JP2001064307A - Photosensitive resin composition - Google Patents
Photosensitive resin compositionInfo
- Publication number
- JP2001064307A JP2001064307A JP23854599A JP23854599A JP2001064307A JP 2001064307 A JP2001064307 A JP 2001064307A JP 23854599 A JP23854599 A JP 23854599A JP 23854599 A JP23854599 A JP 23854599A JP 2001064307 A JP2001064307 A JP 2001064307A
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive resin
- resin composition
- methacrylic acid
- mol
- parts
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高感度で、且つ要
求に応じた硬度が得られる感光性樹脂組成物に関するも
のであり、金属またはプラスチック基材上に該感光性樹
脂組成物層を設けて、感光性樹脂凸版として利用できる
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition having high sensitivity and a required hardness, wherein a photosensitive resin composition layer is provided on a metal or plastic substrate. Thus, it can be used as a photosensitive resin relief printing plate.
【０００２】[0002]
【従来の技術】従来より、感光性樹脂層に透明部分を持
つネガティブまたはポジティブの原図フィルムを通して
活性光線を照射し、原図フィルムの透明部分に対応する
感光性樹脂に光重合を起こさせ、ついで未光重合部分を
適当な溶剤で除去することによってレリーフを形成せし
めること、およびこれを印刷版材として用いることが知
られている。2. Description of the Related Art Conventionally, an actinic ray is irradiated through a negative or positive original film having a transparent portion on a photosensitive resin layer to cause photopolymerization of a photosensitive resin corresponding to the transparent portion of the original film. It is known to form a relief by removing the photopolymerized portion with a suitable solvent, and to use this as a printing plate material.
【０００３】一般に感光性樹脂凸版の印刷品質は、感光
性樹脂層の硬さで大きく左右されることが知られてい
る。感光性樹脂層が硬い場合は印圧によるレリーフ頂部
の変形が小さいために細線や点の画像の再現性は優れて
いるが、樹脂硬度が高くなるにつれてインキ転移性が悪
くなり易い傾向にある。そのために樹脂硬度には最適な
硬度範囲があり、ショアーＤで５０から６５°の間が望
まれている。[0003] It is generally known that the printing quality of a photosensitive resin relief printing plate is greatly affected by the hardness of the photosensitive resin layer. When the photosensitive resin layer is hard, since the deformation of the top of the relief due to the printing pressure is small, the reproducibility of images of fine lines and dots is excellent. However, as the resin hardness increases, the ink transfer property tends to deteriorate. Therefore, there is an optimum hardness range for the resin hardness, and a Shore D of between 50 and 65 ° is desired.
【０００４】一方、充分な樹脂硬度を得るためには光重
合性不飽和化合物としてメタクリル酸エポキシエステル
基を有する化合物が有効であることが知られているが、
光重合速度が遅いために低感度の感光性樹脂組成物にな
るという問題点があった。そこで、上記の問題点を解決
するために、高感度化を目的として光重合開始剤量を増
加することが考えられるが、光重合開始剤の吸収により
ベース（支持体）に近い底部の光硬化が不充分になるた
めに画像再現性が低下するという問題点がある。On the other hand, it is known that a compound having a methacrylic acid epoxy ester group is effective as a photopolymerizable unsaturated compound in order to obtain a sufficient resin hardness.
There is a problem that the photosensitive resin composition has low sensitivity due to a low photopolymerization rate. In order to solve the above problems, it is conceivable to increase the amount of the photopolymerization initiator for the purpose of increasing the sensitivity. Is insufficient, so that image reproducibility is deteriorated.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、従来の感光
性樹脂凸版の問題点を解決するものであり、高硬度で且
つ高感度の感光性樹脂組成物を提供することを課題とす
るものである。SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the conventional photosensitive resin letterpress and to provide a photosensitive resin composition having high hardness and high sensitivity. It is.
