JPH0570536A - Ultraviolet-curable resin composition and optical fiber cladding material comprising the same - Google Patents
Ultraviolet-curable resin composition and optical fiber cladding material comprising the sameInfo
- Publication number
- JPH0570536A JPH0570536A JP3261109A JP26110991A JPH0570536A JP H0570536 A JPH0570536 A JP H0570536A JP 3261109 A JP3261109 A JP 3261109A JP 26110991 A JP26110991 A JP 26110991A JP H0570536 A JPH0570536 A JP H0570536A
- Authority
- JP
- Japan
- Prior art keywords
- ultraviolet
- optical fiber
- resin
- resin composition
- curable 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、光ファイバの被覆材
料などに用いられる紫外線硬化型樹脂組成物に関し、特
に硬化性を向上したものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-curable resin composition used as a coating material for optical fibers and the like, and more particularly to a composition having improved curability.
【０００２】[0002]
【従来の技術】従来より、光ファイバの被覆材料の一種
として紫外線硬化型樹脂組成物（以下、ＵＶ樹脂と略記
する。）が使用されている。このＵＶ樹脂は、ウレタン
−アクリレート系オリゴマーにアクリレート系の反応性
モノマーを配合し、光重合開始剤を添加したものであ
る。このＵＶ樹脂は、紡糸直後の光ファイバ裸線に塗布
され、紫外線を照射することで重合が開始し、硬化して
被覆材となる。2. Description of the Related Art Conventionally, an ultraviolet curable resin composition (hereinafter abbreviated as UV resin) has been used as a kind of coating material for optical fibers. This UV resin is obtained by blending a urethane-acrylate-based oligomer with an acrylate-based reactive monomer and adding a photopolymerization initiator. This UV resin is applied to a bare optical fiber immediately after spinning, and polymerization is started by irradiating with an ultraviolet ray, and the resin is cured to form a coating material.
【０００３】ところで、光ファイバの生産性を高めるた
めに、光ファイバの紡糸速度を高める試みがなされてい
る。しかしながら、紡糸速度を高めるには、紡糸直後に
行われるＵＶ樹脂の塗布、硬化をこれに合せめて速める
必要があり、特にＵＶ樹脂の硬化速度を紡糸速度の高速
化に合わせて高速とする必要がある。In order to increase the productivity of optical fibers, attempts have been made to increase the spinning speed of optical fibers. However, in order to increase the spinning speed, it is necessary to accelerate the application and curing of the UV resin immediately after the spinning, and in particular, it is necessary to increase the curing speed of the UV resin in accordance with the increase in the spinning speed. is there.
【０００４】[0004]
【発明が解決しようとする課題】よって、この発明にお
ける課題は、硬化速度の速いＵＶ樹脂を得ることにあ
る。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to obtain a UV resin having a high curing rate.
【０００５】[0005]
【課題を解決するための手段】かかる課題は、ＵＶ樹脂
中に含まれる光重合開始剤として、紫外線が照射されて
発生するラジカル分子の反応活性点の原子のアトミック
ポピュレーション（以下、ＡＰと略記する。）が−１．
２以下であるものを用いることで解決される。As a photopolymerization initiator contained in a UV resin, this problem is solved by the atomic population of atoms at the reaction active points of radical molecules generated by irradiation with ultraviolet rays (hereinafter abbreviated as AP). ) Is -1.
The problem is solved by using one that is 2 or less.
【０００６】以下、この発明を詳しく説明する。一般に
ＵＶ樹脂の硬化反応の第一段階は、紫外線を照射するこ
とで、光重合開始剤からラジカル分子が発生し、これが
架橋モノマーやオリゴマーと次々に反応していく。この
ラジカル分子と架橋モノマーあるいはオリゴマーとの反
応速度が速ければ速い程ＵＶ樹脂の重合速度、すなわち
硬化速度が速くなることになる。この反応速度の速さ
は、ラジカル分子の反応活性点の原子の電子状態によっ
て推定することができる。本発明者は、鋭意検討の結
果、ラジカル分子の反応活性点の原子のＡＰが−１．２
以下である場合は、ＵＶ樹脂の硬化速度が速いことを見
出した。The present invention will be described in detail below. Generally, in the first step of the curing reaction of the UV resin, by irradiating with ultraviolet rays, radical molecules are generated from the photopolymerization initiator, and these react with the crosslinking monomer and oligomer one after another. The faster the reaction rate between the radical molecules and the crosslinking monomer or oligomer, the faster the polymerization rate of the UV resin, that is, the curing rate. The speed of this reaction can be estimated by the electronic state of the atom at the reaction active point of the radical molecule. As a result of earnest studies, the present inventor has found that the AP of the atom at the reaction active point of the radical molecule is -1.2.
