JPH0618838B2 - Photopolymerizable resin composition - Google Patents
Photopolymerizable resin compositionInfo
- Publication number
- JPH0618838B2 JPH0618838B2 JP58113843A JP11384383A JPH0618838B2 JP H0618838 B2 JPH0618838 B2 JP H0618838B2 JP 58113843 A JP58113843 A JP 58113843A JP 11384383 A JP11384383 A JP 11384383A JP H0618838 B2 JPH0618838 B2 JP H0618838B2
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- Japan
- Prior art keywords
- parts
- resin composition
- heat
- weight
- resin
- 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
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- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 本発明は光重合性樹脂組成物に関し、詳しくは、耐熱性
のみならず耐有機溶剤性にすぐれた成形品を与える光重
合性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photopolymerizable resin composition, and more particularly to a photopolymerizable resin composition which gives a molded article excellent not only in heat resistance but also in organic solvent resistance.
従来よりポリアリレート、ポリスルホン、ポリエーテル
スルホン、ポリエーテルイミド等のような種々の熱可塑
性の耐熱性樹脂が知られている。これらはその成形が容
易であると共に、そのすぐれた耐熱性を活かしてフイル
ム、シート、電線被覆等の多くの分野で使用されている
が、しかし、その成形品は有機溶剤に対する抵抗性が小
さく、特に、有機溶剤に接触する条件下で表面硬度が低
下し、また、容易にクレージングや亀裂を生じる欠点が
あるので、その用途が尚制約されている。Conventionally, various thermoplastic heat-resistant resins such as polyarylate, polysulfone, polyether sulfone, and polyetherimide are known. These are easy to mold and are used in many fields such as films, sheets and wire coatings by taking advantage of their excellent heat resistance, but the molded products have low resistance to organic solvents, In particular, its use is still restricted because of the drawbacks of lowering the surface hardness under the condition of contact with an organic solvent and easily causing crazing and cracking.
本発明は上記のような熱可塑性耐熱性樹脂から得られる
成形品における問題を解決するためになされたものであ
って、耐有機溶剤性にすぐれた耐熱性樹脂成形品を与え
る熱又は活性エネルギー線重合性樹脂組成物を提供する
ことを目的とする。The present invention has been made to solve the problems in molded articles obtained from the thermoplastic heat-resistant resin as described above, and heat or active energy rays that give heat-resistant resin molded articles excellent in organic solvent resistance. It is intended to provide a polymerizable resin composition.
本発明による光重合性樹脂組成物は、耐熱性樹脂１００
重量部についてＮ−ビニルピロリドン５〜５０重量部と
光重合開始剤とを含有することを特徴とする。The photopolymerizable resin composition according to the present invention comprises a heat resistant resin 100
It is characterized by containing 5 to 50 parts by weight of N-vinylpyrrolidone and a photopolymerization initiator with respect to parts by weight.
本発明において用いる耐熱性樹脂は、熱可塑性であるポ
リアリレート、ポリスルホン、ポリエーテルスルホン、
ポリエーテルイミド等を含み、より具体的には、ポリア
リレートとして で表わされる繰返し単位を有する「Ｕポリマー」（ユニ
チカ（株））、ポリエーテルスルホンとして で表わされる繰返し単位を有する「Victrex」１００
Ｐ、２００Ｐ及び３００Ｐ（I.C.I.社）、ポリエーテル
イミドとして で表わされる繰返し単位を有する「Ultem」１０００
（G.E.社）等を挙げることができる。The heat resistant resin used in the present invention is thermoplastic polyarylate, polysulfone, polyether sulfone,
Including polyether imide, more specifically, as polyarylate As a "U polymer" (Unitika Ltd.) having a repeating unit represented by "Victrex" 100 having a repeating unit represented by
P, 200P and 300P (ICI), as polyetherimide "Ultem" 1000 having a repeating unit represented by
(GE company) and the like.