【０００６】[0006]
【課題を解決するための手段】上記の課題を解決するた
め、本発明者らは先に従来例として示した光重合性不飽
和化合物としてメタクリル酸エポキシエステルを有する
化合物が高硬度化には有効であるが、欠点として低感度
になる問題があることに着目し、欠点の解決のため鋭意
研究を重ねた。その結果、メタクリル酸エポキシエステ
ル基による低感度化の欠点を解決するために光重合性に
優れたアクリル酸エポキシエステル基とメタクリル酸エ
ポキシエステル基とを特定の範囲で含有させることで高
硬度で且高感度の感光性樹脂組成物を達成し、遂に本発
明を完成することができた。即ち本発明は、 少なくとも
可溶性合成高分子化合物、光重合性不飽化合物および光
重合開始剤を含有する感光性樹脂組成物であって、前記
光重合性不飽和化合物が多価アルコールのポリグリシジ
ルエーテルとメタアクリル酸及びアクリル酸との開環付
加反応生成物であり、かつメタアクリル酸の反応比率が
２５〜７５モル％の範囲にあることを特徴とする感光性
樹脂組成物である。Means for Solving the Problems To solve the above-mentioned problems, the present inventors have found that a compound having an epoxy ester of methacrylic acid as a photopolymerizable unsaturated compound previously shown as a conventional example is effective for increasing the hardness. However, they paid attention to the problem of low sensitivity as a drawback, and conducted intensive research to solve the drawback. As a result, in order to solve the drawback of lowering the sensitivity due to the methacrylic acid epoxy ester group, high hardness and high hardness can be achieved by containing the acrylic acid epoxy ester group and the methacrylic acid epoxy ester group having excellent photopolymerizability in a specific range. A highly sensitive photosensitive resin composition was achieved, and the present invention was finally completed. That is, the present invention is a photosensitive resin composition containing at least a soluble synthetic polymer compound, a photopolymerizable unsaturated compound and a photopolymerization initiator, wherein the photopolymerizable unsaturated compound is a polyglycidyl ether of a polyhydric alcohol. A reaction product of methacrylic acid and methacrylic acid and acrylic acid, and the reaction ratio of methacrylic acid is in the range of 25 to 75 mol%.
【０００７】本発明において、可溶性合成高分子化合物
としては公知の可溶性合成高分子化合物を使用出来る。
例えばポリエーテルアミド（例えば特開昭 55 − 79437
号公報等 )、ポリエーテルエステルアミド（例えば特開
昭58−113537公報等 )、三級窒素含有ポリアミド（例え
ば特開昭50−76055公報等 )、アンモニウム塩型三級窒
素原子含有ポリアミド（例えば特開昭53−36555公報等
)、アミド結合を一つ以上有するアミド化合物と有機ジ
イソシアネート化合物の付加重合体（例えば特開昭58−
140737公報等）、アミド結合を有しないジアミンと有機
ジイソシアネート化合物の付加重合体（例えば特開平 4
−97154公報等 )等があげられ、その中でも三級窒素原
子含有ポリアミド及びアンモニウム塩型三級窒素原子含
有ポリアミドが好ましい。In the present invention, known soluble synthetic polymer compounds can be used as the soluble synthetic polymer compound.
For example, polyether amide (for example, JP-A-55-79437)
), Polyetheresteramides (for example, JP-A-58-113537, etc.), tertiary nitrogen-containing polyamides (for example, JP-A-50-76055, etc.), and ammonium salt-type tertiary nitrogen atom-containing polyamides (for example, Kaisho 53-36555, etc.
), An addition polymer of an amide compound having at least one amide bond and an organic diisocyanate compound (for example,
140737), an addition polymer of a diamine having no amide bond and an organic diisocyanate compound (for example, JP-A No.
And the like. Of these, a tertiary nitrogen atom-containing polyamide and an ammonium salt type tertiary nitrogen atom-containing polyamide are preferable.
【０００８】次に本発明における光重合性不飽和化合物
としては、多価アルコールのポリグリシジルエーテルと
メタアクリル酸及びアクリル酸との開環付加反応生成物
であり、前記多価アルコールとして具体的には、ジペン
タエリスリトール、ペンタエリスリトール、トリメチロ
ールプロパン、グリセリン、エチレングリコール、ジエ
チレングリコール、トリエチレングリコール、フタル酸
のエチレンオキサイド付加物等が挙げられ、その中でも
トリメチロールプロパンが好ましい。Next, the photopolymerizable unsaturated compound in the present invention is a product of a ring-opening addition reaction of polyglycidyl ether of a polyhydric alcohol with methacrylic acid and acrylic acid. Examples thereof include dipentaerythritol, pentaerythritol, trimethylolpropane, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, and ethylene oxide adducts of phthalic acid. Of these, trimethylolpropane is preferable.