It has been found that the curing rate of the UV resin is high when it is below.
【０００７】つぎに、この発明におけるＡＰについて説
明する。ＡＰは、量子化学の分野では公知で、一般的に
使われており、（例えば、「量子化学入門（上）」米沢
貞次郎他著，（株）化学同人，８２頁参照）、分子中の
各原子における電子の分布状態を表わし、この値が正で
かつ大きくなれば、電子受容性が大きくなり、負でかつ
大きくなれば、電子供与性が大きくなる。ＡＰの計算方
法としては、この発明では拡張ヒュッケル法を採用し
た。Next, the AP in the present invention will be described. AP is well known and commonly used in the field of quantum chemistry (see, for example, “Introduction to Quantum Chemistry (1)”, Sadajiro Yonezawa et al., Kagaku Dojin Co., Ltd., p. 82), each in the molecule. It represents the distribution state of electrons in an atom. When this value is positive and large, the electron accepting property is large, and when it is negative and large, the electron donating property is large. As the AP calculation method, the extended Hückel method is adopted in the present invention.
【０００８】本発明では、ラジカル分子の反応活性点の
原子のＡＰが−１．２以下である反光重合開始剤を選択
することで、これを含むＵＶ樹脂の硬化速度が高められ
る。この条件に合致する光重合開始剤の例としては、下
記化学式（Ｉ）で表わされるアシルホスフィンオキサイ
ド、下記化学式（ＩＩ）で表わされる２−エチルアンス
ラキノン、下記化学式（ＩＩＩ）で表わされるα−アシ
ロキシムエステルなどが挙げられる。例えばアシルホス
フィンオキサイドに紫外線を照射して発生する２個のラ
ジカル分子の構造は下記化学式（Ｉ〓）で表わされ、そ
の反応活性点の炭素原子およびリン原子のＡＰは−０．
９および−１．４である。ＡＰが−１．４であることは
電子供与性が大きく、架橋モノマーやオリゴマーとの反
応性が高い光重合開始剤であり、結果的にＵＶ樹脂の重
合速度、すなわち硬化速度が速くなる。In the present invention, by selecting an anti-photopolymerization initiator in which the AP of the atom at the reaction active point of the radical molecule is -1.2 or less, the curing rate of the UV resin containing the same can be increased. Examples of the photopolymerization initiator which meets this condition include acylphosphine oxide represented by the following chemical formula (I), 2-ethylanthraquinone represented by the following chemical formula (II), and α-represented by the following chemical formula (III). An acyloxime ester etc. are mentioned. For example, the structure of two radical molecules generated by irradiating an acylphosphine oxide with ultraviolet rays is represented by the following chemical formula (I〓), and the AP of the carbon atom and the phosphorus atom of the reaction active point is −0.
9 and -1.4. AP of -1.4 is a photopolymerization initiator having a large electron donating property and a high reactivity with the crosslinking monomer or oligomer, and as a result, the polymerization rate of the UV resin, that is, the curing rate is increased.
【０００９】[0009]
【化１】 [Chemical 1]
【００１０】（ここで式中Ｍｅはメチル基を示す。）(Here, Me represents a methyl group.)
【００１１】[0011]
【化２】 [Chemical 2]
【００１２】[0012]
【化３】 [Chemical 3]
【００１３】[0013]
【化４】 [Chemical 4]
【００１４】（ここで式中Ｍｅはメチル基を示す。）(Here, Me represents a methyl group.)
