JPS5929246A - Composition for forming ultraviolet-cured pattern - Google Patents

Abstract

PURPOSE:To obtain the titled composition giving a cured film which is easily stripped off with an aqueous alkali soln. without requiring difficult treatment of waste water by blending specified two kinds of monoesterified compounds with dicyclopentenyloxyalkyl (meth)acrylate and a photosensitizer. CONSTITUTION:A monoesterified compound (A) prepared from an acid anhydride represented by formula I [where R is H or formula II (n is 1-4)] and a monomer having hydroxyl and (meth)acryloyl groups is blended with a monoesterified compound (B) prepared from an acid anhydride represented by formula III or IVand a monomer having hydroxyl and (meth)acryloyl groups, dicyclopentenyloxyalkyl (meth)acrylate (C), and a photosensitizer (D). Hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride or the like is used as the acid anhydride represented by the formula I , and phthalic anhydride, 3-methyltetra- hydrophthalic anhydride or the like is used as the acid anhydride represented by the formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a UV-cured 1-
The present invention relates to an ultraviolet-curable pattern-forming composition that is peeled off with an alkaline aqueous solution.

In recent years, ultraviolet curable compositions have begun to be frequently used for forming various patterns. This is because it is practically advantageous in terms of productivity, energy saving, pollution-free, etc., compared to conventionally used thermosetting compositions.

Further, regarding the peeling of the ultraviolet cured film after pattern formation, due to reasons such as pollution of the working environment and economic efficiency, there has been a shift from peeling using a solvent to peeling using an alkaline aqueous solution. Under these circumstances, various UV-curable compositions have been investigated. However, when attempting to improve the removability of a UV-cured film using an alkaline aqueous solution, it tends to result in a decrease in crosslinking density and excessive retention of hydrophilicity, resulting in a decrease in UV-curability and a hardening of the film in an etching solution. Problems arise in wastewater treatment due to a decrease in strength or fragmentation or dissolution of the cured film peeled off by an alkaline aqueous solution, and so far no product that fully satisfies the required performance has been developed.

As a result of intensive research to solve the above problems, the inventors of the present invention have found that a 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. The present inventors have discovered an ultraviolet-curable pattern-forming composition that 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 has completed the present invention.

That is, the present invention provides an acid anhydride represented by (A) general formula (1) (wherein R represents hydrogen or an alkyl group represented by Ω+1 when n=1 to 4) and a small amount in one molecule. A monoesterified compound with a monomer having both one hydroxyl group and at least one (ivy) acryloyl group, (B) general formula (II) (wherein R is hydrogen or cnH2, n-1 ~ 4 represents n+1 an alkyl group) and a monomer having at least one hydroxyl group and at least one (meth)acryloyl group in one molecule. This is a composition for forming an ultraviolet curable pattern, comprising a compound, (C) dicyclopentenyloxyalkyl (meth)acrylate, and (D) a photosensitizer.

(A) A monoester of an acid anhydride represented by general formula (1) and a monomer having at least one hydroxyl group and at least one (meth)acryloyl group in one molecule used in the present invention Examples of compounds include hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhegizahydrophthalic anhydride, 6-methylhexahydrophthalic anhydride,
-Ethyl hexahydrophthalic anhydride, 4-ethyl hexahydrophthalic anhydride, 6-propyl hexahydrophthalic anhydride, 6-ituproyl hexahydrophthalic anhydride, 4-propyl hexahydrophthalic anhydride acid anhydride, 4
- Acid anhydrides such as isopropyl-xahydrophthalic anhydride, ro-butylhexahydrophthalic anhydride, 4-butylhexahydrophthalic acid, preferably hexahydrophthalic anhydride, 6-methylhexahydrophthalic anhydride. Phthalic anhydride, 4-methylhexahydrophthalic anhydride and e.g.
-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate , monoesterified compounds with monomers such as polycaprolactone mono(meth)acrylate. These monoesterified compounds (A) can be used alone or in combination of two or more in any proportion.

