JPH0623233B2 - Method for producing acid pendant type epoxy acrylate resin - Google Patents
Method for producing acid pendant type epoxy acrylate resinInfo
- Publication number
- JPH0623233B2 JPH0623233B2 JP1150295A JP15029589A JPH0623233B2 JP H0623233 B2 JPH0623233 B2 JP H0623233B2 JP 1150295 A JP1150295 A JP 1150295A JP 15029589 A JP15029589 A JP 15029589A JP H0623233 B2 JPH0623233 B2 JP H0623233B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- epoxy acrylate
- acrylate resin
- resin
- type epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
- H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
Landscapes
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、活性エネルギー線特に紫外線硬化樹脂のうち
弱アルカリ性液に可溶で光硬化必要に応じて後加熱する
ことによって不溶、不融となる酸ペンダント型エポキシ
アクリレート樹脂の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to an active energy ray, particularly an ultraviolet curable resin, which is soluble in a weak alkaline liquid and photocurable. The present invention relates to a method for producing an acid pendant type epoxy acrylate resin.
エポキシアクリレート樹脂を含めアクリレートオリゴマ
ー類はその光硬化特性が優れていることから広く産業界
に応用されている。その内でもエポキシアクリレート樹
脂は光硬化性と共に被着体との密着性、耐熱性、耐薬品
性が他のアクリルオリゴマー類に比べ優れているため金
属コーティングやプリント配線基板のソルダーレジスト
用として広く利用されてきた。Acrylate oligomers, including epoxy acrylate resins, are widely used in industry due to their excellent photo-curing properties. Among them, epoxy acrylate resin is widely used for metal coating and solder resist for printed wiring boards because it has excellent photocurability, adhesion to adherends, heat resistance and chemical resistance compared to other acrylic oligomers. It has been.
特にソルダーレジストに関しては、基板の情報量の増加
につれてパターンの細密化が世の中の流れであり、従来
用いられてきたスクリーン印刷法では細密化への対応が
困難であり、写真製版法によるソルダーレジストが開発
されつつある。In particular, with regard to solder resists, pattern miniaturization is a trend in the world as the amount of information on the substrate increases, and it is difficult to deal with finer patterns with the conventionally used screen printing method. It is being developed.
その手法として未露光部インキを溶剤や希アルカリ液で
現像する方法があるが、コスト面や溶剤の公害問題の点
で希アルカリ液現像型が主流となりつつある。As a method therefor, there is a method of developing the unexposed area ink with a solvent or a dilute alkaline solution, but the dilute alkaline solution developing type is becoming mainstream in terms of cost and pollution of the solvent.
これら希アルカリ現像型ソルダーレジストとしては、エ
ポキシアクリレート樹脂の水酸基に酸無水物を反応させ
てカルボキシル基をペンダント化させたいわゆる酸ペン
ダント型エポキシアクリレート樹脂が主成分であり、こ
の樹脂の製法やそれを利用した塗装方法はすでに公知で
ある。そしてソルダーレジスト硬化皮膜としての耐水性
や電気的特性を向上させる目的でインキ中にカルボキシ
ル基を封鎖するエポキシ樹脂を配合し紫外線照射時の輻
射熱を利用するかまたは120〜150℃雰囲気で後加熱する
ことで架橋密度を向上させ強靭な皮膜を形成する方法が
とられている。The main component of these dilute alkaline development type solder resists is a so-called acid pendant type epoxy acrylate resin obtained by reacting an acid anhydride with a hydroxyl group of an epoxy acrylate resin to pendant a carboxyl group. The coating method used is already known. And for the purpose of improving the water resistance and electrical properties as a solder resist cured film, an epoxy resin that blocks the carboxyl group is blended into the ink and radiant heat at the time of ultraviolet irradiation is used, or it is post-heated in an atmosphere of 120 to 150 ° C. Therefore, a method of increasing the crosslink density to form a tough film is used.