【００１５】本発明において、ラジカル分子の反応活性
点の原子のＡＰを−１．２以下と規定したのは、−１．
２より大きいとラジカル分子と架橋モノマーあるいはオ
リゴマーとの反応性が低く、ＵＶ樹脂の硬化速度の向上
が得られないためである。従来のＵＶ樹脂に配合される
光重合開始剤としては、ベンジルジメチルケタール（例
えばチバガイギー社製イルガキュア６５１）、２−ヒド
ロキシ−２−メチルー１−フェニルプロパン−１−オン
（例えばメルク社製ダロキュアー１１７３）、ベンゾイ
ンメチルエーテル、ベンゾインイソプロピルエーテル等
があるが、これらの光重合開始剤に紫外線が照射されて
発生するラジカル分子の反応活性点の原子のＡＰは約−
１．０〜−０．２であり、架橋モノマーやオリゴマーと
の反応性の低いものである。In the present invention, the AP of the atom at the reaction active point of the radical molecule is defined to be -1.2 or less, because -1.
If it is greater than 2, the reactivity between the radical molecule and the cross-linking monomer or oligomer is low, and the curing rate of the UV resin cannot be improved. As a photopolymerization initiator compounded in a conventional UV resin, benzyl dimethyl ketal (for example, Irgacure 651 manufactured by Ciba Geigy), 2-hydroxy-2-methyl-1-phenylpropan-1-one (for example, Darocur 1173 manufactured by Merck). , Benzoin methyl ether, benzoin isopropyl ether, etc., but the AP of the atom at the reaction active point of the radical molecule generated by irradiating these photopolymerization initiators with ultraviolet rays is about −
It is 1.0 to -0.2 and has low reactivity with the crosslinking monomer and oligomer.
【００１６】また、光重合開始剤は紫外線が照射される
と１個以上のラジカル分子を発生するが、そのうちのす
べてのラジカル分子が上記条件を満足するものである必
要はなく、すくなくとも１個のラジカル分子がその条件
を満たさせばよい。Further, the photopolymerization initiator generates one or more radical molecules when it is irradiated with ultraviolet rays, but it is not necessary that all the radical molecules among them satisfy the above conditions, and at least one radical molecule is required. The radical molecule should satisfy the condition.
【００１７】このような光重合開始剤を配合したＵＶ樹
脂では、ラジカル分子と架橋モノマーあるいはオリゴマ
ーとの反応速度が高くなり、ＵＶ樹脂全体の硬化速度が
高くなる。このため、このＵＶ樹脂を光ファイバの被覆
材料とすることで溶融紡糸速度を十分に高めることがで
き、光ファイバの全体の製造速度を高めることができ
る。In the UV resin containing such a photopolymerization initiator, the reaction rate between the radical molecule and the cross-linking monomer or oligomer increases, and the curing rate of the entire UV resin increases. Therefore, by using this UV resin as a coating material for the optical fiber, the melt spinning speed can be sufficiently increased, and the manufacturing speed of the entire optical fiber can be increased.
【００１８】（実施例）表１に示す配合組成の２種のＵ
Ｖ樹脂（Ｉ，II）を調製した。これらのＵＶ樹脂の各成
分の配合比は同一とした。なお、アシルホスフィンオキ
サイドから生じたラジカル分子の反応活性点の原子のＡ
Ｐは−０．９と−１．４であり、イルガキュア６５１か
ら生じたラジカル分子の反応活性点の原子のＡＰは−
０．９と−０．８である。(Example) Two types of U having the composition shown in Table 1
V resin (I, II) was prepared. The compounding ratio of each component of these UV resins was the same. In addition, A of the atom at the reaction active point of the radical molecule generated from acylphosphine oxide
P is -0.9 and -1.4, and AP of the atom at the reaction active point of the radical molecule generated from Irgacure 651 is-.
0.9 and -0.8.
【００１９】[0019]
【表１】 [Table 1]
【００２０】これら２種のＵＶ樹脂について、紫外線照
射量２５ｍＪ／ｃｍ2 と５００ｍＪ／ｃｍ2 とでそれぞ
れ紫外線照射し厚さ０．２ｍｍのシートサンプルを作成
し、表２に示す試験を行った。結果を表２に併せて示
す。These two kinds of UV resins were respectively irradiated with ultraviolet rays at an ultraviolet irradiation dose of 25 mJ / cm 2 and 500 mJ / cm 2 to prepare sheet samples having a thickness of 0.2 mm, and the tests shown in Table 2 were conducted. The results are also shown in Table 2.
