JP2005320435A - Ultraviolet-curable resin composition - Google Patents
Ultraviolet-curable resin composition Download PDFInfo
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- JP2005320435A JP2005320435A JP2004139549A JP2004139549A JP2005320435A JP 2005320435 A JP2005320435 A JP 2005320435A JP 2004139549 A JP2004139549 A JP 2004139549A JP 2004139549 A JP2004139549 A JP 2004139549A JP 2005320435 A JP2005320435 A JP 2005320435A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 22
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 6
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 claims description 4
- -1 oxetane compound Chemical class 0.000 description 24
- 239000003822 epoxy resin Substances 0.000 description 22
- 229920000647 polyepoxide Polymers 0.000 description 22
- 230000003287 optical effect Effects 0.000 description 20
- 238000002834 transmittance Methods 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- Polyethers (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、光通信分野にて使用される光学部品や光学部品組み立て用に用いられる透明樹脂において、光信号を低損失で通す透明性と優れた接着力を有し、光電気混載基板等に使用される場合の半田耐熱信頼性が高く、また耐湿信頼性に優れた紫外線硬化型樹脂組成物に関するものである。特に、レンズの固定、光デバイスパッケージのシールやＶ溝基板への光ファイバーの固定、光導波路やレンズ等の光学部品材料等として有用な紫外線硬化型樹脂組成物に関するものである。 The present invention is an optical component used in the field of optical communication and a transparent resin used for assembling an optical component, has transparency and excellent adhesive strength for passing an optical signal with low loss, and is suitable for an opto-electric hybrid board or the like. The present invention relates to an ultraviolet curable resin composition having high solder heat resistance reliability and excellent moisture resistance reliability when used. In particular, the present invention relates to an ultraviolet curable resin composition useful as a lens fixing, an optical device package seal, an optical fiber fixing to a V-groove substrate, an optical component material such as an optical waveguide or a lens.
近年、高透明な光学用接着剤はもとより、高分子材料を用いた光導波路が提案され、実用化されつつある。このように、各種光学材料としては、加工が容易である、広範囲の用途に使用可能である、屈折率の調整が容易である等種々の利点を有することから、高分子材料が用いられている。このような状況のなか、例えば、オキセタン環を有する化合物を用いた高分子材料が提案されている（特許文献１参照）。
しかしながら、上記高分子材料は、耐熱性および耐湿性の点で充分なものとは言えず、より優れた特性の向上が望まれている。 However, it cannot be said that the polymer material is sufficient in terms of heat resistance and moisture resistance, and improvement of more excellent characteristics is desired.
本発明は、このような事情に鑑みなされたもので、耐熱性および耐湿性に優れ、透過率に優れた紫外線硬化型樹脂組成物の提供をその目的とする。 This invention is made | formed in view of such a situation, The objective is to provide the ultraviolet curable resin composition which was excellent in heat resistance and moisture resistance, and excellent in the transmittance | permeability.
上記の目的を達成するため、本発明の紫外線硬化型樹脂組成物は、下記の（Ａ）〜（Ｃ）を含有するという構成をとる。
（Ａ）下記の構造式（１）で表される３−エチル−３−（フェノキシメチル）オキセタン。
(A) 3-ethyl-3- (phenoxymethyl) oxetane represented by the following structural formula (1).
すなわち、本発明者は、優れた耐熱性および耐湿性を有する紫外線硬化型樹脂組成物を得るために鋭意検討を重ねた。その結果、上記特定のオキセタン化合物（Ａ）を用いるとともに、エポキシ樹脂として、上記特定のエポキシ樹脂（Ｂ）を用いると、上記特定のオキセタン化合物（Ａ）は１官能性化合物でフェニル基を有するために硬化物のガラス転移温度（Ｔｇ）が低く、高分子量の硬化物を形成することが可能となる。一方、上記特定のエポキシ樹脂（Ｂ）はフッ素化エポキシ樹脂であり透明性が高いが反応性が低く、また通常、オキセタン類の化合物とは相溶しないものであるが、上記特定のオキセタン化合物（Ａ）および上記特定のエポキシ樹脂（Ｂ）は相溶性が良好で、両者を併用することにより、耐熱性が著しく向上し、透明性の良好な硬化物が得られるようになるため、上記のような所期の目的が達成されることを見出し本発明に到達した。 That is, the present inventor has intensively studied to obtain an ultraviolet curable resin composition having excellent heat resistance and moisture resistance. As a result, when using the specific oxetane compound (A) and using the specific epoxy resin (B) as an epoxy resin, the specific oxetane compound (A) is a monofunctional compound and has a phenyl group. In addition, the glass transition temperature (Tg) of the cured product is low, and a high molecular weight cured product can be formed. On the other hand, the specific epoxy resin (B) is a fluorinated epoxy resin and has high transparency but low reactivity, and is usually incompatible with oxetane compounds, but the specific oxetane compound ( A) and the specific epoxy resin (B) have good compatibility, and by using both in combination, the heat resistance is remarkably improved and a cured product having good transparency can be obtained. The present invention has been achieved by finding that a desired purpose is achieved.
