JPS58153930A - Composition for forming pattern hardenable by ultraviolet rays irradiation - Google Patents

Abstract

PURPOSE:To enhance strippability of a hardened film with an aq. alkaline soln., by using a compsn. of specified 2 kinds of monoester compd. and dicyclopentadienyloxyalkyl (meth)acrylate. CONSTITUTION:The entitled compsn. consists of (A) a monoester compd. of an acid anhydride represented by general formula (1), such as hexahydrophthalic anhydride or 3-methylhexahydrophthalic anhydride, and a monomer having at least one OH, and at least one (meth)acryloyl group in the molecule, (B) a monoester compd. of an acid anhydride represented by general formula (2), such as phthalic anhydride, and the same monomer as mensioned above, (C) dicyclopentadienyloxyalkyl (meth)acrylate, and (D) a photosensitizier. This compsn. is patternwise printed and then, the film exposed to UV rays and hardened can be removed with an aq. alkaline soln.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ultraviolet-curable pattern-forming composition that is cured by ultraviolet light and peeled off by an alkaline aqueous solution, and is used for processing printed circuit boards and nameplates or for forming ξ turns on photosensitive printing plates.

In recent years, ultraviolet curable compositions have begun to be frequently used for the formation of various types of . This is because it is practically advantageous in terms of productivity, energy saving, pollution-free, etc., compared to conventionally used thermosetting compositions. Furthermore, with regard to the peeling of the ultraviolet cured film after the formation of the turn, there has been a shift from peeling using a solvent to using an alkaline aqueous solution due to reasons such as contamination of the working environment and economic efficiency. Under these circumstances, various UV-curable compositions have been investigated. but,
Attempts to improve the removability of UV-cured coatings using aqueous alkaline solutions tend to result in a decrease in crosslinking density and excessive retention of hydrophilicity, resulting in a decrease in UV-curing properties,
Wastewater treatment problems arise due to a decrease in the strength of the cured film in the etching solution or fragmentation or dissolution of the cured film peeled off by an alkaline aqueous solution, and a product that fully satisfies the required performance has yet to be developed. has not yet been achieved.

The inventors of the present invention have made efforts to solve the above-mentioned problems, and as a result, they have found that the cured film with an alkaline aqueous solution has excellent removability, and also has excellent curing properties with ultraviolet rays and strength of the cured film during etching. We have discovered Purple 51 (external line cured pattern forming composition) which does not cause fragmentation or dissolution of the cured film when it is peeled off, and which is easy to treat in waste water, and have completed the present invention.

That is, the present invention provides the following conditions: (However, R is hydrogen or CnH2H+1 t n -1
- represents an alkyl group represented by 4. ) A monoesterified compound of an acid anhydride represented by (B) with a monomer having at least one hydroxyl group and at least one (meth)acryloyl group in one molecule, (B) general formula (II) (However, R is hydrogen or ": nH21+1 + n -
It represents an alkyl group represented by 1 to 4. ) A monoesterified compound of an acid anhydride represented by (C) with a monomer having at least one hydroxyl group and at least one (meth)acryloyl group in one molecule, (C) dicyclopentadienyl This is an ultraviolet curing/zottle-forming composition containing an oxyalkyl (meth)acrylate and a (Di) photosensitizer.

The present invention: monoester of an acid anhydride represented by the general formula (I) and a monomer having at least one hydroxyl group and at least one (meth)acryloyl group in one molecule Examples of compounds include hexahydrontalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrontalic anhydride, 3-methylhexahydrophthalic anhydride,
-Ethyl hexahydrophthalic anhydride, 4-ethyl hexahydrophthalic anhydride, 3-propyl hexahydrophthalic anhydride, 3-isopropyl hexahydrophthalic anhydride, 4-propyl hexahydrophthalic anhydride acid anhydride, 4
-Isozolobil hexahydrophthalic anhydride, 3-butylhexahydrophthalic anhydride, 4-butylhexahydrophthalic anhydride
With an acid anhydride such as phthalic acid, preferably hexahydronthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, e.g.
-Hydroxylthyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxylthyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate , monoesterified compounds with monomers such as polycasilolactone mono(meth)acrylate. . These monoesterified compounds (A) can be used alone or in combination of two or more in any ratio.