上記した酸ペンダント型エポキシアクリレート樹脂にエ
ポキシ樹脂を配合してインキや塗料に用いる場合、エポ
キシ基とカルボキシル基が反応し、経時的に増粘したり
ゲル化に至るといった傾向があり、インキの安定性の面
から使用直前に配合する方法がとられている。When an epoxy resin is blended with the above acid pendant type epoxy acrylate resin and used in inks and paints, the epoxy group and the carboxyl group react with each other, and there is a tendency that viscosity increases or gelation occurs over time, and ink stability From the viewpoint of sex, a method of blending just before use is adopted.
また通常配合されるインキは作業性の面から、溶剤又は
必要に応じ少量のアクリルモノマーが配合されており、
ネガフィルムによるパターン化前に塗布したインキを70
〜80℃雰囲気で加熱して溶剤を揮散、除去した後露光に
よるパターン化の工程がとられるが、この工程で上記し
たカルボキシル基とエポキシ基の反応が一部進行すると
露光後の現像が不充分になる場合が多く、配合及び溶剤
除去、温度、時間に制約が多いという難点があった。
〔課題を解決するための手段〕 本発明者らは、前述したインキの安定性並びに揮発成分
の除去のための加熱における現像精度、現像化安定性に
ついて鋭意研究を重ねた結果、エポキシアクリレート樹
脂製造時即ちエポキシ樹脂と不飽和−塩基酸との反応に
おけるエステル化のための触媒並びに生成したエポキシ
アクリレート中の水酸基と飽和又は不飽和二塩基酸無水
物との酸ペンダント化のためのエステル化触媒が大きく
影響していることを見出し本発明に至った。In addition, the ink usually blended contains a solvent or a small amount of an acrylic monomer as necessary from the viewpoint of workability,
Ink applied before patterning with negative film
Although a step of patterning by exposure is performed after volatilizing and removing the solvent by heating in an atmosphere of ~ 80 ° C, if the reaction of the carboxyl group and epoxy group described above partially proceeds in this step, the development after exposure is insufficient. In many cases, there are many restrictions on compounding, solvent removal, temperature and time.
[Means for Solving the Problems] The inventors of the present invention have conducted intensive studies on the stability of the above-mentioned ink and the development accuracy and development stability in heating for removing volatile components, and as a result, the production of epoxy acrylate resin A catalyst for esterification during the reaction of an epoxy resin with an unsaturated-basic acid and an esterification catalyst for acid pendant formation of a hydroxyl group in a formed epoxy acrylate with a saturated or unsaturated dibasic acid anhydride are used. The inventors have found that it has a great influence and have reached the present invention.
即ち、本発明は、１分子中にエポキシ基２個以上有する
エポキシ樹脂と不飽和−塩基酸とを反応させて得られた
エポキシアクリレート樹脂の水酸基1.0当量当り0.1〜1.
0当量となる量の二塩基酸無水物を反応させて酸ペンダ
ント型エポキシアクリレート樹脂を製造するに当り、エ
ステル化触媒として有機酸の金属塩を使用することを特
徴とする酸ペンダント型エポキシアクリレート樹脂製造
法に関し、かかる酸ペンダント型エポキシアクリレート
樹脂を使用することによって、前記課題が解決された。That is, in the present invention, 0.1 to 1.1 per 1.0 equivalent of hydroxyl group of an epoxy acrylate resin obtained by reacting an epoxy resin having two or more epoxy groups in one molecule with an unsaturated basic acid.
An acid pendant type epoxy acrylate resin characterized by using a metal salt of an organic acid as an esterification catalyst in producing an acid pendant type epoxy acrylate resin by reacting an amount of 0 equivalent of a dibasic acid anhydride. Regarding the manufacturing method, the above-mentioned problems have been solved by using such an acid pendant type epoxy acrylate resin.