【０００９】なお、本発明における光重合性不飽和化合
物のメタアクリル酸の反応比率は、２５〜７５モル％の
範囲、好ましくは３０〜７０モル％、特に３５〜６５モ
ル％であることが望ましく、反応比率が２５モル％未満
では、硬度が低くなり、一方７５モル％を超えると、感
度が低くなるので好ましくない。前記メタアクリル酸の
反応比率が２５〜７５モル％の範囲にある光重合性不飽
和化合物を得る方法としては、多価アルコールのポリグ
リシジルエーテルとメタクリル酸との付加反応物を多価
アルコールのポリグリシジルエーテルとアクリル酸との
反応物に対して２５〜７５モル％の比率で混合してもよ
いが、製造の面から多価アルコールのポリグリシジルエ
ーテルとの付加反応時にメタアクリル酸とアクリル酸を
適切な範囲で混合することが望ましい。なお、メタアク
リル酸及びアクリル酸の反応比率は２５〜７５モル％で
あるが、要求される感光性樹脂組成物の硬度によって適
度に選定すればよい。In the present invention, the reaction ratio of the photopolymerizable unsaturated compound to methacrylic acid is in the range of 25 to 75 mol%, preferably 30 to 70 mol%, and more preferably 35 to 65 mol%. If the reaction ratio is less than 25 mol%, the hardness becomes low, while if it exceeds 75 mol%, the sensitivity becomes low, which is not preferable. As a method for obtaining a photopolymerizable unsaturated compound in which the reaction ratio of methacrylic acid is in the range of 25 to 75 mol%, an addition reaction product of polyglycidyl ether of polyhydric alcohol and methacrylic acid is used for polyhydric alcohol polymethod. The reaction product of glycidyl ether and acrylic acid may be mixed in a ratio of 25 to 75 mol%, but methacrylic acid and acrylic acid are added during the addition reaction of polyhydric alcohol with polyglycidyl ether from the viewpoint of production. It is desirable to mix in an appropriate range. In addition, the reaction ratio of methacrylic acid and acrylic acid is 25 to 75 mol%, but may be appropriately selected depending on the required hardness of the photosensitive resin composition.
【００１０】なお、本発明感光性樹脂組成物において、
製造時または保存時の安定性を向上させるために公知の
熱重合禁止剤を配合することは可能である。熱重合禁止
剤の具体的な例としては、フェノール類、ハイドロキノ
ン類、カテコール類、フェノチアジン類等が挙げられ
る。その他、可塑剤、染料、顔料、紫外線吸収剤、香料
などを添加することができる。[0010] In the photosensitive resin composition of the present invention,
It is possible to incorporate a known thermal polymerization inhibitor in order to improve the stability during production or storage. Specific examples of the thermal polymerization inhibitor include phenols, hydroquinones, catechols, phenothiazines and the like. In addition, a plasticizer, a dye, a pigment, an ultraviolet absorber, a fragrance, and the like can be added.
【００１１】[0011]
【発明の実施の態様】本発明の感光性樹脂組成物を製造
する方法としては、可溶性高分子化合物、光重合性不飽
和化合物及び光重合開始剤などの混合は、公知の任意の
方法に従って行なうことができる。例えば、溶融状態で
混合する方法、或いはアルコールなどの適当な溶媒で混
合したのちに溶剤を除去する方法などが挙げられる。ま
た本発明の組成物は、例えば熱プレス、注型、或いは溶
融押し出し、溶液キャストなどの任意の方法により、所
望の厚みの板、フィルム、又は箔などシート状物とする
ことに積層することができる。支持体としては、スチー
ル、アルミニウム、ガラス、ポリエステルフィルムなど
のプラスチックフィルム、アルミ蒸着したフィルムなど
任意のものが使用できる。BEST MODE FOR CARRYING OUT THE INVENTION As a method for producing the photosensitive resin composition of the present invention, mixing of a soluble polymer compound, a photopolymerizable unsaturated compound and a photopolymerization initiator is carried out according to any known method. be able to. For example, a method of mixing in a molten state, a method of mixing with an appropriate solvent such as alcohol, and then removing the solvent can be used. Further, the composition of the present invention can be laminated on a sheet, such as a plate, film, or foil, having a desired thickness by any method such as hot pressing, casting, or melt extrusion, and solution casting. it can. As the support, any material such as steel, aluminum, glass, a plastic film such as a polyester film, an aluminum vapor-deposited film and the like can be used.
