JPS58221841A - Photosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition suitable especially for use as ink for an etching resist, by blending a specified polymer having ethylenic unsatd. groups with a hydroxyalkyl acrylic hemiester of a polybasic acid, a vinyl monomer and a photopolymn. initiator. CONSTITUTION:A specified polymer represented by formula I (where R1 is CH3 or H; R2 is CH3, C2H5 or H; l is 0, 1 or 2; m is 1-3; and n is 6-8) is obtd. by reacting a compound represented by formula II (where R1 and R2 are said R1 and R2) with a styrene-maleic acid copolymer having 10-50mol% maleic acid content in general. The compound represented by formula II is obtd. by the addition reaction of hydroxyalkyl acrylate r methacrylate with epsilon-caprolactone.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a light, particularly an ultraviolet curable resin composition, and relates to an ultraviolet curable resin composition which is particularly suitable as an etching resist ink for manufacturing printed wiring boards.

Conventionally, ultraviolet curing inks for etching resists have been disclosed in Japanese Patent Laid-Open Nos. 51-2503 and 1982-13444. In other words, polyester is used to impart acid resistance and coating hardness, hydroxyalkyl acrylate (or methacrylate) is used to impart removability to the film using an alkali, and carboxylic acid or polybasic acid containing 2 to 36 carbon atoms is used. Resist inks made of hydroxyalkyl acrylate (or methacrylate) semi-esters have excellent properties such as fast curing, no pollution, no heating, and high reliability, so their usage is increasing.

Over the past few years, electrical and electronic devices have rapidly become smaller and more sophisticated, and there is a demand for thinner and higher reliability wiring on printed wiring boards. There is a need for a device that can be etched into thinner wiring patterns and has higher reliability.

Conventional ultraviolet curable etching resist inks have excellent alkaline removability as etching resists,
Moreover, the paint film has a pencil hardness of HB or higher, but if the wiring of the printed wiring board is etched with fine wires of 0.21 or less, the paint film may peel off, or the paint film and the printed wiring board An etching solution, for example,
Liquids such as ferric chloride aqueous solution, cupric chloride aqueous solution, ammonium persulfate aqueous solution, nitric acid aqueous solution, etc. can enter, causing disconnection defects in printed wiring board circuits, making it difficult to meet demands for thinner wiring and higher reliability. That's the reality.

The inventors of the present invention have conducted intensive research to meet such requirements, and have found that the releasability of the paint film with dilute alkali and the hardness of the paint film are approximately the same as those of conventional ultraviolet curable etching resist inks, and the hardness of the paint film is H or higher on a pencil hardness scale. We have discovered a new photocurable resin composition which has the same characteristics as the above, and which also allows the printed wiring board to sufficiently withstand etching of a 0.1% fine line pattern.

The polymer having an ethylenically unsaturated group in the present invention is a copolymer of the compound represented by the general formula (1), styrene, and maleic anhydride (usually the maleic anhydride content is 10 to 10%).
It is a polymer obtained by reacting the general formula c1 □ (however, each symbol in the formula is the same as the above formula [I] and 1
The same is true. (m: number from 1 to 3, n: number from 6 to 8) The compound represented by the general formula CII is hydroxyalkyl acrylate (or methacrylate) or c) hydroxyalkyl acrylate (or methacrylate) and nibsilone caprolactone. obtained by the addition reaction of As the hydroxyalkyl acrylate (or methacrylate), 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, and the corresponding methacrylates are used. An example of the synthesis of a reaction product of the general formula III) and a copolymer of styrene and maleic anhydride is shown below.

Synthesis example of a polymer having an ethylenically unsaturated group: Synthesis example 1
゜Mitsuro flask equipped with a stirrer, thermometer, and reflux condenser, 1! In the reactor, use materials with the following structure (manufactured by Daicel Chemical Industries, Ltd.) (product name: PJacceJ FMI 244.1?) and styrene/maleic anhydride copolymer (manufactured by ARCO/chemical company in the United States, product name SMA resin, SMA-1000) 202 .0P
C, acid value 480) and 0.223 g of hydroquinone monomethyl ether were charged and reacted at 90 to 100 C for 4 hours. Acid value Synthesis Example 2 In the same reactor used in Synthesis Example 1, 2-hydroxyethyl acrylate 116.17 and styrene Maleic anhydride copolymer (USA CO/chemical comp
-manufactured by any, product name: SM Av Gin, SMA-10
00) Prepare 202.05' (acid value 480) and 0.159 g of hydroquinone monomethyl ether, 90-10
React at 0C for 15 hours to form the following structure u with an acid value of 174.0.
'(;M2uj'12-u--t, -t-n=t-n
2 The polybasic acid (or
A hydroxyalkyl acrylate (or methacrylate) half-ester of a polybasic acid (or its anhydride) is obtained as an equimolar reaction product of a polybasic acid (or its anhydride) and a hydroxyalkyl acrylate (or methacrylate).