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, 6-methyltetrahydrophthalic anhydride,
4-Methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, 3-propyltetrahydrophthalic anhydride, 4
Acid anhydrides such as -propyltetrahydrophthalic anhydride, ro-butyltetrahydrophthalic anhydride, 4-butyltetrahydrophthalic anhydride, preferably phthalic anhydride, 6-methyltetrahydrophthalic anhydride, 4-butyltetrahydrophthalic anhydride, etc. −
Methyltetrahydrophthalic anhydride and, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (
meth)acrylate-1, polyethylene glycol mono(
Examples include monoesterified compounds with molecular entities such as meth)acrylate, polypropylene mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, and polycaprolactone mono(meth)acrylate.
These (B) monoesterified compounds can be used singly or in combination of two or more -F in any proportion.

- Synthesis of the monoesterified compound of (A) and the monoesterified compound of (B) is carried out by a ring-opening addition reaction between an acid anhydride and a monomer (preferably carried out by a conventional method). It can also be synthesized by esterification reaction.When synthesizing these monoesterified compounds, it is preferable to use 1 mole of monomer per 1 mole of acid anhydride, but even if one is used in excess, The reaction temperature in the above ring-opening addition reaction is usually 50 to 150°C, preferably 80 to 150°C.
The temperature range is 10°C.

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.

Furthermore, in order to prevent polymerization from occurring during the reaction, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, t-butylcatechol, benzoquinone, and phenothiazine can also be used.

The progress of the ring-opening addition reaction can be easily determined from the infrared absorption spectrum of the acid anhydride, and it can be considered that the reaction is substantially completed when the infrared absorption spectrum peak of the acid anhydride disappears.

The amount of the monoesterified compound (A) is preferably 5 to 87% by weight based on the pattern 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.

Further, the total amount of the monoesterified compound (A) and the monoesterified compound (B) is preferably 42 to 922 to 92% by weight based on the composition for forming knots. (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. Then, the cured film peeled off by the alkaline aqueous solution is fragmented and dissolved. If the total number of monoesterified compounds (A) and monoesterified compounds (B) is less than 50% by weight, the removability with an alkaline aqueous solution will be significantly reduced.

Examples of dicyclopentenyloxyalkyl (meth)acrylate (C) used in the present invention include dicyclopenotenyl (meth)acrylate, synclopentenyloxyethyl (meth)acrylate, and dicyclopentenyloxy7butyl (meth)acrylate. , dicyclopentenyl ox-7butyl (meth)acrylate, and the like. These (C) dicyclopentenyloxyalkyl (
One type of meth)acrylate or a mixture of two or more types can be used in any ratio.

(C) The mold of dicyclopentenyloxyalkyl (meth)acrylate is preferably 2 to 49% by weight, more preferably 5 to 4% by weight, based on the pattern forming composition of the present invention.
It is 5% by weight. When the amount of dicyclopentenyloxyalkyl (meth)acrylate (C) increases by 50% by weight or more, the removability of the cured film with an aqueous alkaline 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 benzoin ethyl ether, pensoin phthyl ether, and benzoin isopropyl ether, 2,2-diethoxyacetophenone, and 4'-
Acetophenone photosensitizers such as phenoxy-2,2-dichloroacetophenone; propiophenone photosensitizers such as 2-hydroxy-2-methylpropiophenone and 4'-isopropyl-2-hydroxy-2-methylpropiophenone; Photosensitizers include anthraquinone photosensitizers such as 2-ethylanthraquinone, 2-1-butylanthraquinone, and 2-chloroanthraquinone, thioxanthone photosensitizers, and benzyl dimethyl ketal. These photosensitizers can be used alone or in a mixture of two or more in any ratio. (D) The amount of the photosensitizer can be adjusted to On the other hand, it is preferable to pay 1 to 15 times,
More preferably, the weight ratio is 3 to 13.