Monoester of (B) acid anhydride represented by general formula (II) used in the present invention and a monomer having at least one hydroxyl group and at least one (meth)acryloyl group in one molecule Examples of compounds include phthalic anhydride, 3-methyltetrahydrophthalic anhydride,
4-methyltetrahydrophthalic acid, 3-ethyltetrahyP-phthalic anhydride, 4-ethyltetrahydrophthalic anhydride, 3-propyltetrahydrophthalic anhydride,
Acid anhydrides such as 4-propyltetrahydrophthalic anhydride, 3-butyltetrahydrophthalic anhydride, 4-butyltetrahydrophthalic anhydride, preferably phthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4
- Methyltetrahydrophthalic anhydride and, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, polyethylene glycol mono(
Examples include monoesterified compounds with monomers such as meth)acrylate, polypropylene mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, and polycasilolactone mono(meth)acrylate. These monoesterified compounds (B) can be used alone or in combination of two or more in any proportion.

The monoesterified compound of (N) and the monoesterified compound of (B) are preferably synthesized by a ring-opening addition reaction between an acid anhydride and a monomer, but they can also be synthesized by a normal esterification reaction. When synthesizing these monoesterified compounds, it is preferable to use 1 mol of the monomer per 1 mol of the acid anhydride, but an excess of one may be used.The above ring-opening addition The reaction temperature in the reaction is usually 50 to 150°C, preferably 80 to 110°C.
is within the range of

When carrying out the above ring-opening addition reaction, tertiary amines such as triethylamine, morpholine, pentamethyldiethylenetriamine, triethanolamine, or their quaternary ammonium salts can be used as promoters.

Additionally, mono-inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-zotylhyproquinone, t-butylcatechol, benzoquinone, and pro-notiazine may be used to prevent polymerization from occurring during the reaction. can.

The progress of the ring-opening addition reaction described above can be easily determined from the infrared absorption spectrum of the acid anhydride, and the disappearance of the infrared absorption spectrum of the acid anhydride indicates that the reaction has been substantially completed. I can see it.

The amount of the monoesterified compound (A) is preferably 5 to 87% by weight based on the turn-forming composition of the present invention, and the amount of the monoesterified compound (B) is preferably 5 to 87% by weight based on the pattern-forming composition of the present invention. It is preferably 5 to 87% by weight, based on the composition. Furthermore, it is preferable that the total amount of the monoesterified compound of (N) and the monoesterified compound of (B) is 42 to 92% by weight based on the composition for forming a pattern.(A
If the amount of the monoesterified compound (B) is less than 5% by weight, the strength of the cured film in the etching solution will decrease significantly, and if the amount of the monoesterified compound (B) is less than 5% by weight. , fragmentation and dissolution of the cured film peeled off by the alkaline aqueous solution occur.

If the total amount of the monoesterified compound (A) and the monoesterified compound (B) is less than 50% by weight, the removability with an alkaline aqueous solution will be significantly reduced.

(C) Dicyclopentadienyloxyalkyl (meth)acrylate used in the present invention includes, for example, cyclopentadienyl (meth)acrylate, dicyclopentadienyloxyethyl (meth)acrylate, dicyclopentagenyloxyethyl (meth)acrylate, Genyloxyzorobyl (meth)acrylate, dicyclopentadienyloxybutyl acrylate, etc. These dicyclopentadienyloxyalkyl (meth)acrylates (C) can be used alone or in combination of two or more in any proportion.

(C) Dicyclopentadienyloxyalkyl (meth)
The amount of acrylate is preferably 2 to 49% by weight, more preferably 5% by weight, based on the nogturn-forming composition of the present invention.
~45% by weight and weight. C) dicyclopentadienyloxyalkyl (meth)7 9L/-17;) amount is 50
When the amount exceeds % by weight, the removability of the cured film with an alkaline aqueous solution is significantly reduced.

