JP2008260898A - Curable resin composition and its cured product - Google Patents
Curable resin composition and its cured product Download PDFInfo
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Abstract
Description
本発明は、硬化物が柔軟で、かつ重合時の硬化収縮率が低く、密着性、電気絶縁性、耐水性が良好であり、さらに、透明性に優れ、熱及び光に対して安定であり、光又は熱により硬化が可能な硬化性樹脂組成物及びその硬化物に関する。 The present invention is a cured product that is flexible, has a low cure shrinkage during polymerization, has good adhesion, electrical insulation and water resistance, and is excellent in transparency and stable to heat and light. The present invention relates to a curable resin composition that can be cured by light or heat and a cured product thereof.
近年の電子材料分野では、機器の高性能化に伴い、電気絶縁性に優れ、かつ基材との密着強さが高く、耐湿性が良好な接着性樹脂が求められている。さらに、光学分野に使用される部品の場合、これらの特徴に加えて透明性が必要であり、熱及び光に対して長期的に安定な樹脂が求められている。また、電子材料及び光学材料の分野における材料のフレキシブル化に伴い、両分野で使用される接着剤及びコーティング剤なども先に掲げた性能に加えて柔軟性が求められている。さらに、樹脂組成物の硬化収縮などに起因する内部応力が被着体となるプラスチック部品に及ぼす影響は無視できないため、柔軟性に優れ、かつ硬化収縮の低い接着性樹脂の開発が望まれている。 In the field of electronic materials in recent years, an adhesive resin having excellent electrical insulation properties, high adhesion strength with a base material, and good moisture resistance has been demanded as performance of devices has been improved. Furthermore, in the case of components used in the optical field, transparency is necessary in addition to these characteristics, and a resin that is stable over the long term against heat and light is required. In addition, with the flexibility of materials in the fields of electronic materials and optical materials, the adhesives and coating agents used in both fields are required to have flexibility in addition to the performance described above. Furthermore, since the influence of internal stress due to curing shrinkage of the resin composition on the plastic parts that are the adherends cannot be ignored, development of an adhesive resin that has excellent flexibility and low curing shrinkage is desired. .
このような接着性樹脂として、ＦＲＰ、被覆用樹脂又は土木建築用途などに用いられるウレタン（メタ）アクリレートがいくつか提案されている（例えば、特許文献１、２参照）。
しかしながら、これらの特許文献に記されているポリエーテル又はポリエステル構造のものは、吸水性が高く、また、電気絶縁性が劣る傾向にあり、電子部品などに適用した場合、回路の腐食を生じる恐れがある。
また、吸水性、電気絶縁性を改善するために、ゴム系オリゴマーと（メタ）アクリロイル基とをウレタン結合によって結合させた液状ポリジエン系（メタ）アクリレートがいくつか提案されている（例えば、特許文献３、４、５参照）。ここで提案されている樹脂の硬化物は柔軟であり、耐水性、電気絶縁性、密着性は見られるが、ポリマー主鎖に不飽和基が残存することから、熱又は光により、着色、変形、ひび割れが発生するため、長期的な安定性にかける。
さらに、これらに関連してゴム系オリゴマーの水素添加物と（メタ）アクリロイル基とをウレタン結合によって結合させた液状水添ポリジエン系（メタ）アクリレートがいくつか提案されている（例えば、特許文献６、７、８参照）。ここで提案されている樹脂の硬化物は低収縮性があり、耐水性、電気絶縁性に優れているが、脂環式(メタ)アクリルモノマーを多量に含んでいる影響で、硬化物の柔軟性が十分でなく、さらに密着性も満足なものが得られない。
As such an adhesive resin, several urethane (meth) acrylates used for FRP, coating resin, civil engineering and building applications have been proposed (see, for example, Patent Documents 1 and 2).
However, those having a polyether or polyester structure described in these patent documents have high water absorption and tend to be poor in electrical insulation, and may cause circuit corrosion when applied to electronic components. There is.
In addition, in order to improve water absorption and electrical insulation, some liquid polydiene (meth) acrylates in which a rubber oligomer and a (meth) acryloyl group are bonded by a urethane bond have been proposed (for example, Patent Documents). 3, 4, 5). The cured product of the resin proposed here is flexible, and water resistance, electrical insulation, and adhesion can be seen, but since unsaturated groups remain in the polymer main chain, it is colored or deformed by heat or light. Because it cracks, long-term stability.
Further, in connection with these, several liquid hydrogenated polydiene (meth) acrylates in which hydrogenated products of rubber oligomers and (meth) acryloyl groups are bonded by urethane bonds have been proposed (for example, Patent Document 6). , 7, 8). The cured product of the resin proposed here has low shrinkage and excellent water resistance and electrical insulation, but the cured product is flexible due to the large amount of alicyclic (meth) acrylic monomer. Insufficient properties and satisfactory adhesion cannot be obtained.
本発明は、柔軟な硬化物が得られ、かつ重合時の硬化収縮率が低く、密着性、電気絶縁性、耐水性が良好で、さらに透明性に優れ、熱及び光に対して安定であり、光又は熱により硬化が可能な樹脂組成物及びその硬化物を提供することを目的とする。 The present invention provides a flexible cured product, has a low cure shrinkage during polymerization, has good adhesion, electrical insulation and water resistance, is excellent in transparency, and is stable against heat and light. It aims at providing the resin composition which can be hardened | cured with light or a heat | fever, and its hardened | cured material.