本発明におけるエポキシ樹脂と不飽和−塩基酸との反応
及び酸ペンダント化反応についてはすでに公知であり、
エステル化触媒を除いてそのまま採用可能である。通
常、１分子中にエポキシ基２個以上有するエポキシ樹脂
としてビスフェノール型エポキシ樹脂、ノボラック型エ
ポキシ樹脂ハロゲン化ビスフェノール型エポキシ樹脂、
ハロゲン化ノボラック型エポキシ樹脂等と、不飽和−塩
基酸としてアクリル酸又はメタアクリル酸とを、エポキ
シ基とカルボキシ基がほぼ当量になるように仕込み安定
剤として例えばハイドロキノン、メチルハイドロキノ
ン、トリメチルハイドロキノン、ターシャリブチルハイ
ドロキノン、銅塩、フェノチアジン等の存在下、80〜15
0℃、好ましくは90〜130℃で酸価がほぼ零になる迄反応
する。その後、水酸基1.0当量当り0.1〜1.0当量の割合
で飽和又は不飽和酸無水物例えば無水マレイン酸、無水
フタル酸、無水コハク酸、無水テトラヒドロフタル酸、
無水ヘキサヒドロフタル酸、無水トリメリット酸、無水
ヘット酸、無水メチルナジック酸、無水イタコン酸等を
仕込み常温から150℃、好ましくは40〜130℃で反応しペ
ンダントエステル化する。反応終了は赤外分光スペクト
ル1770cm-1及び1850cm-1の酸無水物ピークが消失するこ
とで確認する。反応中攪拌効率を良くするためにベンゼ
ン、トルエン、キシレン、ブチルセロソルブアセテー
ト、セロソルブアセテート、カルビトールアセテート等
の溶剤を加えて反応を行っても良い。又反応後粘度調整
等の必要に応じてヒドロキシアルキル（メタ）アクリレ
ート等のアクリルモノマーが添加される。The reaction between the epoxy resin and the unsaturated-basic acid and the acid pendant reaction in the present invention are already known,
It can be used as it is, except for the esterification catalyst. Usually, as an epoxy resin having two or more epoxy groups in one molecule, a bisphenol type epoxy resin, a novolac type epoxy resin, a halogenated bisphenol type epoxy resin,
Halogenated novolac type epoxy resin and the like, and acrylic acid or methacrylic acid as the unsaturated-basic acid, and charged as a stabilizer such that the epoxy group and the carboxy group are almost equivalent, for example, hydroquinone, methylhydroquinone, trimethylhydroquinone, tarsha. 80 to 15 in the presence of ributylhydroquinone, copper salt, phenothiazine, etc.
The reaction is carried out at 0 ° C, preferably 90 to 130 ° C until the acid value becomes almost zero. Then, saturated or unsaturated acid anhydride such as maleic anhydride, phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride in a ratio of 0.1 to 1.0 equivalent per 1.0 equivalent of hydroxyl group.
Hexahydrophthalic anhydride, trimellitic anhydride, hettic anhydride, methyl nadic acid anhydride, itaconic anhydride and the like are charged and reacted at room temperature to 150 ° C, preferably 40 to 130 ° C to form a pendant ester. Completion of the reaction is confirmed by disappearance of the acid anhydride peaks at infrared spectrum 1770 cm -1 and 1850 cm -1 . During the reaction, the reaction may be carried out by adding a solvent such as benzene, toluene, xylene, butyl cellosolve acetate, cellosolve acetate or carbitol acetate in order to improve the stirring efficiency. Further, after the reaction, an acrylic monomer such as hydroxyalkyl (meth) acrylate is added as necessary for adjusting viscosity.