このように、本発明は、上記特定のオキセタン化合物（Ａ）と、上記特定の液状エポキシ樹脂（Ｂ）を用いた紫外線硬化型樹脂組成物である。このため、高い透明性を有し、かつ半田温度相当の高温放置下においても透過率の減少がほとんどなく、低損失となる。また、プレッシャークッカー試験（ＰＣＴ）のような過酷な耐湿信頼性試験においても剥離等が生じることもなく優れた密着性を備えている。したがって、本発明の紫外線硬化型樹脂組成物を、光通信系におけるＶグルーヴや光導波路（ＡＷＧ）等の精密光部品の接着およびファイバーアレイの接着用途、また光導波路およびレンズ等の成形材料として用いると、高信頼性の良好な光学系を得ることができる。 Thus, this invention is an ultraviolet curable resin composition using the said specific oxetane compound (A) and the said specific liquid epoxy resin (B). For this reason, it has high transparency, and the transmittance hardly decreases even when left at a high temperature corresponding to the solder temperature, resulting in low loss. Further, even in a severe moisture resistance reliability test such as a pressure cooker test (PCT), it has excellent adhesion without causing peeling. Therefore, the ultraviolet curable resin composition of the present invention is used for adhesion of precision optical parts such as V grooves and optical waveguides (AWG) in optical communication systems and fiber arrays, and as a molding material for optical waveguides and lenses. Thus, a highly reliable optical system can be obtained.
さらに、上記成分に加えて３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレートを用いると、上記特定のオキセタン化合物（Ａ）と特定のエポキシ樹脂（Ｂ）の相溶性を高め、均一でより透明性の高い硬化物を得ることができる。 Further, when 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is used in addition to the above components, the compatibility between the specific oxetane compound (A) and the specific epoxy resin (B) is increased and uniform. A cured product with higher transparency can be obtained.
本発明の紫外線硬化型樹脂組成物は、特定のオキセタン化合物（Ａ）と、特定の液状エポキシ樹脂（Ｂ）と、光重合開始剤（Ｃ）とを用いることにより得られる。 The ultraviolet curable resin composition of this invention is obtained by using a specific oxetane compound (A), a specific liquid epoxy resin (B), and a photoinitiator (C).
上記特定のオキセタン化合物（Ａ）は、下記の構造式（１）で表される３−エチル−３−（フェノキシメチル）オキセタンである。 The specific oxetane compound (A) is 3-ethyl-3- (phenoxymethyl) oxetane represented by the following structural formula (1).
上記構造式（１）で表される３−エチル−３−（フェノキシメチル）オキセタンとしては、例えば、東亞合成社製のＯＸＴ−２１１等があげられる。 Examples of 3-ethyl-3- (phenoxymethyl) oxetane represented by the structural formula (1) include OXT-211 manufactured by Toagosei Co., Ltd.
上記構造式（１）で表される３−エチル−３−（フェノキシメチル）オキセタン（Ａ）の含有割合は、この特定のオキセタン化合物（Ａ）および特定のエポキシ樹脂（Ｂ）の合計量の４０〜８０重量％の範囲内となるよう設定することが好ましい。特に好ましくは５０〜７０重量％である。すなわち、４０重量％未満では、充分な硬化性を得ることが困難であり、８０重量％を超えると、未反応の揮発成分量が増加し硬化物物性が低下する傾向がみられるからである。 The content ratio of 3-ethyl-3- (phenoxymethyl) oxetane (A) represented by the structural formula (1) is 40% of the total amount of the specific oxetane compound (A) and the specific epoxy resin (B). It is preferable to set it within the range of ˜80% by weight. Particularly preferred is 50 to 70% by weight. That is, if it is less than 40% by weight, it is difficult to obtain sufficient curability, and if it exceeds 80% by weight, the amount of unreacted volatile components tends to increase and the physical properties of the cured product tend to decrease.