本発明者らは、上記の課題を解決するべく、鋭意検討を重ねた。その結果、（Ａ）末端に１個又は２個の水酸基を有する水素添加ポリジエン樹脂（ａ１）、有機ジイソシアネート（ａ２）及びヒドロキシアルキル（メタ）アクリレート（ａ３）を反応させてなる水素添加ポリジエン含有ウレタン（メタ）アクリレート樹脂及び（Ｂ）炭素数が６以上の脂肪族アルキル基をもつモノ（メタ）アクリレートからなる硬化性樹脂組成物、その硬化物が上記課題を解決できることを見出し、この知見に基づいて本発明を完成した。 In order to solve the above-described problems, the present inventors have made extensive studies. As a result, (A) hydrogenated polydiene-containing urethane obtained by reacting hydrogenated polydiene resin (a1) having one or two hydroxyl groups at the terminal, organic diisocyanate (a2) and hydroxyalkyl (meth) acrylate (a3). Based on this finding, a curable resin composition comprising a (meth) acrylate resin and (B) a mono (meth) acrylate having an aliphatic alkyl group having 6 or more carbon atoms, the cured product thereof can solve the above problems. The present invention has been completed.
すなわち、本発明は、
（１）末端に１個又は２個の吸い酸基を有する水素添加ポリジエン樹脂（ａ１）、有機ジイソシアネート（ａ２）及びヒドロキシアルキル（メタ）アクリレート（ａ３）を反応させてなる水素添加ポリジエン含有ウレタン（メタ）アクリレート樹脂（Ａ）及び炭素数が６以上の脂肪族アルキル基をもつモノ（メタ）アクリレート（Ｂ）とからなる硬化性樹脂組成物、
（２）水素添加ポリジエン含有ウレタン（メタ）アクリレート樹脂（Ａ）と、炭素数が６以上の脂肪族アルキル基をもつモノ（メタ）アクリレート（Ｂ）との配合割合（質量比）（Ａ）／（Ｂ）が９０／１０〜４０／６０である上記（１）に記載の硬化性樹脂組成物、（３）さらに、重合開始剤（Ｃ）を含む上記（１）又は（２）に記載の硬化性樹脂組成物、（４）上記（１）又は（２）に記載の硬化性樹脂組成物を硬化させてなる硬化物、
である。
That is, the present invention
(1) Hydrogenated polydiene-containing urethane obtained by reacting a hydrogenated polydiene resin (a1) having one or two absorbing acid groups at the terminal, an organic diisocyanate (a2) and a hydroxyalkyl (meth) acrylate (a3) ( A curable resin composition comprising a (meth) acrylate resin (A) and a mono (meth) acrylate (B) having an aliphatic alkyl group having 6 or more carbon atoms,
(2) Compounding ratio (mass ratio) of hydrogenated polydiene-containing urethane (meth) acrylate resin (A) and mono (meth) acrylate (B) having an aliphatic alkyl group having 6 or more carbon atoms (A) / The curable resin composition according to (1) above, wherein (B) is 90/10 to 40/60, (3) and (1) or (2) further including a polymerization initiator (C) A curable resin composition, (4) a cured product obtained by curing the curable resin composition according to the above (1) or (2),
It is.
本発明によれば、柔軟な硬化物が得られ、かつ重合時の硬化収縮率が低く、密着性、電気絶縁性、耐水性が良好で、さらに透明性に優れ、熱及び光に対して安定であり、光又は熱により硬化が可能な樹脂組成物及びその硬化物を提供することができる。 According to the present invention, a flexible cured product can be obtained, the curing shrinkage rate during polymerization is low, adhesion, electrical insulation and water resistance are good, and transparency is excellent and stable against heat and light. The resin composition which can be hardened | cured with light or a heat | fever, and its hardened | cured material can be provided.
以下に、本発明について詳細に説明する。
本発明で用いられる水素添加ポリジエン含有ウレタン（メタ）アクリレート樹脂（Ａ）の反応原料である、末端に１個又は２個の水酸基を有する水素添加ポリジエン樹脂（ａ１）としては、特に限定されるものではないが、ポリブタジエン、ポリイソプレン等の共役ポリジエン樹脂の水素添加物の末端に１個又は２個の水酸基を有する樹脂、ポリペンタジエン、ポリヘキサジエン、ポリオクタジエン等の非共役ポリジエン樹脂の水素添加物の末端に１個又は２個の水酸基を有する樹脂、ポリシクロペンタジエン、ポリジシクロペンタジエン、ポリエチリデンノルボルネン等の環状ポリジエン樹脂等の水素添加物の末端に１個又は２個の水酸基を有する樹脂等を挙げることができるが、柔軟性の点から、ポリブタジエン、ポリイソプレンなどの共役ポリジエンの水素添加物の末端に１個又は２個の水酸基を有する樹脂が特に好ましい。
ここで、末端に２個の水酸基を有する水素添加ポリジエン樹脂とは、２個の水酸基が水素添加ポリジエン樹脂の両末端にそれぞれ１個結合した構造の樹脂をいう。
また、水素添加ポリジエン樹脂とは、ポリジエン樹脂の不飽和結合を水素化して飽和させた樹脂のことをいう。
The present invention is described in detail below.