この際従来法では、エステル化触媒として通常トリエチ
ルアミン、トリスジメチルアミノメチルフェノール、ベ
ンジルジメチルアミン等の第三級アミン、トリメチルベ
ンジルアンモニウムクロライド等の第四級アンモニウム
塩、２−エチル−４−メチルイミダゾールで代表される
イミダゾール化合物、ジエチルアミン塩酸塩、ジアザビ
スシクロウンデセン等の窒素化合物、トリフェニルフォ
スフィンに代表されるリン化合物が使用されてきた。At this time, in the conventional method, usually, as an esterification catalyst, a tertiary amine such as triethylamine, trisdimethylaminomethylphenol, benzyldimethylamine, a quaternary ammonium salt such as trimethylbenzylammonium chloride, or 2-ethyl-4-methylimidazole is used. Representative imidazole compounds, diethylamine hydrochloride, nitrogen compounds such as diazabiscycloundecene, and phosphorus compounds typified by triphenylphosphine have been used.
本発明者らは、これら通常のエステル化触媒に替えて、
金属石けんと称されている有機酸の金属塩、例えばナフ
テン酸、ラウリン酸、ステアリン酸、オレイン酸やオク
トエン酸のリチウム、クロム、ジルコニウム、カリウ
ム、ナトリウム等の塩を使用することで、特に酸無水物
のペンダント化をスムーズに行うために上記エステル化
触媒を併用（例えばナフテン酸クロムとナフテン酸リチ
ウムの併用）することで、この樹脂を基本とするインキ
や塗料にエポキシ樹脂を配合した場合の現像性管理幅が
大幅に広がり現像不良が大幅に減らせることが判明し
た。The present inventors have replaced these ordinary esterification catalysts with
By using a metal salt of an organic acid called metal soap, such as naphthenic acid, lauric acid, stearic acid, lithium, chromium, zirconium, potassium, sodium salts of oleic acid and octoenoic acid, particularly acid anhydride is used. By using the above esterification catalysts together (for example, chromium naphthenate and lithium naphthenate together) in order to make the pendant of the product smooth, the development when the epoxy resin is mixed with the ink or paint based on this resin It has been revealed that the property control range can be greatly expanded and development defects can be significantly reduced.
本発明による酸ペンダント型エポキシアクリレート樹脂
及びエポキシ樹脂を含むインキや塗料は、現像前の溶剤
を揮散する予備乾燥時間が従来のインキや塗料では70〜
80℃雰囲気中20〜30分位が限界でそれ以上行うとその後
のアルカリ現像工程で不良ケ所が発生する場合が多かっ
たのに比べ、乾燥時間を80〜90分と大幅に延長してもア
ルカリ現像性の低下は見られなかった。The ink or paint containing the acid pendant type epoxy acrylate resin and the epoxy resin according to the present invention has a predrying time of volatilizing the solvent before development to 70 to 70% for the conventional ink or paint.
In the atmosphere of 80 ° C, the limit is about 20 to 30 minutes, and if it is performed longer than that, defects often occur in the subsequent alkali development process, whereas even if the drying time is greatly extended to 80 to 90 minutes, No decrease in developability was observed.
この現像については、本発明による酸ペンダント型エポ
キシアクリレート樹脂と所定量のエポキシ樹脂を混合
し、試験管に入れ70〜80℃のオイルバス中に放置し混合
した系の酸価の経時変化を検べた結果、通常の第三級ア
ミン等の塩基性触媒を使用した従来品に比べ酸価の低下
速度は５分の１以下であった事実とも一致した。このこ
とは、本発明において使用される有機酸の金属塩触媒が
70〜80℃雰囲気中ではエポキシ基とカルボキシル基の反
応を従来の塩基性触媒を使用した物に比べ極力押えてい
ることの証明であるが、その理由は明確ではない。因み
に、120〜150℃雰囲気中での酸価の低下速度は塩基性触
媒を使用した物と同程度であり、同温度での硬化に遜色
はなかった。For this development, the acid pendant type epoxy acrylate resin according to the present invention and a predetermined amount of the epoxy resin were mixed, placed in a test tube and allowed to stand in an oil bath at 70 to 80 ° C, and the time course of the acid value of the mixed system was examined. As a result, the result was in agreement with the fact that the rate of decrease in acid value was 1/5 or less as compared with the conventional product using a basic catalyst such as a usual tertiary amine. This means that the metal salt catalyst of the organic acid used in the present invention is
This is a proof that the reaction between the epoxy group and the carboxyl group is suppressed as much as possible in the atmosphere of 70 to 80 ° C as compared with the one using the conventional basic catalyst, but the reason is not clear. By the way, the rate of decrease of the acid value in the atmosphere of 120-150 ℃ was the same as that of using the basic catalyst, and the curing at the same temperature was comparable.