Examples of polybasic acids (or anhydrides thereof) include adipic acid, sepatic acid, azelaic acid, dodecane dicarboxylic acid, dimer acid, succinic anhydride, dodecenyl succinic anhydride, maleic anhydride, fumaric acid, itaconic acid, terephthalic acid, Citraconic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, methyl endomethylene Φ tetrahydro Phthalic anhydride, endo-methylene-tetrahydrophthalic anhydride, etc. are used, and as acrylates or methacrylates having a hydroxyalkyl group, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate,
-Hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, diethylene glycol monoacrylate, glycerin diacrylate, pentaerythritol triacrylate, and their corresponding methacrylates are used. Next, a synthesis example of a hydroxyalkyl acrylate (or methacrylate) half-ester of a polybasic acid will be shown. - Synthesis example 2 of hydroxyalkyl acrylate (or methacrylate) half-ester of polybasic acid Synthesis example 3゜ In the same reactor used in synthesis example 1, 130.0 g of 2-hydroxyethyl methacrylate and 148 g of phthalic anhydride, I
jil- and hydroquinone monomethyl ether 0.13
9.5' was charged and reacted for 17 hours at 90 to Iooc to obtain a half-esterified product with an acid value of 205.1.

Ethyl urea, acrylate 116.1Li- and phthalic anhydride 148.1f! - and hydroquinone monomethyl ether 0.132P were charged and reacted at 90~]OOt;' for 19 hours to obtain a half-esterified product with an acid value of 2]6.7.

Synthesis Example 5゜In the same reactor used in Synthesis Example 1, 2-hydroxyethyl acrylate 116.19-, hexahydrophthalic anhydride 1541, and hydroquinone monomethyl ether O,]3
5P was prepared and reacted at 90 to 100C for 17 hours to reach an acid value of 2.
A half-esterified product of 11.9 was obtained.

Synthesis Example 6 Into the same reactor used in Synthesis Example 1, 116.15' of 2-hydroxyethyl acrylate, 178.29' of methylendomethylenetetrahydrophthalic anhydride, and 0.0% of hydroquinone monomethyl ether were added. I47. Prepare gL 9o-1
A half-esterified product having an acid value of 194.5 was obtained by reacting with OOC for 29 hours.

The vinyl monomer having an ethylenically unsaturated double bond in the present invention includes various acrylic esters (or methacrylic esters), such as methoxyethyl acrylate (or methacrylate), ethoxyethyl acrylate (or methacrylate) ), tetrahydrofurfuryl acrylate (or methacrylate)
, stearyl acrylate (or methacrylate), phenoxyethyl acrylate (or methacrylate),
2-hydroxyethyl acrylate (or methacrylate), nibsilone caprolactone modified product of 2-hydroxyethyl acrylate (or nibsilone caprolactone modified product of methacrylate), 2-hydroxypropyl acrylate (or methacrylate), nibsilone of 2-hydroxypropyl acrylate caprolactone modified product (or nibsilone caprolactone modified product of methacrylate), nonylphenoxyethyl acrylate (or methacrylate), polyethylene glycol diacrylate (or methacrylate), polypropylene glycol diacrylate (or methacrylate), 1,6-hexanediol diacrylate ( or methacrylate), trimethylolpropane triacrylate (or methacrylate), hydroxypivalate neopentyl glycol diacrylate (or methacrylate), dipentaerythritol hexaacrylate, and the like.

Next, the photoinitiator used in the present invention can be any of the known photoinitiators including, for example, diacetyl, benzoin, acyloin ethers, and aromatic ketones and aldehydes. A suitable photoinitiator is
For example, benzyl dimethyl ketal (trade name, Irgacure 65), which can be obtained manually from Ciba-Geigy,
1). In addition to the composition of the present invention, the ultraviolet curable resin composition of the present invention may optionally contain a polymerization inhibitor, a thickener, a leveling agent, a fluidity improver, a matting agent, a plasticizer,
Fillers, coloring agents such as pigments or dyes, and other auxiliary agents can be used in combination.