The hydrogenated polydiene resin (a1) having one or two hydroxyl groups at the terminal, which is a reaction raw material of the hydrogenated polydiene-containing urethane (meth) acrylate resin (A) used in the present invention, is particularly limited. Not, but hydrogenated products of non-conjugated polydiene resins such as polypentadiene, polyhexadiene, polyoctadiene, etc. A resin having one or two hydroxyl groups at the end of a hydrogenated product such as a resin having one or two hydroxyl groups at the terminal, a cyclic polydiene resin such as polycyclopentadiene, polydicyclopentadiene, polyethylidene norbornene, etc. From the viewpoint of flexibility, polybutadiene, polyisoprene, etc. Resins having one or two hydroxyl-terminated hydrogenated products useful polydiene is particularly preferred.
Here, the hydrogenated polydiene resin having two hydroxyl groups at the ends refers to a resin having a structure in which two hydroxyl groups are bonded to both ends of the hydrogenated polydiene resin.
Further, the hydrogenated polydiene resin refers to a resin in which unsaturated bonds of the polydiene resin are hydrogenated and saturated.
また、水素添加ポリジエン含有ウレタン（メタ）アクリレート樹脂（Ａ）の反応原料である有機ジイソシアネート（ａ２）としては、特に限定されるものではないが、例えば、芳香族系、脂肪族系、環式脂肪族系、脂環式系等のジイソシアネートが挙げられ、中でもトリレンジイソシアネート、ジフェニルメタンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、変性ジフェニルメタンジイソシアネート、水素添加キシリレンジイソシアネート、キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、テトラメチルキシリレンジイソシアネート、イソホロンジイソシアネート、ノルボルネンジイソシアネート、１，３−ビス（イソシアナトメチル）シクロヘキサン等のジイソシアネート類が挙げられる。 In addition, the organic diisocyanate (a2) that is a reaction raw material of the hydrogenated polydiene-containing urethane (meth) acrylate resin (A) is not particularly limited, and examples thereof include aromatic, aliphatic, and cyclic fats. Examples include diisocyanates such as alicyclic, alicyclic, etc., among which tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, Such as tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane Isocyanates, and the like.
また、水素添加ポリジエン含有ウレタン（メタ）アクリレート樹脂（Ａ）の反応原料であるヒドロキシアルキル（メタ）アクリレート（ａ３）としては、特に限定されるものではないが、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、１，４−ブタンジオールモノ（メタ）アクリレート、１，６−ヘキサンジオールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、カプロラクトン変成ヒドロキシエチル（メタ）アクリレート等のモノ（メタ）アクリレート類、トリメチロールプロパンジ（メタ）アクリレート等のジ（メタ）アクリレート類、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等の多官能（メタ）アクリレート類が挙げられる。
なお、本明細書において、（メタ）アクリレートはアクリレート及びメタクリレートを表す。
The hydroxyalkyl (meth) acrylate (a3), which is a reaction raw material of the hydrogenated polydiene-containing urethane (meth) acrylate resin (A), is not particularly limited, but 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, caprolactone-modified hydroxyethyl (meth) acrylate, etc. Mono (meth) acrylates, di (meth) acrylates such as trimethylolpropane di (meth) acrylate, polyfunctionality such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate ( Data) acrylates and the like.
In the present specification, (meth) acrylate represents acrylate and methacrylate.
本発明で用いられる水素添加ポリジエン含有ウレタン（メタ）アクリレート樹脂（Ａ）の製法は特に限定されるものではないが、例えば、末端に１個又は２個の水酸基を有する水素添加ポリジエン樹脂（ａ１）の水酸基ｎモル（ｎは１以上の整数である）に対し、有機ジイソシアネート（ａ２）のＮＣＯ基２ｎモルのモル比で反応させた後に、更に、該反応生成物にヒドロキシアルキル（メタ）アクリレート（ａ３）ｎモルを反応させることが好ましい。 The production method of the hydrogenated polydiene-containing urethane (meth) acrylate resin (A) used in the present invention is not particularly limited. For example, the hydrogenated polydiene resin (a1) having one or two hydroxyl groups at the terminals is used. Is reacted at a molar ratio of 2 nmol of NCO group of the organic diisocyanate (a2) to n mol of hydroxyl group (n is an integer of 1 or more), and then the reaction product is further reacted with hydroxyalkyl (meth) acrylate ( a3) It is preferable to react n moles.
また、これらの反応においては、反応触媒として、以下に示す公知のものを使用することができる。すなわち、トリエチルアミン、トリエチレンジアミン、Ｎ−メチルモルホリン等の第三級アミンやナフテン酸亜鉛、ナフテン酸コバルト、オクトエ酸銅、ジブチルチンジラウレート等の有機酸塩及び有機金属化合物を使用することができる。 In these reactions, the following known catalysts can be used as reaction catalysts. That is, tertiary amines such as triethylamine, triethylenediamine, and N-methylmorpholine, and organic acid salts and organometallic compounds such as zinc naphthenate, cobalt naphthenate, copper octoate, and dibutyltin dilaurate can be used.
水素添加ポリジエン含有ウレタン（メタ）アクリレート樹脂（Ａ）の重量平均分子量は、３，０００〜２５，０００が好ましく、８，０００〜２０，０００がより好ましい。重量平均分子量が３，０００〜２５，０００の範囲内であると硬化物が脆くなることもなく、硬化性が悪化することもない。なお、重量平均分子量はゲル パーミエーション クロマトグラフィー法（ＧＰＣ法）（標準ポリスチレン換算）等で測定される。 The weight average molecular weight of the hydrogenated polydiene-containing urethane (meth) acrylate resin (A) is preferably 3,000 to 25,000, and more preferably 8,000 to 20,000. When the weight average molecular weight is within the range of 3,000 to 25,000, the cured product does not become brittle and the curability is not deteriorated. The weight average molecular weight is measured by gel permeation chromatography method (GPC method) (standard polystyrene conversion) or the like.