実施例 １ 米国ダウケミカル社製フェノールノボラック型エポキシ
樹脂ＤＥＮ438 188ｇ（1.0当量）、アクリル酸72.0ｇ
（1.0当量）、ヒドロキノン0.1ｇ、ナフテン酸クロム
（金属クロム３％）0.8ｇ、溶剤ブチルセロソルブアセ
テート70ｇを仕込み空気を吹き込みながら110〜120℃で
９時間反応するとエステルの酸価がほぼ零となった。次
いで無水マレイン酸98ｇ（1.0モル）を仕込み110℃〜12
0℃で３時間反応すると赤外分光分析で1850及び1770cm
-1の酸無水物の吸収がなくなり反応を終了した。この時
点でエステルの酸価は155であった。ブチルセロソルブ
アセテートを122ｇ添加し粘度600ポアズ／25℃の粘稠な
樹脂を得た。以下この物を樹脂Ａとする。Example 1 188 g (1.0 equivalent) of DEN438, a phenol novolac type epoxy resin manufactured by Dow Chemical Company, USA, 72.0 g of acrylic acid
(1.0 equivalent), 0.1 g of hydroquinone, 0.8 g of chromium naphthenate (3% metal chromium), and 70 g of solvent butyl cellosolve acetate were charged and the acid value of the ester became almost zero after reacting for 9 hours at 110-120 ° C while blowing air. . Next, 98 g (1.0 mol) of maleic anhydride was charged and 110 ° C-12
Infrared spectroscopic analysis shows 1850 and 1770cm when reacted at 0 ℃ for 3 hours.
The reaction was terminated by the absorption of the acid anhydride of -1 disappeared. The acid value of the ester at this point was 155. 122 g of butyl cellosolve acetate was added to obtain a viscous resin having a viscosity of 600 poise / 25 ° C. Hereinafter, this product is referred to as resin A.
上記配合物をロールで混練りしインキを調整し銅張り積
層板の全面にロールコーターで約40μｍの厚さに塗布し
た。インキを塗布した積層板を80℃の乾燥器中に60分放
置し、溶剤を揮散させた。この上にネガフィルムを介し
て、２kW（80Ｗ／cm）高圧水銀灯を用いて10秒間露光し
た。次いで１％炭酸ソーダ水溶液に120秒浸漬し紫外線
未露光部の現像性を目視にて検べた。結果は表−１に示
す。 The above mixture was kneaded with a roll to adjust the ink, and the entire surface of the copper-clad laminate was coated with a roll coater to a thickness of about 40 μm. The laminated plate coated with the ink was left in a dryer at 80 ° C. for 60 minutes to volatilize the solvent. It was exposed for 10 seconds through a negative film using a 2 kW (80 W / cm) high pressure mercury lamp. Then, it was immersed in a 1% aqueous solution of sodium carbonate for 120 seconds, and the developability of the unexposed portion of ultraviolet rays was visually inspected. The results are shown in Table-1.