Next, the above content will be specifically explained by citing reference examples and working examples.

Reference example 1゜A Mitsuro flask equipped with a stirrer, a thermometer, and a water separator with a condenser! 80g of propylene glycol in the reactor
- (1.05 mol), isophthalic acid 25P (0.15 mol), and maleic anhydride 99p (0.85 mol) and reacted for 18 hours at 50 to 200 C in a N2 gas atmosphere. 12.0% by weight of polyester with a point of 60.5C and an acid value of 53, and 3% of the half-esterified product of Synthesis Example 30.
' 5.1% by weight, 2-hydroxyethyl acrylate 10.0% by weight, trimethylolpropane triacrylate (vinyl monomer with ethylenically unsaturated bond)
2.0% by weight, barium sulfate (filler) 33.4% by weight, benzyl dimethyl ketal (photopolymerization initiator) 5.0%
ft% by weight, Modaflow (leveling agent manufactured by Monsando) 2.0% by weight, cyanine green (organic pigment) 0.
After uniformly mixing a composition consisting of 5% by weight at 70 to 80C, the mixture was sufficiently kneaded with a three-roll roll (manufactured by Bengami Seisakusho) and was coated on a silk screen with 0.1.0.15.0.
2.0.3.0.8. Using a pattern with 5 lines each having a width of 1.0 mm, it was printed on a copper foil of a printed wiring board using the screen printing method, and when cured with ultraviolet light, a sample with a hardness of the paint film of 2H on a pencil hardness scale was obtained. It was done. When this sample was treated with cupric chloride etching solution at 50C for 30 minutes, 0.
．． The coating film peeled off at the thin line portions of 1 and 0.15 mm.

The coating film was peeled off in 9 seconds with a 3% aqueous sodium hydroxide solution of 55tZ'.

Reference Example 2゜ 12.0% by weight of the same polyester as Reference Example 1, 2.6% by weight of 2-hydroxyethyl acrylate, 1.6-
hexanethiol diacrylate) 10.5% by weight, half-esterified product of Synthesis Example 4 30.1% by weight, benzyl dimethyl ketal 50% by weight, barium sulfate 28.0% by weight,
A composition consisting of 1.2% by weight of Modaflow and 1.0% by weight of methyl violet was stirred at 70 to 80C to mix uniformly, and then thoroughly kneaded and homogenized using three rolls (manufactured by Bengami Seisakusho).

The following sample was printed on a copper foil of a printed wiring board by the screen printing method in the same manner as in Reference Example 1, and cured with ultraviolet rays, resulting in a sample having a pencil hardness of 2H. When this sample was treated with ferric chloride etching solution at 5°C for 30 minutes,
Peeling of the coating occurred at O, L and thin line parts with a width of 0.15 mm. The coating film was peeled off in 11 seconds using a 3% aqueous solution of 55C sodium hydroxide.

Example 1゜Synthesis Example 10 20.0% by weight of the polymer, 393% by weight of the half-esterified product of Synthesis Example 6, 40% by weight of trimethylolpropane triacrylate, 8.5% by weight of nonylphenoxyethyl acrylate, benzyl dimethyl ketal (light Polymerization initiator) 50% by weight, barium sulfate (filler) 18.5
Weight %, Modaflow (Leveling agent manufactured by Monsanto) 1
．． After uniformly mixing 70 to 80 U of a composition consisting of 5% by weight and 1.0% by weight of cyanine green (organic pigment),
Thoroughly knead with three rolls (manufactured by Bengami Seisakusho) and apply 0.1, 0.15, 0.2.o to the silk screen.
, 3゜0.8.1.0 mm wide pattern with 5 lines each was printed on the copper foil of a printed wiring board by screen printing method, and when cured with ultraviolet rays, the hardness of the coating film was that of a pencil. A sample with a hardness of 3H was obtained. When this sample was treated with cupric chloride etching solution at 500 for 30 minutes, the results were 0.1 to 1.
．． There was no abnormality in the condition of all coating films. The coating film was peeled off with a 3% sodium hydroxide aqueous solution of 55C, and the film was peeled off in 7 seconds.