本発明の硬化性樹脂組成物を構成する成分（Ｂ）である炭素数が６以上の脂肪族アルキル基を持つ（メタ）アクリレートとしては、例えば、２−エチルヘキシル(メタ）アクリレート、イソデシル(メタ）アクリレート、ラウリル(メタ）アクリレート、ステアリル(メタ）アクリレートなどが挙げられ、該成分（Ｂ）の成分（Ａ）との配合割合（質量比）Ａ／Ｂは９０／１０〜４０／６０が好ましく、８０／２０〜５０／５０がより好ましい。該配合割合が、９０／１０〜４０／６０の範囲内であると、初期においても充分な接着性が得られ、内部応力が大きくなることもなく、接着性が十分に保持される。また、成分（Ｂ）が炭素数６以上であっても、シクロヘキシル(メタ)アクリレートジシクロペンテニルアクリレートなどの脂環式構造を含むモノ（メタ）アクリレートの場合は、十分な柔軟性、密着強度が得られない。 Examples of the (meth) acrylate having an aliphatic alkyl group having 6 or more carbon atoms, which is the component (B) constituting the curable resin composition of the present invention, include 2-ethylhexyl (meth) acrylate and isodecyl (meth). Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like. The blending ratio (mass ratio) A / B of the component (B) with the component (A) is preferably 90/10 to 40/60, 80 / 20-50 / 50 is more preferable. When the blending ratio is in the range of 90/10 to 40/60, sufficient adhesiveness is obtained even in the initial stage, and the adhesiveness is sufficiently maintained without increasing internal stress. In addition, even if the component (B) has 6 or more carbon atoms, the mono (meth) acrylate containing an alicyclic structure such as cyclohexyl (meth) acrylate dicyclopentenyl acrylate has sufficient flexibility and adhesion strength. I can't get it.
本発明の硬化性樹脂組成物を硬化させるには、従来からウレタンアクリレート樹脂で用いられている硬化方法、すなわち、重合開始剤（Ｃ）例えば、光重合開始剤を用いた光硬化法や有機過酸化物開始剤を用いた加熱硬化法の通常の方法を用いることができる。 In order to cure the curable resin composition of the present invention, a curing method conventionally used for urethane acrylate resins, that is, a polymerization initiator (C), for example, a photocuring method using a photopolymerization initiator or an organic catalyst. A normal method of heat curing using an oxide initiator can be used.
本発明の硬化性樹脂組成物を硬化させるのに用いる光重合開始剤としては、特に限定されず、例えば、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、ベゾフェノン、２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパノン−１、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−1、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、２，４，６−トリメチルベンゾイルジフェニル−フォスフィンオキサイドなどが挙げられる。 The photopolymerization initiator used for curing the curable resin composition of the present invention is not particularly limited, and examples thereof include 2,2-dimethoxy-1,2-diphenylethane-1-one and 1-hydroxy-cyclohexyl. -Phenyl-ketone, bezophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, and the like.
本発明の硬化性樹脂組成物を硬化させるのに用いる有機過酸化物開始剤としては、特に限定されるものではないが、例えば、ジアルキルパーオキサイド、アシルパーオキサイド、ハイドロパーオキサイド、ケトンパーオキサイド、パーオキシエステルなど公知のものを用いることができ、具体的には以下のようなものを例示することができる。ベンゾイルパーオキサイド、ｔ−ブチルパーオキシ−２−エチルヘキサネート、２，５−ジメチル−２，５−ジ(２−エチルヘキサノイル)パーオキシヘキサン、ｔ−ブチルパーオキシベンゾエート、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ジクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジブチルパーオキシヘキサンなどが挙げられる。 The organic peroxide initiator used for curing the curable resin composition of the present invention is not particularly limited, and examples thereof include dialkyl peroxides, acyl peroxides, hydroperoxides, ketone peroxides, Known materials such as peroxyesters can be used, and specific examples include the following. Benzoyl peroxide, t-butylperoxy-2-ethylhexanate, 2,5-dimethyl-2,5-di (2-ethylhexanoyl) peroxyhexane, t-butylperoxybenzoate, t-butylhydroper Examples thereof include oxide, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, and the like.
上記光重合開始剤や有機過酸化物開始剤などの重合開始剤（Ｃ）の使用量は硬化性樹脂組成物に対して０．８〜１０質量％程度の範囲が好ましい。 The amount of the polymerization initiator (C) such as the photopolymerization initiator or organic peroxide initiator used is preferably in the range of about 0.8 to 10% by mass relative to the curable resin composition.
上記の成分（Ａ）、成分（Ｂ）及び成分（Ｃ）以外に硬化性樹脂組成物の粘度を調整するために、希釈用重合性ビニルモノマーを、本発明の効果を損なわない範囲で使用してもよい。
該希釈用重合性ビニルモノマーとしては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、テトラヒドロフルフリル（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、スチレン等が挙げられる。
In order to adjust the viscosity of the curable resin composition in addition to the components (A), (B) and (C), a polymerizable vinyl monomer for dilution is used within a range not impairing the effects of the present invention. May be.
Examples of the polymerizable vinyl monomer for dilution include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and tetrahydrofurfuryl (meth). Examples include acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and styrene.