【００１２】[0012]
【実施例】次に本発明を実施例を用いて具体的に説明す
るが、本発明はこれらの実施例によってなんら制限され
るものではない。なお、部とあるのは重量部を意味す
る。硬度及び感度は、以下の方法で測定した。 １）硬度：西独ツビック社製、ショアー式デュロメータ
ー（ショアーＤタイプ）を用いて室温下（２５℃）で測
定した。 ２）感度：ストッファー社製２１段のグレースケールを
感光性樹脂表面に乗せて日本電子精機社製ケミカルラン
プ露光機で２分間露光した後、２５℃の中性水で現像
し、７０℃で１０分間乾燥後に４分間の後露光を行って
得たレリーフの硬化段数で表した。EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In addition, "parts" means parts by weight. Hardness and sensitivity were measured by the following methods. 1) Hardness: Measured at room temperature (25 ° C.) using a Shore durometer (Shore D type) manufactured by Zubik Co., Ltd. 2) Sensitivity: A 21-step gray scale manufactured by Stoffer was placed on the photosensitive resin surface and exposed for 2 minutes with a chemical lamp exposing machine manufactured by JEOL Ltd., developed with neutral water at 25 ° C., and then developed at 70 ° C. for 10 minutes. The relief was obtained by performing post-exposure for 4 minutes after drying for 1 minute, and expressed by the number of curing steps of the relief obtained.
【００１３】実施例１ ε−カプロラクタム５００重量部、Ｎ，Ｎ’−ビスアミ
ノプロピルピペラジンとアジピン酸とのナイロン塩４５
０重量部、１，３−ビス（アミノメチル）シクロヘキサ
ンとアジピン酸のナイロン塩５０部とを重合せしめて、
比粘度２．４０の３級窒素原子を有するポリアミドを得
た。このようにして得られたポリアミド５５部をメタノ
ール２００部に溶解し、この溶液にメタクリル酸３部、
トリメチロールプロパントリグリシジルエーテルとアク
リル酸５０モル％及びメタクリル酸５０モル％との反応
物３６部、Ｎ−エチル−Ｐ−トルエンスルホンアミド５
部、ハイドロキノンモノメチルエーテル０．１部、ベン
ジルジメチルケタール１部を加え、感光性樹脂組成物溶
液を得た。この溶液をテフロンコートしたシャーレに流
延し、暗室にてメタノールを除去後、更に一昼夜４０℃
で減圧乾燥し、厚み約８００μの組成物シートを得た。
このシートを褐色顔料入り接着剤を２０μコートした２
５０μのペットフィルムに張り合わせ、更に組成物の上
面にポリビニルアルコールを２μコートした厚さ１２５
μのペットフィルムでカバーし、１１０℃で熱プレスし
て感光性樹脂層の厚みが７００μの感光性樹脂原版を作
成した。次いでこの原版よりカバーフィルムを剥離し、
感光性樹脂表面に検査ネガを密着させ２分間露光した。
ネガを取り除いた後、２５℃の中性水で３分間現像し、
７０℃で１０分間乾燥した。得られた感光性樹脂の感度
は１５段、樹脂硬度はショアーＤで６０であり、満足で
きるものであった。Example 1 Nylon salt 45 of N, N'-bisaminopropylpiperazine and adipic acid, 500 parts by weight of ε-caprolactam
0 parts by weight of 1,3-bis (aminomethyl) cyclohexane and 50 parts of adipic acid nylon salt are polymerized,
A polyamide having a specific viscosity of 2.40 and having a tertiary nitrogen atom was obtained. 55 parts of the polyamide thus obtained was dissolved in 200 parts of methanol, and 3 parts of methacrylic acid was added to this solution.