実施例 ２ 大日本インキ化学工業製クレゾールノボラック型エポキ
シ樹脂エピクロンＮ−680 213ｇ（1.0当量）、アクリ
ル酸72ｇ（1.0当量）、ヒドロキノン0.1ｇ、ナフテン酸
クロム0.8ｇ、ナフテン酸リチウム（金属１％）0.4ｇ、
溶剤（メチルセロソルブアセテート）80ｇを仕込み、空
気を吹き込みながら110〜120℃で８時間反応するとエス
テルの酸価がほぼ零となった。次いで無水マレイン酸49
ｇ（0.5モル）を仕込み110〜120℃で２時間反応すると
実施例１と同様赤外分光分析で1850及び1770cm-1の酸無
水物の吸収が消失し反応を終了した。この時点のエステ
ル酸価は84であった。メチルセロソルブアセテート100
ｇを添加し粘度300ポアズ／25℃の粘稠な樹脂を得た。
以下これを樹脂Ｂとする。Example 2 Dainippon Ink and Chemicals Incorporated cresol novolac type epoxy resin Epicron N-680 213 g (1.0 equivalent), acrylic acid 72 g (1.0 equivalent), hydroquinone 0.1 g, chromium naphthenate 0.8 g, lithium naphthenate (metal 1%). 0.4 g,
When 80 g of a solvent (methyl cellosolve acetate) was charged and reacted at 110 to 120 ° C. for 8 hours while blowing air, the acid value of the ester became almost zero. Then maleic anhydride 49
When g (0.5 mol) was charged and reacted at 110 to 120 ° C. for 2 hours, absorption of acid anhydrides at 1850 and 1770 cm −1 disappeared by infrared spectroscopy as in Example 1, and the reaction was terminated. The ester acid value at this point was 84. Methyl cellosolve acetate 100
g was added to obtain a viscous resin having a viscosity of 300 poise / 25 ° C.
Hereinafter, this is referred to as resin B.
以下、実施例１と同様に試験を行った。結果は表−１に
示す。 Hereinafter, the same test as in Example 1 was performed. The results are shown in Table-1.
実施例 ３ 油化シェル(株)エピコート82ｇ 188ｇ（1.0当量）、ア
クリル酸72ｇ（1.0当量）、ヒドロキノン0.1ｇ、ナフテ
ン酸ジルコニウム（金属ジルコニウム４％）0.8部を添
加し空気を吹き込みながら110〜120℃で６時間反応する
とほぼエステルの酸価は零となった。次いで無水テトラ
ヒドロフタル酸152ｇ（1.0モル）を仕込み110〜120℃２
時間反応すると酸価137となり又、実施例１と同様赤外
分光分析で酸無水物の吸収が消失することを確認した。
これにカルビトールアセテート176ｇを加え粘度450ポア
ズ／25℃の粘稠な樹脂を得た。以下この物を樹脂Ｃとす
る。Example 3 Yuka Shell Co., Ltd. Epicoat 82 g 188 g (1.0 equivalent), acrylic acid 72 g (1.0 equivalent), hydroquinone 0.1 g, and zirconium naphthenate 0.8 parts (metal zirconium 4%) 0.8 parts were added, and air was blown 110-120. After reacting for 6 hours at 0 ° C., the acid value of the ester became almost zero. Next, charge 152 g (1.0 mol) of tetrahydrophthalic anhydride at 110-120 ° C 2
It was confirmed that the acid value became 137 when the reaction was carried out for a time, and the absorption of the acid anhydride disappeared by infrared spectroscopy as in Example 1.
To this was added 176 g of carbitol acetate to obtain a viscous resin having a viscosity of 450 poise / 25 ° C. Hereinafter, this product is referred to as resin C.
以下実施例１と同様の試験を行った。 The same test as in Example 1 was performed below.