上記特定のオキセタン化合物（Ａ）とともに用いられる特定の液状エポキシ樹脂（Ｂ）は、下記の一般式（２）で表されるフッ素化直鎖脂肪族型の液状エポキシ樹脂である。上記エポキシ樹脂は低粘度であり、このエポキシ樹脂を用いることにより樹脂組成物全体の低粘度化を図ることが可能となる。 The specific liquid epoxy resin (B) used together with the specific oxetane compound (A) is a fluorinated linear aliphatic liquid epoxy resin represented by the following general formula (2). The epoxy resin has a low viscosity, and by using this epoxy resin, it is possible to reduce the viscosity of the entire resin composition.
上記式（２）中の繰り返し数ｎは２〜１０の整数であり、好ましくは４〜１０の整数である。 The repeating number n in the above formula (2) is an integer of 2 to 10, preferably an integer of 4 to 10.
さらに、本発明においては、上記特定のエポキシ樹脂（Ｂ）とともに、他のエポキシ樹脂を併用することができる。上記他のエポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、脂環式エポキシ樹脂、水素添加型ビスフェノールＡ型エポキシ樹脂、水素添加型ビスフェノールＦ型エポキシ樹脂等があげられる。これらは単独でもしくは２種以上併せて用いられる。なかでも、透明で耐熱性が高く、相溶性が良好であるという点から、下記の構造式（３）で表される３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレートを併用することが好ましい。 Furthermore, in this invention, another epoxy resin can be used together with the said specific epoxy resin (B). Examples of the other epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, alicyclic epoxy resins, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, and the like. These may be used alone or in combination of two or more. Among them, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate represented by the following structural formula (3) is used in combination because it is transparent, has high heat resistance, and has good compatibility. It is preferable.
これら他のエポキシ樹脂を併用する場合の使用割合は、上記特定のエポキシ樹脂（Ｂ）との合計量の５０重量％以下となるよう設定することが好ましい。すなわち、５０重量％を超えると、透明性が低下したり、高温放置時の黄変がひどくなる傾向がみられるからである。 When using these other epoxy resins in combination, the use ratio is preferably set to be 50% by weight or less of the total amount with the specific epoxy resin (B). That is, when it exceeds 50% by weight, the transparency tends to decrease or yellowing when left at high temperature tends to be severe.
上記一般式（２）で表される液状エポキシ樹脂（Ｂ）の含有割合は、（Ａ）および（Ｂ）の合計量の２０〜６０重量％の範囲内となるよう設定することが好ましい。特に好ましくは３０〜５０重量％である。すなわち、２０重量％未満では、充分な半田耐熱性の向上効果が得られ難く、６０重量％を超えると、上記特定のオキセタン化合物（Ａ）と相溶しにくくなる傾向がみられるからである。 The content ratio of the liquid epoxy resin (B) represented by the general formula (2) is preferably set to be in the range of 20 to 60% by weight of the total amount of (A) and (B). Particularly preferably, it is 30 to 50% by weight. That is, if it is less than 20% by weight, it is difficult to obtain a sufficient effect of improving the solder heat resistance, and if it exceeds 60% by weight, it tends to be difficult to be compatible with the specific oxetane compound (A).
上記特定のオキセタン化合物（Ａ）および特定のエポキシ樹脂（Ｂ）とともに用いられる光重合開始剤（Ｃ）としては、特に限定するものではなく、芳香族ジアゾニウム塩、芳香族スルホニウム塩、芳香族ヨードニウム塩、芳香族スルホキソニウム塩、メタロセン化合物あるいは鉄アレーン系化合物等を用いることができる。その中でも、光硬化性の観点から、芳香族スルホニウム塩が好ましく、特に芳香族スルホニウム・ヘキサフロロホスホニウム化合物、芳香族スルホニウム・ヘキサフロロアンチモネート化合物、またはその両者の併用が、硬化性、接着性等の観点から好ましい。さらに、上記光重合開始剤（Ｃ）とともに、光増感剤や酸増殖剤等も必要に応じて添加することができる。 The photopolymerization initiator (C) used together with the specific oxetane compound (A) and the specific epoxy resin (B) is not particularly limited, and is an aromatic diazonium salt, aromatic sulfonium salt, aromatic iodonium salt. Aromatic sulfoxonium salts, metallocene compounds, iron arene compounds, and the like can be used. Among these, from the viewpoint of photocurability, aromatic sulfonium salts are preferable, and aromatic sulfonium / hexafluorophosphonium compounds, aromatic sulfonium / hexafluoroantimonate compounds, or a combination of both, are curable, adhesive, etc. From the viewpoint of Furthermore, a photosensitizer, an acid proliferator, etc. can be added with the said photoinitiator (C) as needed.