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

Examples of unsaturated compounds capable of increasing thrust 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, methylselonulp(meth)acrylate, butyl cellosolve (meth)acrylate, carpitol (meth)acrylate, methylcarpitol (meth)acrylate, butylcarpitol (meth)acrylate, fenoquinethyl (meth)acrylate, monofunctional unsaturated compounds such as phenylgrindyl ether (meth)acrylic acid adducts, polyethylene glycol di(meth)acrylate,
Polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, polycaprolactone di(meth)acrylate, 1.6 hexane di(meth)acrylate, neopentyl glycol di(
Examples include bifunctional unsaturated compounds such as meth)acrylate; however, it is preferable to use this compound until it accounts for 40% or more of the composition for forming a bright pattern in the water valve because the removability with an aqueous alkaline solution decreases. do not have.

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 200
Curing can be completed by short-time irradiation within 30 seconds using a W/cm high-pressure mercury lamp or metal halide lamp. Next, the exposed metal portions are removed by etching with an acidic metal etching solution such as cupric chloride, ferric chloride, or mineral acid, and then the ultraviolet-cured coating of the composition of the present invention is removed with an alkaline aqueous solution to form the metal pattern. Form.

After plating metals such as gold, nickel, and gold on the exposed metal parts using an acidic or neutral plating solution, and removing the ultraviolet-cured coating of the composition of the present invention using an alkaline aqueous solution, 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 the metal under the hardened film using an alkaline metal etching solution such as ammonium persulfate.

The ultraviolet curable pattern 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 become fragmented or dissolved, the waste alkali aqueous solution can be easily treated, and it is extremely excellent as an ultraviolet curable composition for forming metal patterns.

Hereinafter, the present invention will be explained by examples.

Example 1 Hexahydrophthalic anhydride 154 fl (1 mol)
, 2-hydroxyethyl acrylate 116 y (1
Mol) and hydroquinone 027 were placed in a flask 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, 6-methyltetrahydrophthalic anhydride 168
f (1 mol), 2hydroxyethyl methacrylate)-
130y (1 mol) and hydroquinone O2 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 above monoesterified compound (A-1), 10 parts of the above monoesterified compound (B-1), 5 parts of dicyclopentenyl acrylate, and 2 parts of benzoin ethyl ether and 1 part of t-butylanthraquinone as photosensitizers. were blended to prepare a pattern-forming composition. To provide screen printing properties, 30 parts of talc as fillers, 60 parts of barium sulfate, 05 parts of Ecosil as a thixotropic agent, and 05 parts of phthalocyanine blue as a coloring pigment were added to 10 parts of the above composition for pattern formation, and screen printing for pattern formation was performed. Ink was created. The above pattern-forming screen printing ink was printed on a copper plate by 1-noon printing. The thickness of the printed coating film was 15μ. This coating film was cured by irradiating it with ultraviolet rays using six high-pressure mercury lamps with a bow of 7 cm. 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 pencil hardness of the cured film after etching was H. The cured film was peeled off from the copper surface using a 3918 sodium hydroxide aqueous 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 above sodium hydroxide aqueous solution for 48 hours.

Example 2 Methylhexahydrontalic anhydride 168 (1 mol), 2-hydroxybutyrmethacrylate) 173f
(1.2 mol) was reacted in the same manner as in Example 1 to obtain a monoesterified compound (A-2).

Also 148 ft (1 mole) of phthalic anhydride and 2-
Hydroxyethyl acrylate) 139f (1.2 mol)
was also reacted in the same manner to form a monoesterified compound (B-
2) Got it.