比較例 １ 米国ダウケミカル社製フェノールノボラック型エポキシ
樹脂ＤＥＮ438 188ｇ（1.0当量）、アクリル酸72ｇ
（1.0当量）ヒドロキノン0.1ｇ、ベンジルジメチルアミ
ン0.8ｇ、溶剤ブチルセロソルブアセテート70ｇを仕込
み空気を吹き込みながら120℃で９時間反応するとエス
テルの酸価がほぼ零となった。次いで無水マレイン酸98
ｇ（1.0モル）を仕込み110〜120℃で２〜３時間反応す
ると赤外分光分析で1850及び1770cm-1の酸無水物の吸収
が消失しエステルの酸価は156となった。更にブチルセ
ロソルブアセテートを122ｇ添加し粘度595ポアズ／25℃
の粘稠な樹脂を得た。以下この物を樹脂Ｄとする。Comparative Example 1 Phenolic novolac type epoxy resin DEN438 188 g (1.0 equivalent), acrylic acid 72 g manufactured by Dow Chemical Company, USA
(1.0 eq.) Hydroquinone 0.1 g, benzyldimethylamine 0.8 g, and solvent butyl cellosolve acetate 70 g were charged, and the reaction was carried out at 120 ° C. for 9 hours while blowing air, and the acid value of the ester became almost zero. Then maleic anhydride 98
When g (1.0 mol) was charged and reacted at 110 to 120 ° C. for 2 to 3 hours, absorption of acid anhydrides at 1850 and 1770 cm −1 disappeared by infrared spectroscopic analysis, and the acid value of the ester became 156. Furthermore, 122 g of butyl cellosolve acetate was added, and the viscosity was 595 poise / 25 ° C.
A viscous resin was obtained. Hereinafter, this product is referred to as resin D.
以下実施例１と同様な試験を行った。結果は表−１に示
す。 The same test as in Example 1 was performed below. The results are shown in Table-1.
上記表−１のようにエポキシアクリレート樹脂合成時の
エステル化触媒に比較例１の三級アミン触媒を使用した
物で配合したインキは溶剤乾燥時間が30分が限度である
が実施例１〜３の金属塩触媒を使用した物は溶剤乾燥時
間が90分でも現像性が良好であり、溶剤揮散の管理幅を
を大幅にひろげることができた。 As shown in Table 1 above, the ink prepared by using the tertiary amine catalyst of Comparative Example 1 as the esterification catalyst during the synthesis of the epoxy acrylate resin has a solvent drying time of 30 minutes at the maximum, but Examples 1 to 3 The product using the above metal salt catalyst had good developability even when the solvent drying time was 90 minutes, and the control range of solvent volatilization could be greatly expanded.
〔発明の効果〕 本発明の酸無水物ペンダントエポキシアクリレート樹脂
を基本に配合したアルカリ現像型インキや塗料は溶剤の
予備乾燥の時間を長くとることができるため、塗膜中に
溶剤が残存することがなく、特に硬化した塗膜の性能が
要求される電子部品関係のソルダーレジスト用等に有用
である。[Advantages of the Invention] The alkali developing type ink or paint based on the acid anhydride pendant epoxy acrylate resin of the present invention can take a long time for pre-drying of the solvent, so that the solvent remains in the coating film. It is especially useful for solder resists for electronic parts, etc., where the performance of a cured coating film is required.
Claims (1)
キシ樹脂と不飽和一塩基酸とを反応させて得られたエポ
キシアクリレート樹脂の水酸基1.0当量当り0.1〜1.0当
量となる量の二塩基酸無水物を反応させて酸ペンダント
型エポキシアクリレート樹脂を製造するに当り、エステ
ル化触媒として有機酸の金属塩を使用することを特徴と
する酸ペンダント型エポキシアクリレート樹脂の製造
法。1. A dibasic acid in an amount of 0.1 to 1.0 equivalent per 1.0 equivalent of hydroxyl groups of an epoxy acrylate resin obtained by reacting an epoxy resin having two or more epoxy groups in one molecule with an unsaturated monobasic acid. A method for producing an acid pendant epoxy acrylate resin, which comprises using a metal salt of an organic acid as an esterification catalyst in producing an acid pendant epoxy acrylate resin by reacting an anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1150295A JPH0623233B2 (en) | 1989-06-13 | 1989-06-13 | Method for producing acid pendant type epoxy acrylate resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1150295A JPH0623233B2 (en) | 1989-06-13 | 1989-06-13 | Method for producing acid pendant type epoxy acrylate resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0314817A JPH0314817A (en) | 1991-01-23 |
| JPH0623233B2 true JPH0623233B2 (en) | 1994-03-30 |
Family