硬化性樹脂組成物の硬化速度や硬化物の架橋度をコントロールするために、架橋用重合性モノマーを使用してもよい。架橋用重合性モノマーとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート等が挙げられる In order to control the curing rate of the curable resin composition and the degree of crosslinking of the cured product, a polymerizable monomer for crosslinking may be used. Examples of the polymerizable monomer for crosslinking include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. Be
本発明の硬化性樹脂組成物には、必要に応じて、シランカップリング剤や酸性リン酸エステル等の密着性向上剤、貯蔵安定性を向上させるための酸化防止剤、その他、硬化促進剤、消泡剤、染料、充填剤、顔料、チキソトロピー付与剤、可塑剤、界面活性剤、滑剤、帯電防止剤などの添加剤を加えることができる。 In the curable resin composition of the present invention, if necessary, an adhesion improver such as a silane coupling agent or an acidic phosphate ester, an antioxidant for improving storage stability, other, a curing accelerator, Additives such as antifoaming agents, dyes, fillers, pigments, thixotropic agents, plasticizers, surfactants, lubricants and antistatic agents can be added.
実施例によって本発明を更に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限定されるものではない。 The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
下記の要領でウレタンアクリレート樹脂を製造した。
合成例１
温度計、撹拌器、滴下ロート、乾燥管付き冷却管を備えた四つ口フラスコにイソホロンジイソシアネート（ａ２）１５２．９ｇ及び末端に水酸基を有する水素添加ポリイソプレン樹脂（ａ１、出光興産株式会社製、エポール）を７６４．５ｇ仕込み、６０℃で反応させた。残存イソシアネート基が１モル％以下となった時点で、２−ヒドロキシエチルメタクリレート（ａ３）８１．７ｇを仕込み、７０℃まで昇温して反応を行なった。イソシアネート基がなくなった時点で反応を終了させ、水素添加ポリイソプレン含有ウレタンアクリレート樹脂（ＵＡ１、重量平均分子量１８０００）を得た。
A urethane acrylate resin was produced in the following manner.
Synthesis example 1
A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, a cooling tube with a drying tube, 152.9 g of isophorone diisocyanate (a2) and a hydrogenated polyisoprene resin having a hydroxyl group at the terminal (a1, manufactured by Idemitsu Kosan Co., Ltd., 764.5 g of Epol) was charged and reacted at 60 ° C. When the residual isocyanate group became 1 mol% or less, 81.7 g of 2-hydroxyethyl methacrylate (a3) was charged, and the reaction was performed by raising the temperature to 70 ° C. When the isocyanate group disappeared, the reaction was terminated to obtain a hydrogenated polyisoprene-containing urethane acrylate resin (UA1, weight average molecular weight 18000).
合成例２
温度計、撹拌器、滴下ロート、乾燥管付き冷却管を備えた四つ口フラスコにイソホロンジイソシアネート（ａ２）１０１．２ｇ及び末端に水酸基を有する水素添加ポリブタジエン樹脂（ａ１）を８４４．３ｇ仕込み、６０℃で反応させ、残存イソシアネート基が１モル％以下となった時点で、２−ヒドロキシエチルメタクリレート５３．９ｇを仕込み７０℃まで昇温して反応を行なった。イソシアネート基がなくなった時点で反応を終了させ、水素添加ポリブタジエン含有ウレタンアクリレート樹脂（ＵＡ２、重量平均分子量１５０００）を得た。
Synthesis example 2
A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube is charged with 101.2 g of isophorone diisocyanate (a2) and 844.3 g of hydrogenated polybutadiene resin (a1) having a hydroxyl group at the end, 60 When the residual isocyanate group became 1 mol% or less at a temperature of 5 ° C., 53.9 g of 2-hydroxyethyl methacrylate was charged and the reaction was performed by raising the temperature to 70 ° C. The reaction was terminated when the isocyanate group disappeared, and a hydrogenated polybutadiene-containing urethane acrylate resin (UA2, weight average molecular weight 15000) was obtained.
比較合成例
温度計、撹拌器、滴下ロート、乾燥管付き冷却管を備えた四つ口フラスコに、イソホロンジイソシアネート（ａ２）１４０．９ｇ及び末端に水酸基を有するポリイプレン樹脂（出光興産株式会社製、Ｐｏｌｙ ｉｐ）を７８２．７ｇ仕込み、６０℃で反応させ、残存イソシアネート基が１モル％以下となった時点で、２−ヒドロキシエチルメタクリレート（ａ３）７５．４ｇを仕込み７０℃まで昇温して反応を行なった。イソシアネート基がなくなった時点で反応を終了させ、ポリイプレン含有ウレタンアクリレート樹脂（ＵＡ３、重量平均分子量１４０００）を得た。
Comparative Synthesis Example A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube was charged with 140.9 g of isophorone diisocyanate (a2) and a polyprene resin having a hydroxyl group at the terminal (made by Idemitsu Kosan Co., Ltd. ip) was charged at 782.7 g and reacted at 60 ° C. When the residual isocyanate group became 1 mol% or less, 75.4 g of 2-hydroxyethyl methacrylate (a3) was charged and the temperature was raised to 70 ° C. to react. I did it. The reaction was terminated when the isocyanate group disappeared, and a polyprene-containing urethane acrylate resin (UA3, weight average molecular weight 14000) was obtained.