本発明による光重合性樹脂組成物は、上記のような熱可
塑性耐熱性樹脂１００重量部について重合性単量体とし
てＮ−ビニルピロリドンを５〜５０重量部、好ましくは
１０〜３０重量部を含有する。この重合性単量体は前記
耐熱性樹脂の溶解性にすぐれているので、耐熱性樹脂と
均一な組成物を形成し、後述する光重合開始剤の存在下
に紫外線、電子線等の活性エネルギー線の照射によって
耐熱性樹脂のマトリックス内で重合して、耐熱性樹脂に
目的とする耐有機溶剤性を付与する。しかし、組成物に
おけるその量が、耐熱性樹脂１００重量部について５重
量部よりも少ないときは、かかる耐有機溶剤性の改善の
効果に乏しく、一方、５０重量部を越えるときは、樹脂
組成物における耐熱性樹脂の量が相対的に少なくなっ
て、得られる成形品が本来の耐熱性に劣るようになるの
で好ましくない。The photopolymerizable resin composition according to the present invention contains 5 to 50 parts by weight, preferably 10 to 30 parts by weight of N-vinylpyrrolidone as a polymerizable monomer with respect to 100 parts by weight of the thermoplastic heat resistant resin as described above. To do. Since this polymerizable monomer has excellent solubility in the heat-resistant resin, it forms a uniform composition with the heat-resistant resin, and in the presence of the photopolymerization initiator described later, ultraviolet rays, active energy such as electron beam, etc. By irradiation with rays, the polymer is polymerized in the matrix of the heat resistant resin to impart the desired resistance to the organic solvent to the heat resistant resin. However, when the amount in the composition is less than 5 parts by weight with respect to 100 parts by weight of the heat-resistant resin, the effect of improving the organic solvent resistance is poor, while when it exceeds 50 parts by weight, the resin composition The amount of the heat-resistant resin in (3) becomes relatively small, and the resulting molded article becomes inferior in original heat resistance, which is not preferable.
本発明の光重合性樹脂組成物においては、上記したＮ−
ビニルピロリドン１００重量部について２０重量部以下
の範囲で他の重合性単量体を用いることができる。かか
る重合性単量体としては、例えば、ベンジルアクリレー
ト、カルビトールアクリレート、シクロヘキシルアクリ
レート等のアクリレート単量体やテトラヒドロフルフリ
ルアルコール等を挙げることができる。これら重合性単
量体は前記耐熱性重合体の溶解性がＮ−ビニルピロリド
ンほど良好でないので、Ｎ−ビニルピロリドン１００重
量部について２０重量部を越えて多量に用いることは好
ましくない。In the photopolymerizable resin composition of the present invention, the above N-
Other polymerizable monomers can be used within the range of 20 parts by weight or less per 100 parts by weight of vinylpyrrolidone. Examples of such a polymerizable monomer include acrylate monomers such as benzyl acrylate, carbitol acrylate, and cyclohexyl acrylate, and tetrahydrofurfuryl alcohol. Since the solubility of the heat resistant polymer of these polymerizable monomers is not as good as that of N-vinylpyrrolidone, it is not preferable to use a large amount exceeding 20 parts by weight per 100 parts by weight of N-vinylpyrrolidone.
本発明による光重合性樹脂組成物は、適宜量の光重合開
始剤を含有する。光重合開始剤としては、従来よりビニ
ル単量体の光重合のために用いられるものから任意に選
ばれるが、特に、芳香族ケトン系のものが好ましい。か
かる光重合開始として、例えば、２−メチルプロピオフ
エノン、４−イソプロピル−２−ヒドロキシ−２−メチ
ルプロピオフエノン等を挙げることができる。また、そ
の配合量も特に限定されるものではないが、通常、Ｎ−
ビニルピロリドン１００重量部について0.1〜２重量部
である。The photopolymerizable resin composition according to the present invention contains an appropriate amount of a photopolymerization initiator. The photopolymerization initiator is arbitrarily selected from those conventionally used for photopolymerization of vinyl monomers, but aromatic ketone-based ones are particularly preferable. Examples of such photopolymerization initiation include 2-methylpropiophenone and 4-isopropyl-2-hydroxy-2-methylpropiophenone. Further, the amount thereof is not particularly limited, but usually N-
It is 0.1 to 2 parts by weight per 100 parts by weight of vinylpyrrolidone.
更に、本発明においては、樹脂成分として、前記熱可塑
性耐熱性樹脂に加えて、必要に応じてエポキシ樹脂、ポ
リエステル樹脂、ポリエステルイミド樹脂等の熱硬化性
樹脂を耐熱性樹脂１００重量部について５０重量部以下
の範囲で樹脂組成物に含有させてもよい。５０重量部を
越えて含有させることは、成形後の樹脂製品が柔軟性に
欠けるようになって、用途によっては好ましくないから
である。Further, in the present invention, as a resin component, in addition to the thermoplastic heat resistant resin, a thermosetting resin such as an epoxy resin, a polyester resin or a polyester imide resin may be added in an amount of 50 parts by weight per 100 parts by weight of the heat resistant resin. You may make it contain in a resin composition in the range below a part. If the content exceeds 50 parts by weight, the resin product after molding will lack flexibility, which is not preferable for some applications.