ID=15493876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1150295A Expired - Lifetime JPH0623233B2 (en) | 1989-06-13 | 1989-06-13 | Method for producing acid pendant type epoxy acrylate resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0623233B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3637987B2 (en) * | 1995-11-20 | 2005-04-13 | ジャパンエポキシレジン株式会社 | Epoxy resin for casting and epoxy resin composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3564074A (en) | 1966-11-28 | 1971-02-16 | Dow Chemical Co | Thermosetting vinyl resins reacted with dicarboxylic acid anhydrides |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4017429A (en) * | 1973-08-17 | 1977-04-12 | Aerojet-General Corporation | Preparation of 2-hydroxyalkyl esters |
| JPS6033098B2 (en) * | 1977-07-26 | 1985-08-01 | 株式会社日本触媒 | Production method of high purity maleic acid monoalcohol ester |
| JPS581716A (en) * | 1981-06-25 | 1983-01-07 | Mitsubishi Electric Corp | Curable resin composition for radiation-resistant material |
| JPS5936118A (en) * | 1982-08-23 | 1984-02-28 | Mitsubishi Gas Chem Co Inc | Thermosetting epoxy acrylate resin composition |
| JPS61157520A (en) * | 1984-12-28 | 1986-07-17 | Showa Highpolymer Co Ltd | Curable composition |
-
1989
- 1989-06-13 JP JP1150295A patent/JPH0623233B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3564074A (en) | 1966-11-28 | 1971-02-16 | Dow Chemical Co | Thermosetting vinyl resins reacted with dicarboxylic acid anhydrides |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0314817A (en) | 1991-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3190251B2 (en) | Photocurable and thermosetting resin composition for alkali-developed flexible printed wiring boards | |
| JP3543409B2 (en) | Active energy ray-curable epoxy acrylate resin composition | |
| JP3673321B2 (en) | Photosensitive resin composition capable of alkali development | |
| JP2878486B2 (en) | Resin composition, solder resist resin composition and cured product thereof | |
| JPS60121444A (en) | Alkali-developable photosensitive resin composition | |
| US5990189A (en) | Coating compositions | |
| JP2000109541A (en) | Photosensitive and thermosetting resin composition | |
| JP2937800B2 (en) | Composition for solder photoresist ink | |
| JP4011885B2 (en) | Method for producing curable resin and composition containing curable resin | |
| JP2001166468A (en) | Photosensitive resin composition and multilayer printed wiring board | |
| JPH0882930A (en) | Photosetting and thermosetting resin composition | |
| JP2963069B2 (en) | Solder photoresist ink composition | |
| JP3403511B2 (en) | Manufacturing method of resist pattern and etching pattern | |
| JPH0623233B2 (en) | Method for producing acid pendant type epoxy acrylate resin | |
| JP2003167331A (en) | Resin composition and cured body thereof | |
| JP2001264977A (en) | Photosensitive resin composition | |
| JP2786533B2 (en) | Unsaturated group-containing polycarboxylic acid resin, resin composition containing the same, solder resist resin composition, and cured product thereof | |
| JP2533557B2 (en) | Photosensitive resin composition | |
| JP4202171B2 (en) | Low dielectric photocurable resin composition | |
| JPH03100009A (en) | Unsaturated polycarboxylic acid resin, resin composition containing same, solder resist resin composition and cured product thereof | |
| JP2002069140A (en) | Alkali developable photosetting and thermosetting composition | |
| JPH02285354A (en) | Photosensitive composition | |
| JP2695359B2 (en) | Photosensitive resin composition and use | |
| JP2000256428A (en) | Hardening resin and composition thereof | |
| JP2896636B2 (en) | Composition for solder photoresist ink |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080330 Year of fee payment: 14 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090330 Year of fee payment: 15 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090330 Year of fee payment: 15 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100330 Year of fee payment: 16 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100330 Year of fee payment: 16 |