実施例１
合成例１で得られたＵＡ１樹脂６０質量部、２−エチルヘキシルアクリレート（Ｂ）４０質量部及び重合開始剤（Ｃ）ダロキュア（登録商標、チバ・スペシャルティ・ケミカルズ株式会社製）１１７３ ４質量部からなる硬化性樹脂組成物を調製し、該硬化性樹脂組成物をガラス板の間にはさんで、高圧水銀灯（５ｋＷ）の照射装置を用いて紫外線３６５ｎｍ、積算光量２０００ｍＪ／ｃｍ2の硬化条件で硬化せしめて、厚さ３ｍｍ、縦１００ｍｍ、横１００ｍｍの透明な硬化物を成形した。
Example 1
It consists of 60 parts by mass of UA1 resin obtained in Synthesis Example 1, 40 parts by mass of 2-ethylhexyl acrylate (B), and 4 parts by mass of polymerization initiator (C) Darocur (registered trademark, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1173. A curable resin composition was prepared, and the curable resin composition was sandwiched between glass plates and cured under curing conditions of ultraviolet rays of 365 nm and an integrated light amount of 2000 mJ / cm 2 using an irradiation device of a high-pressure mercury lamp (5 kW). A transparent cured product having a thickness of 3 mm, a length of 100 mm, and a width of 100 mm was molded.
実施例２
合成例２で得られたＵＡ２樹脂７０質量部、２−エチルヘキシルアクリレート（Ｂ）３０質量部及び重合開始剤（Ｃ）ダロキュア（登録商標、チバ・スペシャルティ・ケミカルズ株式会社製）１１７３ ４質量部からなる硬化性樹脂組成物を調製し、該硬化性樹脂組成物をガラス板の間にはさんで、高圧水銀灯（８ｋＷ）の照射装置を用いて紫外線３６５ｎｍ、積算光量２０００ｍＪ／ｃｍ2の硬化条件で硬化せしめて、厚さ３ｍｍ、縦１００ｍｍ、横１００ｍｍの透明な硬化物を成形した。
Example 2
It consists of 70 parts by mass of UA2 resin obtained in Synthesis Example 2, 30 parts by mass of 2-ethylhexyl acrylate (B), and 4 parts by mass of polymerization initiator (C) Darocur (registered trademark, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1173. A curable resin composition is prepared, and the curable resin composition is sandwiched between glass plates and cured under curing conditions of ultraviolet rays of 365 nm and an integrated light amount of 2000 mJ / cm 2 using an irradiation device of a high-pressure mercury lamp (8 kW). A transparent cured product having a thickness of 3 mm, a length of 100 mm, and a width of 100 mm was molded.
実施例３
合成例１で得られたＵＡ１樹脂６０質量部、２−エチルヘキシルアクリレート（Ｂ）４０質量部及び重合開始剤（Ｃ）であるパーオクタ（登録商標、日本油脂株式会社製）０．１質量部とパーロイル（登録商標、日本油脂株式会社製）ＴＣＰ ０．５質量部とからなる硬化性樹脂組成物をガラス板の間にはさんで、１００℃の硬化炉に１時間入れて加熱硬化せしめて、厚さ３ｍｍ、縦１００ｍｍ、横１００ｍｍの透明な硬化物を成形した。
Example 3
60 parts by mass of UA1 resin obtained in Synthesis Example 1, 40 parts by mass of 2-ethylhexyl acrylate (B) and 0.1 part by mass of perocta (registered trademark, manufactured by NOF Corporation) as a polymerization initiator (C) and paroyl (Registered trademark, manufactured by Nippon Oil & Fats Co., Ltd.) TCP A curable resin composition consisting of 0.5 part by mass is sandwiched between glass plates, placed in a curing furnace at 100 ° C. for 1 hour, and cured by heating to a thickness of 3 mm. A transparent cured product having a length of 100 mm and a width of 100 mm was molded.
比較例１
合成例１で得られたＵＡ１樹脂６０質量部、ジシクロペンテニルアクリレート４０質量部及び重合開始剤（Ｃ）ダロキュア（登録商標、チバ・スペシャルティ・ケミカルズ株式会社製）１１７３ ４質量部からなる硬化性樹脂組成物をガラス板の間にはさんで、高圧水銀灯（８ｋＷ）の照射装置を用いて紫外線３６５ｎｍ、積算光量２０００ｍＪ／ｃｍ2の硬化条件で硬化せしめて、厚さ３ｍｍ、縦１００ｍｍ、横１００ｍｍの透明な硬化物を成形した。
Comparative Example 1
Curable resin comprising 60 parts by weight of UA1 resin obtained in Synthesis Example 1, 40 parts by weight of dicyclopentenyl acrylate, and 4 parts by weight of polymerization initiator (C) Darocur (registered trademark, manufactured by Ciba Specialty Chemicals) 1173 The composition is sandwiched between glass plates and cured using a high-pressure mercury lamp (8 kW) irradiation device under ultraviolet curing conditions of 365 nm and an integrated light quantity of 2000 mJ / cm 2 to obtain a transparent film having a thickness of 3 mm, a length of 100 mm, and a width of 100 mm. A cured product was formed.
比較例２
比較合成例で得られたＵＡ３樹脂６０質量部、２−エチルヘキシルアクリレート（Ｂ）４０質量部及び重合開始剤（Ｃ）ダロキュア（登録商標、チバ・スペシャルティ・ケミカルズ株式会社製）１１７３ ４質量部からなる硬化性樹脂組成物をガラス板の間にはさんで、高圧水銀灯（８ｋＷ）の照射装置を用いて紫外線３６５ｎｍ、積算光量２０００ｍＪ／ｃｍ2の硬化条件で硬化せしめて、厚さ３ｍｍ、縦１００ｍｍ、横１００ｍｍの透明な硬化物を成形した。
Comparative Example 2
It consists of 60 parts by mass of UA3 resin obtained in Comparative Synthesis Example, 40 parts by mass of 2-ethylhexyl acrylate (B) and 4 parts by mass of polymerization initiator (C) Darocur (registered trademark, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1173. The curable resin composition is sandwiched between glass plates and cured using a high-pressure mercury lamp (8 kW) irradiation device under curing conditions of ultraviolet rays of 365 nm and an integrated light quantity of 2000 mJ / cm 2. The thickness is 3 mm, the length is 100 mm, and the width is 100 mm. A transparent cured product was molded.