As the photosensitizer (D) used in the present invention, any known photosensitizer can be used, but it is desirable that the photosensitizer has good storage stability after being blended. Examples of such photosensitizers include benzoin alkyl ether photosensitizers such as Pency 7 ethyl ether, benzoin butyl ether, and benzoin isopropyl ether;
-jetoxyacetophenone, 4'-phenoxy-2,
Acetophenone photosensitizers such as 2-dichloroacetophenone, propiophenone photosensitizers such as 2-hyroxy-2-methylprobiophenone, and 4'-inpropyl-2-hydroxy-2-methylzorobiophenone. Sensitizer, 2
Examples include anthraquinone photosensitizers such as -ethylanthraquinone, 2-t-butylanthraquinone, and 2-chloroanthraquinone, thioxanthone photosensitizers, and pendyl dimer ketal. These photosensitizers can also be used singly or in combination of two or more in any proportion. (The amount of the sunlight sensitizer is preferably 1 to 15% by weight, more preferably 3 to 13% by weight based on the pattern forming composition of the present invention.

The above (A), (B) and C for the composition of the present invention
It is also possible to add unsaturated compounds other than ).

Examples of unsaturated compounds that can be added include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polybutylene glycol mono(meth)acrylate.
meth)acrylate, polycaprolactone mono(meth)
Acrylate, cellosolve (meth)acrylate, methyl cellosolve (meth)acrylate, butyl cellosolve (meth)acrylate, carpitol (meth)acrylate, methylcarpitol (meth)acrylate, butylcarpitol (meth)acrylate, phenoxyethyl (meth)acrylate, Monofunctional unsaturated compounds such as phenylglycidyl ether (meth)acrylic acid adducts, polyprolene glycol di(meth)acrylate,
polyethylene glycol di(meth)acrylate-1,
Examples include bifunctional unsaturated compounds such as polyethylene glycol di(meth)acrylate, polycasololactone di(meth)acrylate), 1.6 hexane di(meth)acrylate, and neopentyl glycol di(meth)acrylate. If this is used to the extent that it accounts for 40% by weight or more of the turn-forming composition of the present invention, it is not preferable because the removability with an alkaline aqueous solution is reduced.

The composition of the present invention is used by being printed or coated, and in order to improve printing performance and coating suitability, an extender pigment, a leveling agent, an antifoaming agent, a coloring pigment, a thixotropic agent, etc. are added to the composition of the present invention. Can be used in addition to compositions.

The composition of the present invention is screen printed on a metal surface such as copper or brass, and then cured by irradiation with ultraviolet rays to form a film. UV irradiation is usually 50 to 2.0
After removing the exposed metal portion by etching with an etching solution within 30 seconds using a high pressure mercury lamp or a metal halide lamp of 0 W/(+l11), the ultraviolet cured coating of the composition of the present invention is removed with an alkaline aqueous solution to form a metal pattern. , plating metals such as solder, nickel, and gold using an acidic or neutral plating solution on exposed metal parts, and removing the ultraviolet-cured coating of the composition of the present invention with an alkaline aqueous solution, and then plating metals such as ammonium persulfate. It is also possible to form a metal pattern using metal plating by etching away the metal surface of copper, brass, etc. that is not plated with metal under the cured film using an alkaline etching solution.

The ultraviolet curing/guttan-forming composition of the present invention has excellent curing properties and film strength, and also has good removability of the film with an aqueous alkaline solution. Furthermore, since the release film does not fragment or dissolve, the waste alkaline aqueous solution can be easily treated, making it extremely excellent as an ultraviolet curable composition for forming metal grout.

Hereinafter, the present invention will be explained by examples.

Example l Hexahydrophthalic anhydride t54.9 (1 mol), 2
-Hydroxyethyl acrylate 116Il (1 mol)
and hydroquinone 0.27.9 were placed in a flask equipped with a stirrer, and reacted at 95°C for 8 hours until the acid anhydride peak in the infrared absorption spectrum disappeared to obtain a monoesterified compound (A-1). . On the other hand, -3-methyltetrahydrophthalic anhydride 16811 (1 mol), 2hydro, xyethyl methacrylate 130II (1 mol)
and 0.3079 of hydroquinone were reacted in the same manner as in the above monoesterified compound (A-1) to obtain a monoesterified compound (B-1).