上記光重合開始剤（Ｃ）の含有量は、上記特定のオキセタン化合物（Ａ）および特定のエポキシ樹脂（Ｂ）の合計量１００重量部（以下「部」と略す）に対して１〜１５部に設定することが好ましく、特に好ましくは２〜１０部である。 The content of the photopolymerization initiator (C) is 1 to 15 parts with respect to 100 parts by weight (hereinafter abbreviated as “part”) of the total amount of the specific oxetane compound (A) and the specific epoxy resin (B). It is preferable to set to 2 to 10 parts, particularly preferably 2 to 10 parts.
また、本発明の紫外線硬化型樹脂組成物には、上記（Ａ）〜（Ｃ）以外に、接着性を高めるためにシラン系あるいはチタン系のカップリング剤、合成ゴムやシリコーン化合物等の可撓性付与剤等の化合物、さらに酸化防止剤、消泡剤等の他の添加剤を必要に応じて適宜に配合することができる。 In addition to the above (A) to (C), the ultraviolet curable resin composition of the present invention includes flexible materials such as silane-based or titanium-based coupling agents, synthetic rubbers, and silicone compounds in order to improve adhesiveness. A compound such as a property-imparting agent, and other additives such as an antioxidant and an antifoaming agent can be appropriately blended as necessary.
本発明の紫外線硬化型樹脂組成物は、例えば、上記（Ａ）〜（Ｃ）、さらに必要に応じて他の添加剤を用いて、所定の割合で配合し溶融混合することにより得られる。 The ultraviolet curable resin composition of the present invention can be obtained, for example, by blending at a predetermined ratio and melt-mixing using the above-mentioned (A) to (C) and, if necessary, other additives.
このようにして得られる紫外線硬化型樹脂組成物は、例えば、ＵＶランプ等により紫外線を照射した後、所定の温度でのポストキュアを行うことにより硬化させることができる。 The ultraviolet curable resin composition thus obtained can be cured by, for example, irradiating ultraviolet rays with a UV lamp or the like and then performing post-curing at a predetermined temperature.
また、本発明の紫外線硬化型樹脂組成物の硬化後の光透過率は、通常、厚み１４０μｍの場合、２５℃雰囲気下、可視光領域（波長５００〜９００ｎｍ）および赤外領域において９５％以上、特に好ましくは９８％以上である。 Further, the light transmittance after curing of the ultraviolet curable resin composition of the present invention is usually 95% or more in the visible light region (wavelength 500 to 900 nm) and infrared region in a 25 ° C. atmosphere when the thickness is 140 μm. Particularly preferably, it is 98% or more.
つぎに、実施例について比較例と併せて説明する。 Next, examples will be described together with comparative examples.
まず、下記に示す各成分を準備した。 First, each component shown below was prepared.
〔オキセタン化合物１〕
前記構造式（１）で表される３−エチル−３−（フェノキシメチル）オキセタン（東亞合成社製、ＯＸＴ−２１１）
[Oxetane compound 1]
3-ethyl-3- (phenoxymethyl) oxetane represented by the structural formula (1) (OXT-211 manufactured by Toagosei Co., Ltd.)
〔オキセタン化合物２〕
下記の構造式（４）で表される２官能オキセタン化合物（東亞合成社製、ＯＸＴ−１２１）
Bifunctional oxetane compound represented by the following structural formula (4) (OXT-121, manufactured by Toagosei Co., Ltd.)
〔エポキシ化合物１〕
前記一般式（２）で表されるフッ素化直鎖脂肪族エポキシ樹脂（ｎ＝４）
[Epoxy compound 1]
Fluorinated linear aliphatic epoxy resin represented by the general formula (2) (n = 4)
〔エポキシ化合物２〕
下記の式（３）で表される３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート（ダイセル化学社製、セロキサイド２０２１Ｐ）
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate represented by the following formula (3) (Dacel Chemical Co., Celoxide 2021P)
〔エポキシ化合物３〕
ビスフェノールＦ型エポキシ樹脂（ジャパンエポキシレジン社製、ＹＬ−６７５３）
[Epoxy compound 3]
Bisphenol F epoxy resin (Japan Epoxy Resin, YL-6753)
〔光重合開始剤〕
スルホニウム・ヘキサフロロアンチモン系重合開始剤（旭電化社製、ＳＰ−１７０）
(Photopolymerization initiator)
Sulphonium hexafluoroantimony polymerization initiator (Asahi Denka Co., Ltd., SP-170)
〔カップリング剤〕
γ−グリシドキシプロピルトリメトキシシラン（信越シリコーン社製、ＫＢＭ−４０３）
[Coupling agent]
γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone, KBM-403)
〔酸化防止剤〕
ＨＣＡ（三光化学社製）
〔Antioxidant〕
HCA (manufactured by Sanko Chemical Co., Ltd.)