実施例、比較例で得られた硬化性樹脂組成物又は硬化物を用いて下記の方法で、（１）硬化収縮率、（２）吸水率、（３）表面硬度、（４）電気特性、（５）耐候性及び（６）密着性の評価を行い、その結果を表１にまとめて示した。 Using the curable resin compositions or cured products obtained in Examples and Comparative Examples, the following methods were used: (1) cure shrinkage, (2) water absorption, (3) surface hardness, (4) electrical properties, (5) Weather resistance and (6) Adhesion were evaluated, and the results are summarized in Table 1.
（１）硬化収縮率
得られた硬化性樹脂組成物の２３℃における液比重と、上記の各硬化条件で得られた硬化物（試験体）の２３℃における硬化物層の比重を各々測定し、下記の定義に基づいて硬化収縮率を算出し、評価した。
＜硬化収縮率の算出定義＞
２３℃における硬化前の液比重（Ｘ1）と、硬化して得られた硬化物層の２３℃における比重（Ｘ2）をそれぞれ測定し、下記の式（１）により求めた値を硬化収縮率（％）とした。
硬化収縮率（％）＝〔（Ｘ2−Ｘ1）／Ｘ2〕×１００ ・・・式（１）
硬化収縮率が６．５％未満の場合を○、６．５％以上の場合を×とした。
(1) Curing Shrinkage The liquid specific gravity at 23 ° C. of the obtained curable resin composition and the specific gravity of the cured product layer at 23 ° C. of the cured product (test body) obtained under the above curing conditions were respectively measured. The cure shrinkage was calculated and evaluated based on the following definitions.
<Calculation definition of cure shrinkage>
The liquid specific gravity (X 1 ) before curing at 23 ° C. and the specific gravity (X 2 ) at 23 ° C. of the cured product layer obtained by curing were measured, and the values obtained by the following formula (1) were cured shrinkage. Rate (%).
Curing shrinkage (%) = [(X 2 −X 1 ) / X 2 ] × 100 Formula (1)
The case where the curing shrinkage was less than 6.5% was rated as ○, and the case where the shrinkage was 6.5% or more was rated as x.
（２）吸水率
実施例１〜３及び比較例１、２に記載した硬化条件で作成した硬化物（試験体）について、２３℃の水中に２４時間放置し、ＪＩＳ Ｋ７２０９に準拠して吸水率を測定し、下記基準に基づいて評価した。
吸水率が０．１％未満の場合を○、０．１％以上の場合を×とした。
(2) Water absorption rate The cured product (test body) prepared under the curing conditions described in Examples 1 to 3 and Comparative Examples 1 and 2 was left in water at 23 ° C. for 24 hours, and the water absorption rate according to JIS K7209. Were measured and evaluated based on the following criteria.
The case where the water absorption rate was less than 0.1% was rated as ◯, and the case where the water absorption rate was 0.1% or more was rated as x.
（３）表面硬度
実施例１〜３及び比較例１、２で得られた硬化物（試験体）について、ＪＩＳ Ｋ−６２５３に準拠して、デュロメータ硬度計タイプＡを使用して表面硬度を測定し、下記基準に基づいて評価した。
タイプＡ硬度が７０未満の場合を○、タイプＡ硬度が７０以上の場合を×とした。
(3) Surface hardness About the hardened | cured material (test body) obtained in Examples 1-3 and Comparative Examples 1 and 2, surface hardness was measured using durometer hardness tester type A based on JISK-6253. And evaluated based on the following criteria.
The case where the type A hardness was less than 70 was marked with ◯, and the case where the type A hardness was 70 or more was marked with x.
（４）電気特性
実施例１〜３及び比較例１、２で得られた硬化物（試験体）について、ヒューレットパッカード株式会社製ベクトルネットワークアナライザＨＰ８７５３Ｅを用い、１．５ｍｍ×１．５ｍｍ×７５ｍｍの角柱状試験片を用いて空洞共振器摂動法にて測定周波数５ＧＨｚにて誘電率および誘電正接を測定し、下記基準に基づいて評価した。
誘電率が３．０未満かつ誘電正接が０．００５未満の場合を○、
誘電率が３．０未満かつ誘電正接が０．００５以上の場合を×とした。
(4) Electrical characteristics About the hardened | cured material (test body) obtained in Examples 1-3 and Comparative Examples 1 and 2, using Hewlett-Packard Co., Ltd. vector network analyzer HP8753E, it is 1.5 mm x 1.5 mm x 75 mm. Dielectric constant and dielectric loss tangent were measured using a prismatic test piece at a measurement frequency of 5 GHz by a cavity resonator perturbation method, and evaluated based on the following criteria.
A case where the dielectric constant is less than 3.0 and the dielectric loss tangent is less than 0.005.
A case where the dielectric constant was less than 3.0 and the dielectric loss tangent was 0.005 or more was evaluated as x.