82 parts of the monoesterified compound (A-1), 10 parts of the monoesterified compound (B-1), 5 parts of dicyclopentadiene acrylate, 21 parts of benzoin ethyl ether as a photosensitizer, and 1 part of t-butylanthraquinone. A composition for forming turns was prepared. In order to provide screen printing properties, 30 parts of talc as fillers, 30 parts of Norium sulfate as fillers, 05 parts of Erosil as a thixotropic agent, and 0.5 parts of phthalocyanine blue as a coloring pigment were added to 100 parts of the above pattern-forming composition to give screen printing properties. A screen printing ink for formation was prepared. The above screen printing ink for pattern formation (II) was printed on a copper plate by screen printing. The thickness of the printed coating film was 15μ.

This coating film was cured by irradiating ultraviolet rays with three 80 W/am high-pressure mercury lamps. The time required for curing was 5 seconds, and the pencil hardness of the cured film was 3H. Next, the exposed metal portions were removed by etching using a cupric chloride etching solution. The hardness of the cured film after etching was H. The cured film was peeled off from one side using a 3% hydroxide solution at 40° C. to obtain a metal pattern. The time required for peeling was 4 seconds, and the peeled hardened film did not dissolve or dissolve even after being left in the above sodium hydroxide solution or filtration solution for 48 hours.
There was no subdivision.

Example 2 3-Methylhexahydrophthalic anhydride 168.9 (1
mole), 2-hydroxyzorobyl methacrylate 173
1i (1.2 mol) was reacted in the same manner as in Example 1 to obtain a monoesterified compound (A-2). Further, 148 g (1 mol) of phthalic anhydride and 139 # (1.2 mol) of 2-hydroxyethyl acrylate were reacted in the same manner to obtain a monoesterified compound (B-2).

1. 10 parts of the above (A-2), 80 parts of the above (B-2), 5 parts of dicyclopentagenyl methacrylate, and 5 parts of benzyl dimethyl natal as a photosensitizer were blended. A composition for forming an e-turn was prepared. Using the composition, Example 1
A screen printing ink for pattern formation was prepared using the same recipe. This ink was printed and cured in the same manner as in Example 1. The pencil hardness of the cured film is 3H,
The pencil strength of the cured film after etching was F. 40
The cured film was peeled off from the copper surface using an IJium aqueous solution (3% hydroxide) to obtain a metal ξ turn. The time required for peeling was 4 seconds, and the peeled cured film was in the aqueous solution for 48 seconds.
No dissolution or fragmentation occurred even after standing for a long time.

Example 3 Hexahydrophthalic anhydride 1s4.9 (t mol) and 2-hydroxyethyl acrylate 130# (1 mol) were reacted in the same manner as in Example 1 to obtain a monoesterified compound (A-3). . Further, 168 g (1 mol) of 4-methyltetrahydrophthalic anhydride and 144.9 (1 mol) of 2-hydroxyzorobyl methacrylate were reacted in the same manner to obtain a monoesterified compound (B-3).

Contains 25 parts of the above (A-3), 30 parts of the above (B-3), 40 parts of dicyclopentadienyloxyethyl acrylate, and 5 parts of 2-hyProxy-2-methyl-propiophenone as a photosensitizer. A pattern-forming composition was prepared. Using this composition, a screen printing ink for pattern formation was prepared in the same manner as in Example 1, and this ink was printed and cured. The pencil hardness of the cured film was 3H, and the pencil hardness after etching was 2H. The cured film was peeled off from the copper surface using a 3% aqueous sodium hydroxide solution at 40° C. to obtain a metal pattern. The time required for peeling was 6 seconds, and the peeled cured film did not dissolve or fragment even after being left in the aqueous solution for 48 hours.

Example 4 4-Methylhexahydrophthalic anhydride 16819 (1
mole), tetraethylene glycol monoacrylate 3
58. ! 1 liter (1 mol) and 0.5 g of hydroquinone were reacted in the same manner as in Example 1 to obtain a monoesterified compound (A
-4) was obtained. Also, phthalic anhydride 148. p (1 mol)
, 2-hydroxyethyl methacrylate 130.9 (1
mol) and 0.28 g of hydroquinone were reacted in the same manner to obtain a monoesterified compound (B-4).