〔実施例１〜７、比較例１〜６〕
下記の表１〜表２に示す各配合成分を同表に示す割合で配合し溶融混合（条件：２５℃）することにより紫外線硬化型樹脂組成物を作製した。
[Examples 1-7, Comparative Examples 1-6]
The ultraviolet light curable resin composition was produced by mix | blending each compounding component shown in the following Table 1-Table 2 in the ratio shown to the same table, and melt-mixing (condition: 25 degreeC).
このようにして得られた実施例および比較例の各紫外線硬化型樹脂組成物を用いて、硬化後の初期透過率と半田温度（２６０℃）での透過率、さらに透過率の減少率、およびプレッシャークッカー試験（ＰＣＴ）後の剥離観察を下記の方法に従ってそれぞれ測定・評価した。これらの結果を後記の表３〜表４に併せて示す。 Using the ultraviolet curable resin compositions of Examples and Comparative Examples thus obtained, the initial transmittance after curing, the transmittance at the solder temperature (260 ° C.), the transmittance decreasing rate, and The peeling observation after the pressure cooker test (PCT) was measured and evaluated according to the following methods. These results are shown in Tables 3 to 4 below.
〔各透過率および透過率減少率〕
透過率評価用サンプルをつぎのようにして作製した。すなわち、２枚のパイレックス（登録商標）ガラス（大きさ：４０ｍｍ×２０ｍｍ）の間にスペーサーを用いて、１４０μｍの隙間を形成した。つぎに、この隙間に毛細管現象を利用して紫外線硬化型樹脂組成物を充填した後、紫外線照射を行うことにより硬化させて透過率評価用サンプルを作製した。なお、上記紫外線照射による硬化は、５００ＷのＵＶランプ（高圧水銀ランプ）を用いて、９０００ｍＪ／ｃｍ2 で光照射した後、１００℃で１時間のポストキュアを行った。つぎに、このサンプルを用い、波長８５０ｎｍにおける初期透過率（２５℃）を測定した後、２６０℃の乾燥機に３０分間投入した後のサンプルを再度波長８５０ｎｍでの透過率を測定した。そして、上記初期透過率と２６０℃での透過率の各値から透過率の減少率を算出した。なお、透過率の測定には、分光光度計（ＵＶ−３１０１ＰＣ、島津製作所社製）を用いた。
[Each transmittance and transmittance reduction rate]
A transmittance evaluation sample was produced as follows. That is, a gap of 140 μm was formed using a spacer between two Pyrex (registered trademark) glasses (size: 40 mm × 20 mm). Next, this gap was filled with an ultraviolet curable resin composition utilizing a capillary phenomenon, and then cured by irradiating with ultraviolet rays to prepare a transmittance evaluation sample. The curing by ultraviolet irradiation was performed by irradiating light at 9000 mJ / cm 2 using a 500 W UV lamp (high pressure mercury lamp) and then performing post curing at 100 ° C. for 1 hour. Next, the initial transmittance (25 ° C.) at a wavelength of 850 nm was measured using this sample, and then the transmittance at a wavelength of 850 nm was measured again for the sample after being placed in a dryer at 260 ° C. for 30 minutes. And the decreasing rate of the transmittance | permeability was computed from each value of the said initial transmittance and the transmittance | permeability in 260 degreeC. A spectrophotometer (UV-3101PC, manufactured by Shimadzu Corporation) was used for the measurement of transmittance.
〔ＰＣＴ後の剥離観察〕
上記透過率の測定に用いたサンプルと同様のサンプルを準備し、１２１℃×１００％×２０２．６ｋＰａで２４時間の条件にて、プレッシャークッカー試験を行った。その結果、サンプルの剥離の発生の有無を目視により観察した。
[Peeling observation after PCT]
A sample similar to the sample used for the transmittance measurement was prepared, and a pressure cooker test was performed at 121 ° C. × 100% × 202.6 kPa for 24 hours. As a result, the presence or absence of peeling of the sample was visually observed.