（５）耐候性
実施例１〜３及び比較例１、２で得られた硬化物（試験体）を用い、照射前の全光線透過率（村上色彩技術研究所製ヘイズメータＨＭ−１５０）及び表面光沢（村上色彩技術研究所製グロスメータＧＭ−２６ＰＲＯ）を測定した。その後、キセノンウエザーメーター（東洋精機製作所製ＡＬＴＡＳウェザーメータＣｉ−４０００）中（ブラックパネル温度６５℃、照射２時間中降雨１８分、照射エネルギー１００Ｗ／ｍ2）で照射１０００時間後の、全光線透過率および表面光沢の保持率を測定した。表中の○は、１０００時間照射後の全光線透過率保持率が９０％以上でかつ表面光沢の保持率が９０％以上のものを示す。
(5) Weather resistance Using the cured products (test bodies) obtained in Examples 1 to 3 and Comparative Examples 1 and 2, the total light transmittance before irradiation (Haze Meter HM-150 manufactured by Murakami Color Research Laboratory) and the surface The gloss (gross meter GM-26PRO manufactured by Murakami Color Research Laboratory) was measured. Thereafter, total light transmission after 1000 hours irradiation in a xenon weather meter (ALTAS weather meter Ci-4000 manufactured by Toyo Seiki Seisakusho) (black panel temperature 65 ° C., 2 hours of irradiation 18 minutes of rain, irradiation energy 100 W / m 2 ) Rate and surface gloss retention were measured. “◯” in the table indicates that the total light transmittance retention after irradiation for 1000 hours is 90% or more and the surface gloss retention is 90% or more.
（６）密着性
実施例１〜３及び比較例１、２で得られた重合開始剤入りの硬化性樹脂組成物を、厚さ１２５μｍのポリエステルフィルム上に厚みが５０μｍになるように塗布した後、紫外線を１０００ｍＪ／ｃｍ2照射した。実施例３のみ５０μｍになるように塗布した後、１００℃の硬化炉にて２時間加熱硬化させた。これらの塗膜の密着性を碁盤目セロハンテープ〈登録商標〉剥離試験法により、碁盤目１００個中の剥離碁盤目数を測定し、下記の基準で密着性を評価した。
○：密着性非常に良好（９０／１００以上）
△：密着性良好（８０／１００以上９０／１００未満）
×：密着性不良（８０／１００未満）
(6) Adhesion After coating the curable resin composition containing the polymerization initiator obtained in Examples 1 to 3 and Comparative Examples 1 and 2 on a polyester film having a thickness of 125 μm so as to have a thickness of 50 μm. UV rays were irradiated at 1000 mJ / cm 2 . Only Example 3 was applied to a thickness of 50 μm, and then heat-cured in a curing furnace at 100 ° C. for 2 hours. The adhesiveness of these coating films was measured by the cross-cut cellophane tape (registered trademark) peel test method, and the number of peeled cross-cuts per 100 cross-cuts was measured, and the adhesiveness was evaluated according to the following criteria.
○: Very good adhesion (90/100 or more)
Δ: Good adhesion (80/100 or more and less than 90/100)
X: Adhesion failure (less than 80/100)
本発明の硬化性樹脂組成物は、各種基材に対し高い接着強度を有し、高湿度下での強度低下が極めて小さく、且つ硬化時に発生する内部応力が小さく柔軟な硬化性樹脂組成物であることから、内部応力が影響するプラスチック製電子材料への接着の適用が可能となる。また、本発明の硬化性樹脂組成物は、透明性に優れ、且つ熱又は光に対して長期的に安定であるため、内部応力が影響するプラスチック製光学材料の接着にも適応が可能である。 The curable resin composition of the present invention is a flexible curable resin composition that has a high adhesive strength to various substrates, has a very small decrease in strength under high humidity, and has a small internal stress generated during curing. Therefore, it is possible to apply adhesion to a plastic electronic material affected by internal stress. Further, since the curable resin composition of the present invention is excellent in transparency and stable for a long time against heat or light, it can be applied to adhesion of plastic optical materials affected by internal stress. .
Claims (4)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011227154A (en) * | 2010-04-15 | 2011-11-10 | Sony Corp | Optical body, manufacturing method of the same, solar shading material, window material, interior material and fitting |
| JP2013056973A (en) * | 2011-09-07 | 2013-03-28 | Kyoritsu Kagaku Sangyo Kk | Ultraviolet-curable resin having rubber elasticity |
| WO2013187508A1 (en) * | 2012-06-15 | 2013-12-19 | 昭和電工株式会社 | Polymerizable composition, polymer, optical adhesive sheet, image display device, and method for manufacturing image display device |
-
2007
- 2007-04-13 JP JP2007106328A patent/JP2008260898A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011227154A (en) * | 2010-04-15 | 2011-11-10 | Sony Corp | Optical body, manufacturing method of the same, solar shading material, window material, interior material and fitting |
| JP2013056973A (en) * | 2011-09-07 | 2013-03-28 | Kyoritsu Kagaku Sangyo Kk | Ultraviolet-curable resin having rubber elasticity |
| WO2013187508A1 (en) * | 2012-06-15 | 2013-12-19 | 昭和電工株式会社 | Polymerizable composition, polymer, optical adhesive sheet, image display device, and method for manufacturing image display device |
| JPWO2013187508A1 (en) * | 2012-06-15 | 2016-02-08 | 昭和電工株式会社 | Polymerizable composition, polymer, optical pressure-sensitive adhesive sheet, image display device and method for producing the same |
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