36 parts of a reaction product of trimethylolpropane triglycidyl ether with 50 mol% of acrylic acid and 50 mol% of methacrylic acid, N-ethyl-P-toluenesulfonamide 5
Parts, 0.1 part of hydroquinone monomethyl ether and 1 part of benzyldimethyl ketal were added to obtain a photosensitive resin composition solution. The solution was cast on a petri dish coated with Teflon, and methanol was removed in a dark room.
And dried under reduced pressure to obtain a composition sheet having a thickness of about 800 μm.
This sheet was coated with a brown pigment-containing adhesive at 20 μm.
A film having a thickness of 125 μm is attached to a 50 μm pet film and further coated with 2 μm of polyvinyl alcohol on the upper surface of the composition.
Covered with a .mu. pet film and hot-pressed at 110.degree. C. to prepare a photosensitive resin master having a photosensitive resin layer thickness of 700 .mu.m. Next, the cover film was peeled off from this master,
An inspection negative was brought into close contact with the photosensitive resin surface and exposed for 2 minutes.
After removing the negative, develop with neutral water at 25 ° C for 3 minutes,
Dry at 70 ° C. for 10 minutes. The sensitivity of the obtained photosensitive resin was 15 steps, and the resin hardness was 60 at Shore D, which was satisfactory.
【００１４】比較例１ 実施例１において光硬化性不飽和化合物としてトリメチ
ロールプロパンのトリグリシジルロールとアクリル酸８
０モル％及びメタクリル酸２０モル％との反応物を用い
た以外は全て実施例１と同様にして、感光性樹脂組成物
を作成した。得られた感光性樹脂の感度は１６段であっ
たが、樹脂硬度はショアーＤで４８であり、満足できる
ものではなかった。Comparative Example 1 In Example 1, triglycidyl roll of trimethylolpropane and acrylic acid 8 were used as the photocurable unsaturated compound.
A photosensitive resin composition was prepared in the same manner as in Example 1 except that a reaction product of 0 mol% and 20 mol% of methacrylic acid was used. The sensitivity of the obtained photosensitive resin was 16 steps, but the resin hardness was 48 at Shore D, which was not satisfactory.
【００１５】比較例２ 実施例１において光硬化性不飽和化合物としてトリメチ
ロールプロパンのトリグリシジルロールとアクリル酸２
０モル％及びメタクリル酸８０モル％との反応物を用い
た以外は全て実施例１と同様にして感光性樹脂組成物を
作成した。得られた感光性樹脂の樹脂硬度はショアーＤ
で６４と満足できるものであったが、感度は１３段と低
く、満足できるものではなかった。Comparative Example 2 In Example 1, triglycidyl roll of trimethylolpropane and acrylic acid 2 were used as the photocurable unsaturated compound.
A photosensitive resin composition was prepared in the same manner as in Example 1 except that a reaction product of 0 mol% and 80 mol% of methacrylic acid was used. The resin hardness of the obtained photosensitive resin is Shore D
Was 64, which was satisfactory, but the sensitivity was as low as 13 steps, which was not satisfactory.
【００１６】実施例２ 実施例１において光硬化性不飽和化合物としてトリメチ
ロールプロパンのトリグリシジルエーテルとアクリル酸
２５モル％及びメタクリル酸７５モル％との反応物を用
いた以外は全て実施例１と同様にして感光性樹脂組成物
を作成し、レリーフを作成した。得られた感光性樹脂の
感度は１５段で樹脂硬度はショアーＤで６２であり、満
足できるものであった。Example 2 The procedure of Example 1 was repeated except that a reaction product of triglycidyl ether of trimethylolpropane with 25 mol% of acrylic acid and 75 mol% of methacrylic acid was used as the photocurable unsaturated compound. Similarly, a photosensitive resin composition was prepared, and a relief was prepared. The sensitivity of the obtained photosensitive resin was 15 steps, and the resin hardness was 62 at Shore D, which was satisfactory.