上記結果から、実施例品は、両透過率とも高く、したがって透過率減少率も非常に小さいものであった。このことから、耐熱性に優れたものであることがわかる。また、ＰＣＴ後の剥離観察においても完全に密着しているか、わずかにコーナー部分に剥離が確認さたたのみであった。このことから、耐湿性にも優れたものであることがわかる。 From the above results, the example product was high in both transmittances, and thus the transmittance reduction rate was very small. This shows that it is excellent in heat resistance. Further, in the peeling observation after PCT, it was completely adhered or only a slight peeling was confirmed at the corner portion. This shows that it is excellent also in moisture resistance.
これに対して、特定のオキセタン化合物および特定のエポキシ化合物を用いない比較例１，２品、また特定のオキセタン化合物以外のオキセタン化合物と特定のエポキシ化合物を併用した比較例４品、特定のオキセタン化合物および通常のエポキシ化合物を併用した比較例６品、さらには特定のエポキシ化合物のみ、あるいは特定のオキセタン化合物のみを用いた比較例３，５品は、いずれも透過率の減少率が実施例品に比べて高く、しかもＰＣＴ後の剥離観察においても全面に剥離が確認されたが、周辺部に剥離が確認され、耐熱性および耐湿性ともに劣るものであることは明らかである。 In contrast, Comparative Examples 1 and 2 that do not use a specific oxetane compound and a specific epoxy compound, and Comparative Example 4 that uses an oxetane compound other than a specific oxetane compound and a specific epoxy compound, and a specific oxetane compound In addition, Comparative Example 6 using together with a normal epoxy compound, and Comparative Examples 3 and 5 using only a specific epoxy compound or only a specific oxetane compound, both have a decrease in transmittance in the Example products. In comparison with the observation after peeling by PCT, peeling was confirmed on the entire surface, but peeling was confirmed on the peripheral portion, and it is clear that both heat resistance and moisture resistance are inferior.
本発明の紫外線硬化型樹脂組成物は、例えば、光通信分野にて使用される光学部品や光学部品組み立て用に用いられる透明樹脂、特に、レンズの固定、光デバイスパッケージのシールやＶ溝基板への光ファイバーの固定、光導波路（ＡＷＧ）やレンズ等の成形材料等に用いられる。 The ultraviolet curable resin composition of the present invention is, for example, an optical component used in the field of optical communications and a transparent resin used for assembling optical components, particularly for fixing lenses, sealing optical device packages, and V-groove substrates. It is used for fixing optical fibers, molding materials such as optical waveguides (AWG) and lenses.
Claims (2)
（Ａ）下記の構造式（１）で表される３−エチル−３−（フェノキシメチル）オキセタン。
(A) 3-ethyl-3- (phenoxymethyl) oxetane represented by the following structural formula (1).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010507696A (en) * | 2006-10-24 | 2010-03-11 | チバ ホールディング インコーポレーテッド | Thermally stable cationic photocurable composition |
| JP2011132487A (en) * | 2009-11-25 | 2011-07-07 | Nitto Denko Corp | Photocurable resin composition and optical component using the same |
| US9056941B2 (en) | 2009-06-18 | 2015-06-16 | Nitto Denko Corporation | Photocurable resin composition and optical component using the same |
| WO2016043024A1 (en) * | 2014-09-17 | 2016-03-24 | 株式会社ダイセル | Curable composition and optical element obtained using same |
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2004
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010507696A (en) * | 2006-10-24 | 2010-03-11 | チバ ホールディング インコーポレーテッド | Thermally stable cationic photocurable composition |
| US9056941B2 (en) | 2009-06-18 | 2015-06-16 | Nitto Denko Corporation | Photocurable resin composition and optical component using the same |
| JP2011132487A (en) * | 2009-11-25 | 2011-07-07 | Nitto Denko Corp | Photocurable resin composition and optical component using the same |
| WO2016043024A1 (en) * | 2014-09-17 | 2016-03-24 | 株式会社ダイセル | Curable composition and optical element obtained using same |
| JPWO2016043024A1 (en) * | 2014-09-17 | 2017-07-13 | 株式会社ダイセル | Curable composition and optical element using the same |
| US10351663B2 (en) | 2014-09-17 | 2019-07-16 | Daicel Corporation | Curable composition and optical element obtained using same |
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