本発明による光重合性樹脂組成物は、通常、耐熱性樹脂
の粉末にＮ−ビニルピロリドンと光重合開始剤とを加
え、必要に応じて加熱下に均一に混合することにより得
られる。その性状は用いるＮ−ビニルピロリドンの量に
もよるが、これが多いときは耐熱性樹脂が溶解して粘稠
な溶液乃至ゴム状の半固体を呈し、少ないときは粉末状
を呈する。The photopolymerizable resin composition according to the present invention is usually obtained by adding N-vinylpyrrolidone and a photopolymerization initiator to a powder of a heat resistant resin and, if necessary, uniformly mixing with heating. The property depends on the amount of N-vinylpyrrolidone used, but when the amount is large, the heat-resistant resin is dissolved to give a viscous solution or a rubber-like semisolid, and when the amount is small, it is powdery.
また、その成形方法は何ら制限されず、本発明で用いる
熱可塑性耐熱性樹脂に通常適用される成形方法、例え
ば、押出成形、射出成形等、任意の方法によることがで
きる。The molding method is not particularly limited, and any molding method usually applied to the thermoplastic heat-resistant resin used in the present invention, such as extrusion molding and injection molding, can be used.
本発明による光重合性樹脂組成物は、以上のように、耐
熱性樹脂、重合性単量体としてのＮ−ビニルピロリドン
及び光重合開始剤を含有するので、容易に任意の形状の
成形品に成形し得ると共に、このようにして得られた成
形品に紫外線、電子線等の活性エネルギー線を照射する
ことによって、Ｎ−ビニルピロリドンが耐熱性樹脂のマ
トリックス内で重合し、いわば耐熱性樹脂に架橋構造に
類似した３次元構造をもたせるため、その望ましい耐熱
性を保持しつつ、耐有機溶剤性を高めることができる。As described above, the photopolymerizable resin composition according to the present invention contains a heat resistant resin, N-vinylpyrrolidone as a polymerizable monomer, and a photopolymerization initiator, and thus can be easily formed into a molded article of any shape. Along with being moldable, the molded product thus obtained is irradiated with active energy rays such as ultraviolet rays and electron beams, whereby N-vinylpyrrolidone is polymerized in the matrix of the heat-resistant resin, so to speak, into a heat-resistant resin. Since it has a three-dimensional structure similar to the cross-linked structure, it is possible to enhance the organic solvent resistance while maintaining the desired heat resistance.
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。尚、以
下において部は重量部を意味し、また、紫外線は、８０
Ｗ／cmのメタルハイドライドランプにて１０cmの距離か
ら照射した。The present invention is described below with reference to examples, but the present invention is not limited to these examples. In the following, “parts” means “parts by weight”, and ultraviolet rays are 80 parts.
Irradiation was performed from a distance of 10 cm with a W / cm metal hydride lamp.
実施例１ ポリエーテルイミド「Ultem 1000」１００部にＮ−ビニ
ルピロリドン１０部と２−ヒドロキシ−２−メチルプロ
ピオフエノン２部を均一に混合し、本発明の樹脂組成物
を得た。この組成物を厚み３０μのフイルムに成形した
後、紫外線照射した。Example 1 10 parts of N-vinylpyrrolidone and 2 parts of 2-hydroxy-2-methylpropiophenone were uniformly mixed with 100 parts of polyetherimide "Ultem 1000" to obtain a resin composition of the present invention. This composition was molded into a film having a thickness of 30 μm and then irradiated with ultraviolet rays.
実施例２ ポリエーテルスルホン「２００Ｐ」１００部にＮ−ビニ
ルピロリドン１５部と２−ヒドロキシ−２−メチルプロ
ピオフエノン２部を均一に混合し、本発明の樹脂組成物
を得た。この組成物を厚み３０μのフイルムに成形した
後、紫外線照射した。Example 2 15 parts of N-vinylpyrrolidone and 2 parts of 2-hydroxy-2-methylpropiophenone were uniformly mixed with 100 parts of polyether sulfone "200P" to obtain a resin composition of the present invention. This composition was molded into a film having a thickness of 30 μm and then irradiated with ultraviolet rays.