A pattern-forming composition was prepared by blending 10 parts of the above (A-2), 80 parts of the above (B-2), 5 parts of dicyclopentenyl methacrylate, and 5 parts of benzyl dimethyl ketal as a photosensitizer. Using this composition, a pattern-forming screen printing ink was prepared using the same formulation as in Example 1. This ink was printed in the same manner as in Example 1, cured, and the cured film was peeled off from the copper surface with a 3% aqueous sodium hydroxide solution to obtain a metal pattern. 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 154 f (1 mol) and 2-hydroquinethyl methacrylate 1307 (1 mol)
mol) was reacted in the same manner as in Example 1 to obtain a monoesterified compound (A-6). Furthermore, 168 y (1 mol) of 4-methyltetrahydrophthalic anhydride and 144 yen (1 mol) of 2-hydroxypropyl methacrylate were reacted in the same manner to obtain a monoesterified compound (B-3). 25 parts of the above (A-6), the so part of the above (B-3),
A pattern-forming composition was prepared by blending 40 parts of dicyclopentenyloxyethyl acrylate and 5 parts of 2-hydroxy-2-methyl-propiophenone as a photosensitizer. 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 is 3H,
The pencil hardness after etching was 2H. The cured film was peeled off from the copper surface using an aqueous solution of sodium hydroxide 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 1687 (1 mol), tetraethylene glycol monoacrylate 35
B? (1 mol) and hydroquinone 052 were reacted in the same manner as in Example 1 to obtain a monoesterified compound (A-4).
I got it. Still phthalic anhydride 148 y (1 mol), 2
-Hydroxyethyl methacrylate 150f (1 mol)
and Hydroquinone 0282 were reacted in the same manner to obtain a monoesterified compound (B-4). Above (A-
4) 35 parts, 20 parts of the above (B-1), the above (, B-4)
18 parts, 1-15 parts of di/clopentenyloxyglobil methacrylate and 4'-phenoxy- as a photosensitizer.
A pattern-forming composition was prepared by blending 2,2-dichloroacetophenone i2*l. Using the composition, Example 1
A pattern-forming screen printing ink was prepared in the same manner as above, 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 with a 3% aqueous thorium 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 (1 mol) and 2-hydroxyglopylacrylate L501F (1 mol) were reacted in the same manner as in Example to obtain a monoesterified compound (A-5).

Also, phthalic anhydride 148? (1 mol) and 2-
Hydroxyethyl methacrylate 144 fi' (1
mol) was similarly reacted to obtain a monoesterified compound (B-s). 10 parts of the above (A-1), the above (A-
5) 25 parts, 13 parts of the above (B-5), 25 parts of dicyclopentenyl oxy/ethyl methacrylate, 77 parts of 2-chlorothioxane as a photosensitizer, and 20 parts of 2-hydroxyethyl methacrylate as other unsaturated compounds. These were blended to form 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 2H, and the pencil hardness after etching was HB. The cured film was peeled off from the copper surface using a 40°C aqueous solution of sodium hydroxide and metal butter/
I got it. 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 6 4-Methylhexahydrophthalic anhydride 168Li! (
1 mol) and 2-hydroxyethyl methacrylate 1
4-7 (11 mol) was reacted in the same manner as in Example 1 to obtain a monoester compound (A-6). Furthermore, phthalic anhydride 148f (1 mol) and tetraethylene glycol monoacrylate 6947 (11 mol) were reacted in the same manner to obtain a monoesterified compound (8-6). 40 parts of the above (A-6), 40 parts of the above (B-(S)), 10 parts of dicyclopentenyloxypropyl acrylate
1 part, 6 parts of benzyl dimethyl ketal and 72 parts of 2-ethyl anthraquino as a photosensitizer, and 5 parts of tribropylene glycol acrylate as other unsaturated compounds.
A pattern-forming composition was prepared by blending the following parts.

Using this composition, a screen printing ink for pattern formation was prepared in the same manner as in Example 1, and printing with this ink,
hardened. 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 in an aqueous solution of sodium trihydroxide at 40°C to obtain a metal pattern. The time required for peeling is 6 seconds.
The peeled cured film did not dissolve or fragment even when it was left in the aqueous solution for 48 hours.

patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 10\) General formula (1) (However, R is hydrogen or C1H2', n = 1 to 4
represents an alkyl group represented by n→1. ) 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 (11) (However, R represents hydrogen or CnH2n+□, an alkyl group represented by n-1 to 4.) and at least one hydroxyl group and at least one (meth) in one molecule. A composition for forming an ultraviolet curable pattern comprising a monoesterified compound with a monomer having an acryloyl group, (C) dicyclopentenyloxyalkyl (meth)acrylate, and (D) a photosensitizer. thing.