35 parts of the above (A-4), 20 parts of the above (B-1), 18 parts of the above (B-4), 15 parts of dicyclopentadienyloxyzolobyl methacrylate, and 4 parts as a photosensitizer.
-12 parts of phenoxy-2,2-dichloroacetophenone was blended to prepare a pattern-forming composition. Using this composition, a screen printing ink for pattern formation was prepared in the same manner as in Example 1, and this ink was printed and cured. The pencil hardness of the cured film was 3H, and the pencil hardness after etching was H. The cured film was peeled off from the copper surface using a 3% aqueous sodium hydroxide solution at 40°C to obtain a metal pattern. The time required for peeling was 4 seconds, and the peeled cured film did not dissolve or fragment even after being left in the aqueous solution for 48 hours.

Example 5 168 g (1 mol) of 3-methylhexahydrophthalic anhydride and 130 g of 2-hydroxyzorobyl acrylate)
．． 9 (1 mol) was reacted in the same manner as in Example 1 to obtain a monoesterified compound (A-5). Furthermore, phthalic anhydride 14819 (1 mol) and 2-hyP-roxypropyl methacrylate 14419 ('1 mol) were reacted in the same manner to obtain a monoesterified compound (m-s).

10 parts of the above (A-3), 25 parts of the above (A-5), upper He
c 8 5 ) 13 parts, dicyclopentadienyloxyethyl methacrylate 25 parts, 2-chlorothioxanthone 7 parts as a photosensitizer, and 2-hydroquinone thionimethylchloride L/-) 20 parts as other unsaturated compounds were blended to form a pattern-forming i composition. Using this composition, in the same manner as in Example 1, ? A screen printing ink for forming turns was prepared, printed with this ink, and cured.

The pencil hardness of the cured film was 2H, and the pencil hardness after etching was HB. The cured film was peeled off from the copper surface using a 3% sodium hydroxide aqueous solution at 40'C to obtain a metal e-turn. The time required for peeling was 4 seconds, and the peeled cured film did not dissolve or fragment even after being wrinkled in the aqueous solution for 48 hours.

Example 6 168 g (1 mol) of 4-methylhexahydrophthalic anhydride and 14 2-hydroxyethyl methacrylate
a Ii (1.1 mol) was reacted in the same manner as in Example 1 to obtain a monoesterified compound (A-6). In addition, 14 g (1 mole) of phthalic anhydride and 314.9 (1.1 mole) of tetraethylene glycol monoacrylate were reacted in the same manner to form the monoesterified compound (A-6).
I got it. 40 parts of the above (A-6), 40 parts of the above (B-6), 10 parts of dicyclopentadienyloxyprobyl acrylate, 3 parts of benzyl dimethyl ketal and 2 parts of 2-ethylanthraquinone as photosensitizers, and other additives. A pattern-forming composition was prepared by blending 5 parts of tripropylene glycol diacrylate as a saturated compound. Using this composition, a screen printing ink for /e turn formation was prepared in the same manner as in Example 1, and this ink was printed and cured. The pencil hardness of the cured film was 3H, and the pencil hardness after etching was 2H. Peel off the cured film from the copper surface with a 3% sodium hydroxide aqueous solution of 40"C to form Metal 1.
I got the pattern. The time required for peeling was 6 seconds, and the peeled cured film did not dissolve or dissolve even if left in the aqueous solution for 48 hours.
No fragmentation occurred.

Claims (1)

[Claims] 1. (A) General formula (I) (wherein R is hydrogen or cnl(m, nxl~4
represents an alkyl group represented by 11+1. ) A monoesterified compound of an acid anhydride represented by (B) a monomer having at least one hydroxyl group and at least one (meth)acryloyl group in one molecule; [) (However, R is hydrogen or cnH2n+1 * n -1
- represents an alkyl group represented by 4. ) A monoesterified compound of an acid anhydride represented by (C) with a monomer having a small number of traps in one molecule (both having one hydroxyl group and at least one (meth)acryloyl group), (C) dicyclopentageni A composition for ultraviolet curing and turn formation, which comprises a methacrylate (meth)acrylate and (D) a photosensitizer.