実施例３ 実施例１と同じポリエーテルイミド１００部にＮ−ビニ
ルピロリドン１０部と４−イソプロピル−２−ヒドロキ
シ−２−メチルプロピオフエノン２部を均一に混合し、
更にエポキシ樹脂「エピコート１００４」２０部を均一
に混合し、本発明の樹脂組成物を得た。この組成物を厚
み３０μのフイルムに成形し、紫外線照射した後、１８
０℃の温度で３０分間加熱した。Example 3 100 parts of the same polyetherimide as in Example 1 was uniformly mixed with 10 parts of N-vinylpyrrolidone and 2 parts of 4-isopropyl-2-hydroxy-2-methylpropiophenone.
Further, 20 parts of the epoxy resin "Epicoat 1004" was uniformly mixed to obtain a resin composition of the present invention. This composition was molded into a film having a thickness of 30 μm, and after irradiating with ultraviolet rays,
Heat at a temperature of 0 ° C. for 30 minutes.
実施例４ 実施例１と同じポリエーテルイミド１００部にＮ−ビニ
ルピロリドン５０部と４−イソプロピル−２−ヒドロキ
シ−２−メチルプロピオフエノン４部を均一に混合し、
本発明の樹脂組成物を得た。この組成物を銅板上に厚み
３０μに塗布した後、紫外線照射した。Example 4 100 parts of the same polyetherimide as in Example 1 was uniformly mixed with 50 parts of N-vinylpyrrolidone and 4 parts of 4-isopropyl-2-hydroxy-2-methylpropiophenone,
A resin composition of the present invention was obtained. This composition was applied on a copper plate to a thickness of 30 μm and then irradiated with ultraviolet rays.
上で得た各フイルムについてその表面硬度を測定すると
共に、室温で表に示す各有機溶剤中に２４時間浸漬し、
鉛筆硬度を測定すると共にその表 面状態を観察した。結果を表に示す。比較のために、実
施例１と同じポリエーテルイミド及び実施例２と同じポ
リエーテルスルホンをそれぞれ厚み３０μのフイルムに
成形し、上と同様に表面硬度及び耐有機溶剤性を評価
し、その結果をそれぞれ比較例１及び２として表に併せ
て示す。The surface hardness of each of the films obtained above was measured and immersed in each organic solvent shown in the table at room temperature for 24 hours,
The pencil hardness is measured and the table The surface condition was observed. The results are shown in the table. For comparison, the same polyetherimide as in Example 1 and the same polyether sulfone as in Example 2 were each molded into a film having a thickness of 30 μm, and the surface hardness and the organic solvent resistance were evaluated in the same manner as above, and the results were shown. The results are shown in Tables as Comparative Examples 1 and 2, respectively.
比較例による樹脂成形品は有機溶剤に浸漬後、表面硬度
が著しく低下し、また、表面に亀裂が発生するのに対し
て、本発明による樹脂組成物からの成形品は、有機溶剤
に浸漬後も良好な表面硬度と表面状態を保持し、耐有機
溶剤性にすぐれることが明らかである。After the resin molded article according to the comparative example is dipped in an organic solvent, the surface hardness is remarkably reduced, and a crack is generated on the surface, whereas the molded article from the resin composition according to the present invention is dipped in the organic solvent. It is also clear that they maintain good surface hardness and surface condition and have excellent organic solvent resistance.
Claims (1)
Ｎ−ビニルピロリドン５〜５０重量部と光重合開始剤と
を含有することを特徴とする光重合性樹脂組成物。1. A photopolymerizable resin composition comprising 5 to 50 parts by weight of N-vinylpyrrolidone per 100 parts by weight of a thermoplastic heat resistant resin and a photopolymerization initiator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58113843A JPH0618838B2 (en) | 1983-06-23 | 1983-06-23 | Photopolymerizable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58113843A JPH0618838B2 (en) | 1983-06-23 | 1983-06-23 | Photopolymerizable resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS604514A JPS604514A (en) | 1985-01-11 |
| JPH0618838B2 true JPH0618838B2 (en) | 1994-03-16 |
Family
ID=14622441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58113843A Expired - Lifetime JPH0618838B2 (en) | 1983-06-23 | 1983-06-23 | Photopolymerizable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0618838B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0743783B2 (en) * | 1988-07-18 | 1995-05-15 | 沖電気工業株式会社 | Overrun prevention mechanism of ticket issuing device |
| JP2002030125A (en) * | 2000-04-17 | 2002-01-31 | Asahi Medical Co Ltd | New hydrophilized aromatic polymer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55137130A (en) * | 1979-04-12 | 1980-10-25 | Sumitomo Chem Co Ltd | Production of modified polyphenylene oxide |
-
1983
- 1983-06-23 JP JP58113843A patent/JPH0618838B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS604514A (en) | 1985-01-11 |
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