【００２１】[0021]
【表２】 [Table 2]
【００２２】表２の結果から、ＵＶ樹脂Ｉ（本発明品）
は、紫外線の低照射量においてもかなりの硬化が進行し
ており、光重合開始剤としてのアシルホスフィンオキサ
イドの効果が確認された。From the results of Table 2, UV resin I (product of the present invention)
The compound was considerably cured even with a low irradiation amount of ultraviolet rays, and the effect of acylphosphine oxide as a photopolymerization initiator was confirmed.
【００２３】[0023]
【発明の効果】以上説明したように、この発明のＵＶ樹
脂は、ラジカル分子の反応活性点の原子のＡＰが−１．
２以下の光重合開始剤を配合したものであるので、その
ＵＶ樹脂の紫外線による硬化速度が十分に高いものとな
る。また、この発明の光ファイバ用被覆材料は、このＵ
Ｖ樹脂からなるものであるので、被覆層の硬化を短時間
に完了することができ、結果的に光ファイバの溶融紡糸
速度を十分速めることができ、光ファイバの生産性を向
上させることができる。また、これによれば新たな設備
などを設ける必要がなく、生産コストが嵩むこともな
い。As described above, in the UV resin of the present invention, the AP of the atom at the reaction active point of the radical molecule is -1.
Since it contains 2 or less photopolymerization initiators, the UV resin has a sufficiently high curing speed by ultraviolet rays. Further, the coating material for an optical fiber of the present invention is U
Since it is made of V resin, the curing of the coating layer can be completed in a short time, and as a result, the melt spinning speed of the optical fiber can be sufficiently increased, and the productivity of the optical fiber can be improved. . Moreover, according to this, it is not necessary to provide new equipment and the like, and the production cost does not increase.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 5/00 ＰＮＷ 6904−4Ｊ Ｇ０２Ｂ 6/44 ３０１ Ａ 7036−2Ｋ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location C09D 5/00 PNW 6904-4J G02B 6/44 301 A 7036-2K
Claims (2)
樹脂組成物において、光重合開始剤に紫外線が照射され
て生成するラジカル分子の反応活性点の原子のアトミッ
クポピュレーションが−１．２以下であることを特徴と
する紫外線硬化型樹脂組成物。1. An ultraviolet-curable resin composition containing a photopolymerization initiator, wherein the atomic population of the reaction active points of radical molecules produced by irradiating the photopolymerization initiator with ultraviolet rays is -1.2. The following is an ultraviolet-curable resin composition.
からなることを特徴とする光ファイバ用被覆材料。2. An optical fiber coating material comprising the ultraviolet curable resin composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3261109A JPH0570536A (en) | 1991-09-12 | 1991-09-12 | Ultraviolet-curable resin composition and optical fiber cladding material comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3261109A JPH0570536A (en) | 1991-09-12 | 1991-09-12 | Ultraviolet-curable resin composition and optical fiber cladding material comprising the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0570536A true JPH0570536A (en) | 1993-03-23 |
Family
ID=17357214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3261109A Pending JPH0570536A (en) | 1991-09-12 | 1991-09-12 | Ultraviolet-curable resin composition and optical fiber cladding material comprising the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0570536A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773486A (en) * | 1996-09-26 | 1998-06-30 | Lucent Technologies Inc. | Method for the manufacture of optical gratings |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH029732A (en) * | 1988-03-14 | 1990-01-12 | Nippon Kayaku Co Ltd | Coating material for optical glass fiber |
| JPH0234620A (en) * | 1988-07-26 | 1990-02-05 | Mitsui Toatsu Chem Inc | Photocurable resin composition |
| JPH02117910A (en) * | 1988-10-28 | 1990-05-02 | Mitsui Toatsu Chem Inc | Photo-setting resin composition |
-
1991
- 1991-09-12 JP JP3261109A patent/JPH0570536A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH029732A (en) * | 1988-03-14 | 1990-01-12 | Nippon Kayaku Co Ltd | Coating material for optical glass fiber |
| JPH0234620A (en) * | 1988-07-26 | 1990-02-05 | Mitsui Toatsu Chem Inc | Photocurable resin composition |
| JPH02117910A (en) * | 1988-10-28 | 1990-05-02 | Mitsui Toatsu Chem Inc | Photo-setting resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773486A (en) * | 1996-09-26 | 1998-06-30 | Lucent Technologies Inc. | Method for the manufacture of optical gratings |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 19970708 |