【００１７】実施例３ 実施例１の光硬化性不飽和化合物としてトリメチロール
プロパンのトリグリシジルエーテルとアクリル酸７０モ
ル％及びメタクリル酸３０モル％との反応物を用いた以
外は全て実施例１と同様にして感光性樹脂組成物を作成
し、レリーフを作成した。得られた感光性樹脂の感度は
１６段で樹脂硬度はショアーＤで５６であり、満足でき
るものであった。Example 3 The procedure of Example 1 was repeated except that the reaction product of the triglycidyl ether of trimethylolpropane with 70 mol% of acrylic acid and 30 mol% of methacrylic acid was used as the photocurable unsaturated compound of Example 1. Similarly, a photosensitive resin composition was prepared, and a relief was prepared. The sensitivity of the obtained photosensitive resin was 16 steps, and the resin hardness was 56 at Shore D, which was satisfactory.
【００１８】実施例４ 実施例１において光硬化性不飽和化合物としてエチレン
グリコールジエポキシエーテルとアクリル酸３０モル％
及びメタアクリル酸７０モル％との反応物を用いた以外
は全て実施例１と同様にして感光性樹脂組成物を作成
し、レリーフを作成した。得られた感光性樹脂の感度は
１５段、樹脂硬度はショアーＤで５７と満足できるもの
であった。Example 4 In Example 1, ethylene glycol diepoxy ether and acrylic acid 30 mol% as the photocurable unsaturated compound were used.
A photosensitive resin composition was prepared in the same manner as in Example 1 except that a reaction product with methacrylic acid and 70 mol% of methacrylic acid was used, and a relief was prepared. The sensitivity of the obtained photosensitive resin was 15 steps, and the resin hardness was 57, which was satisfactory at Shore D.
【００１９】実施例５ 数平均分子量６００のポリオキシエチレングリコールの
両末端にアクリロニトリルを付加し、これを水素還元し
て得たα、ω−ジアミノポリオキシエチレンとアジピン
酸との当モル塩５５重量部、ε−カプロラクタム２５重
量部、およびヘキサメチレンジアミンとアジピン酸との
当モル塩２０重量部を通常の条件で溶融重合して相対粘
度（ポリマ−１ｇを抱水クロラ−ル１００〓に溶解し、
２５℃で測定した）２．１のポリアミドを得た。得られ
た重合体５５部をメタノール２００部に溶解し、この溶
液に実施例１で用いたトリメチロールプロパントリグリ
シジルエーテルとアクリル酸５０モル％及びメタクリル
酸５０モル％との反応物３９部、Ｎ−エチル−Ｐ−トル
エンスルホンアミド５部、ハイドロキノンモノメチルエ
ーテル０．１部、ベンジルジメチルケタール１部を加
え、感光性樹脂組成物溶液を得た。得られた感光性樹脂
組成物を実施例１と同様にして感光性樹脂組成物を作成
し、レリーフを作成した。得られた感光性樹脂の感度は
１５段、樹脂硬度はショアーＤで５７であり、満足でき
るものであった。Example 5 Acrylonitrile was added to both ends of polyoxyethylene glycol having a number average molecular weight of 600, and the resulting product was reduced with hydrogen to obtain an equimolar salt of α, ω-diaminopolyoxyethylene and adipic acid of 55% by weight. Parts, 25 parts by weight of ε-caprolactam, and 20 parts by weight of an equimolar salt of hexamethylenediamine and adipic acid are melt-polymerized under ordinary conditions to obtain a relative viscosity (1 g of polymer dissolved in 100 ° of chloral hydrate) ,
A polyamide of 2.1 (measured at 25 ° C.) was obtained. 55 parts of the obtained polymer was dissolved in 200 parts of methanol, and 39 parts of a reaction product of the trimethylolpropane triglycidyl ether used in Example 1 with 50 mol% of acrylic acid and 50 mol% of methacrylic acid was dissolved in 200 parts of methanol. -Ethyl-P-toluenesulfonamide (5 parts), hydroquinone monomethyl ether (0.1 parts) and benzyldimethyl ketal (1 part) were added to obtain a photosensitive resin composition solution. A photosensitive resin composition was prepared from the obtained photosensitive resin composition in the same manner as in Example 1, and a relief was prepared. The sensitivity of the obtained photosensitive resin was 15 steps, and the resin hardness was 57 at Shore D, which was satisfactory.
