups in the molecule. 3. Claim No. 3, wherein the adduct of an ethylenically unsaturated carboxylic acid and a diene compound is 6-methylcyclohexane-1,2,5 tricarboxylic acid obtained by an addition reaction between maleic anhydride and sorbic acid. The image forming composition according to item 2. 4. (A) a polybasic acid, a polyhydric alcohol, an ethylenically unsaturated carboxylic acid and the general formula (X(-CH=CH
(Similar An image forming composition comprising: (B) a photopolymerizable unsaturated monomer; and (C1 photopolymerization initiator).