Example 2゜Synthesis Example 10 Polymer 12.2% by weight, Synthesis Example 30 half-esterified product 43.4% by weight, 2-hydroxyethyl methacrylate 3.4%, nonylphenoxyethyl acrylate) 10.3% by weight , benzyl dimethyl ketal 5.0
% by weight, barium sulfate 282% by weight, Modaflow 1.5
When a composition consisting of 1.0% by weight of Shanin Green was mixed, printed, and cured in the same manner as in Example 1, a sample with a coating film hardness of 8H on a pencil hardness was obtained. When this sample was treated with cupric chloride etching solution at 50C for 30 minutes, 0.
．． There was no abnormality in the condition of the coating film over a width of 1 to 1.0 mm. When the coating film was removed with a 3% 55C hydroxide solution, it was removed in 2 seconds.

Example 3 22.0% by weight of Synthesis Example 20 polymer, 40.0% by weight of half-esterified product of Synthesis Example 50, 9.0% by weight of trimethylolpropane triacrylate, 11.0% by weight of nonylphenoxyethyl acrylate %, benzyl dimethyl ketal 5% by weight, barium sulfate 1o, 5% by weight, Modaflow 1
．． A composition consisting of 5 mi% and 10% by weight of Shayungleaf was kneaded, printed and cured in the same manner as in Example 1, yielding a sample with a pencil hardness of 5H.

When this sample was treated with a cupric chloride etching solution at 50C for 30 minutes, there was no abnormality in the condition of all coatings with widths of 0.1 to 1, Q mm. When the coating film was peeled off with a 3% aqueous solution of 55C sodium hydroxide, it was peeled off in 5 seconds.

Example 4 Synthesis Example 20 Polymer 16.0% by weight, Synthesis Example 60 Half-esterified product 51.5% by weight, 2-hydroxyethyl
・Lumethacrylate 5. Example 2: A composition consisting of Oii%, nonylphenoxyethyl acrylate 15.0% by weight, benzyl dimethyl ketal 5.0% by weight, barium sulfate 5.0% by weight, Modaflow 1.5% by weight, and Shayungleaf 10% by weight. After kneading, printing, and curing in the same manner as in Example 1, a sample with a coating film hardness of 4 H on the pencil hardness scale was obtained. This sample was added to a ferric chloride etching solution at 50C for 30 minutes.
When treated for 1 minute, there was no abnormality in the condition of the coating film in all widths of 0, 1 to 1, and Qtnm. The coating film was peeled off in 5 seconds with a 3% aqueous solution of 55C sodium hydroxide.

Example 5゜21.0% by weight of the polymer of Synthesis Example 2, half ester of Synthesis Example 3 (l+ 36.4 ffli%, 3.3% by weight of 2-hydroxyethyl methacrylate, 10.0% by weight of nonylphenoxyethyl acrylate) , 5.0% by weight of benzyl methyl ketal, 21.8% by weight of barium sulfate, 1.5% by weight of Modaflow, and 1.0% by weight of Nyanin Green were kneaded, printed, and cured in the same manner as in Example 1. As a result, a sample with a paint film hardness of 8H on a pencil hardness scale was obtained.When this sample was treated with a ferric chloride etching solution at 50C for 30 minutes, all paint films with a width of 0.1 to 1.0 mm were removed. There was no abnormality in the condition.The coating film was peeled off in 3 seconds with a 55C 3% sodium hydroxide aqueous solution.

Example 6゜22% by weight of the polymer of Synthesis Example 2, Synthesis Example 50 half-Esmo (manufactured by Daicel Chemical Industries, product name: Plaxel FM-1)
), 5.0% by weight of benzyl dimethyl ketal, 10.5% by weight of barium sulfate, 1.5% by weight of Modaflow, and 1.0% by weight of Shayungleaf were mixed, printed, and cured in the same manner as in Example 1. As a result, the paint film had a pencil hardness of 4H.

When this sample was treated with cupric chloride etching solution at 50C for 30 minutes, the results were 0.1-1. There was no abnormality in the condition of the coating film across the entire width of Qmm. When the coating film was removed with 55 tL' of 3% hydroxide solution, it was removed in 7 seconds.

Patent applicant: Nippon Kayaku Co., Ltd.

Claims (1)

[Claims] 1 The following general formula having an ethylenically unsaturated group (where R
, is CH3 or H; R2 is CH3, C2H5 or H; 1
is an integer of 0 or 1 to 2; m is a number of 1 to 3; n is a number of 6 to 8]; and a hydroxyalkyl acrylate (or methacrylate] A photocurable resin composition containing a semi-esterified product, a vinyl monomer having an ethylenically unsaturated bond, and a photopolymerization initiator.