【００２０】実施例６ ２−メチルペンタメチレンジアミン ４部、Ｎ，Ｎ’−
ビス（３−アミノプロピル）ピペラジン１４部をメタノ
ールに溶解し、ポリエチレングリコール（平均分子量６
００）６００部とヘキサメチレンジイソシアネート３７
０部と反応させて末端に実質的に両末端にイソシアネー
ト基を有するウレタンオリゴマーを８２部をジアミンの
溶液に攪拌下に徐々に添加した。両者の反応は１０分間
で完了した。この溶液をテフロンコートしたシャーレに
取り、メタノールを蒸発除去後、減圧乾燥して得られた
重合体は、主鎖にポリエチレングリコール鎖を５０％含
有し、比粘度が１．５５であった。得られた重合体５５
部をメタノール２００部に溶解し、アジピン酸３．１部
を加えて溶解した。この溶液に実施例２で使用したトリ
メチロールプロパンのトリグリシジルエーテルとアクリ
ル酸２５モル％及びメタクリル酸７５モル％との反応物
３４部、Ｎ−エチル−Ｐ−トルエンスルホンアミド５
部、ハイドロキノンモノメチルエーテル０．１部、ベン
ジルジメチルケタール１部を加え、実施例１と用いて同
様に感光性樹脂組成物を作成し、レリーフを作成した。
得られた感光性樹脂の感度は１５段、樹脂硬度はショア
ーＤで５６であり、満足できるものであった。EXAMPLE 6 4 parts of 2-methylpentamethylenediamine, N, N'-
14 parts of bis (3-aminopropyl) piperazine was dissolved in methanol, and polyethylene glycol (average molecular weight: 6
00) 600 parts and hexamethylene diisocyanate 37
After reacting with 0 parts, 82 parts of a urethane oligomer having isocyanate groups at both ends substantially at the ends were gradually added to the diamine solution with stirring. Both reactions were completed in 10 minutes. This solution was placed in a Teflon-coated petri dish, methanol was removed by evaporation, and then dried under reduced pressure. The polymer obtained contained 50% of a polyethylene glycol chain in the main chain and had a specific viscosity of 1.55. The obtained polymer 55
Was dissolved in 200 parts of methanol, and 3.1 parts of adipic acid was added and dissolved. To this solution, 34 parts of a reaction product of triglycidyl ether of trimethylolpropane used in Example 2 with 25 mol% of acrylic acid and 75 mol% of methacrylic acid, N-ethyl-P-toluenesulfonamide 5
Parts, 0.1 part of hydroquinone monomethyl ether and 1 part of benzyldimethyl ketal were added, and a photosensitive resin composition was prepared in the same manner as in Example 1 to prepare a relief.
The sensitivity of the obtained photosensitive resin was 15 steps, and the resin hardness was 56 on the Shore D, which was satisfactory.
【００２１】[0021]
【発明の効果】以上、かかる構成よりなる本発明は、優
れた感度を有するとともに、要求に応じた硬度を得るこ
とができるので、産業界に寄与すること大である。As described above, the present invention having such a constitution has excellent sensitivity and can obtain hardness as required, and therefore greatly contributes to the industry.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小木 浩二 滋賀県大津市堅田二丁目１番１号 東洋紡 績株式会社総合研究所内 (72)発明者 南村 公子 滋賀県大津市堅田二丁目１番１号 東洋紡 績株式会社総合研究所内 (72)発明者 富田 晃 滋賀県大津市堅田二丁目１番１号 東洋紡 績株式会社総合研究所内 Ｆターム(参考） 2H025 AA01 AA04 AB02 AC01 AD01 BC14 BC49 BC82 CA00 CB24 CC01 4J011 AA05 PA96 QA02 QB19 QB24 RA06 SA51 TA01 WA01 4J026 AB28 BA27 BA28 CA09 GA07 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Koji Ogi, Inventor 2-1-1 Katata, Otsu-shi, Shiga Prefecture Toyobo Co., Ltd. Research Institute (72) Kimiko Minamimura 2-1-1 Katata, Otsu-shi, Shiga Prefecture Inside Toyobo Co., Ltd. (72) Inventor Akira Tomita 2-1-1 Katata, Otsu-shi, Shiga F-term inside Toyobo Co., Ltd. (reference) 2H025 AA01 AA04 AB02 AC01 AD01 BC14 BC49 BC82 CA00 CB24 CC01 4J011 AA05 PA96 QA02 QB19 QB24 RA06 SA51 TA01 WA01 4J026 AB28 BA27 BA28 CA09 GA07
Claims (1)
合性不飽化合物および光重合開始剤を含有する感光性樹
脂組成物であって、前記光重合性不飽和化合物が多価ア
ルコールのポリグリシジルエーテルとメタアクリル酸及
びアクリル酸との開環付加反応生成物であり、かつメタ
アクリル酸の反応比率が２５〜７５モル％の範囲にある
ことを特徴とする感光性樹脂組成物。1. A photosensitive resin composition containing at least a soluble synthetic polymer compound, a photopolymerizable unsaturated compound and a photopolymerization initiator, wherein the photopolymerizable unsaturated compound is a polyglycidyl ether of a polyhydric alcohol. And a methacrylic acid and a product of a ring-opening addition reaction of acrylic acid, wherein the reaction ratio of methacrylic acid is in the range of 25 to 75 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23854599A JP4543291B2 (en) | 1999-08-25 | 1999-08-25 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23854599A JP4543291B2 (en) | 1999-08-25 | 1999-08-25 | Photosensitive resin composition |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009214338A Division JP2010015169A (en) | 2009-09-16 | 2009-09-16 | Photosensitive resin composition |
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| Publication Number | Publication Date |
|---|---|
| JP2001064307A true JP2001064307A (en) | 2001-03-13 |
| JP4543291B2 JP4543291B2 (en) | 2010-09-15 |
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ID=17031853
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013117741A (en) * | 2011-09-09 | 2013-06-13 | Toyobo Co Ltd | Water-developable photosensitive resin laminate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5632138A (en) * | 1979-08-23 | 1981-04-01 | Toray Ind Inc | Photosensitive polyamide composition |
| JPH0519459A (en) * | 1991-07-16 | 1993-01-29 | Toyobo Co Ltd | Photosensitive resin composition |
| JPH06322039A (en) * | 1993-05-08 | 1994-11-22 | Takemoto Oil & Fat Co Ltd | Photopolymerizable composition for optical three-dimensional shaping |
| JPH1149840A (en) * | 1997-08-05 | 1999-02-23 | Nippon Shokubai Co Ltd | Curable resin and resin composition |
| JPH11209380A (en) * | 1998-01-23 | 1999-08-03 | Ricoh Co Ltd | Production of metal phthalocyanine |
-
1999
- 1999-08-25 JP JP23854599A patent/JP4543291B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5632138A (en) * | 1979-08-23 | 1981-04-01 | Toray Ind Inc | Photosensitive polyamide composition |
| JPH0519459A (en) * | 1991-07-16 | 1993-01-29 | Toyobo Co Ltd | Photosensitive resin composition |
| JPH06322039A (en) * | 1993-05-08 | 1994-11-22 | Takemoto Oil & Fat Co Ltd | Photopolymerizable composition for optical three-dimensional shaping |
| JPH1149840A (en) * | 1997-08-05 | 1999-02-23 | Nippon Shokubai Co Ltd | Curable resin and resin composition |
| JPH11209380A (en) * | 1998-01-23 | 1999-08-03 | Ricoh Co Ltd | Production of metal phthalocyanine |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013117741A (en) * | 2011-09-09 | 2013-06-13 | Toyobo Co Ltd | Water-developable photosensitive resin laminate |
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| Publication number | Publication date |
|---|---|
| JP4543291B2 (en) | 2010-09-15 |
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