JP2008184538A - Ultraviolet curable resin composition - Google Patents
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Abstract
Description
本発明は、液状紫外線硬化樹脂組成物であって、詳細にはガラス、プラスチック基板、特に、ポリエチレンテレフタレート（以下、ＰＥＴと略記する）フィルムに対する優れた接着性、耐熱性、耐湿性を有する紫外線樹脂硬化物を与え、長期信頼性が要求される各種印刷材料、表示材料、電気電子部品材料、通信用電子光学部品材料、光学部品材料、液晶材料等の分野における接着剤として有用な紫外線硬化樹脂組成物に関する。 The present invention is a liquid ultraviolet curable resin composition, and more specifically, an ultraviolet resin having excellent adhesion, heat resistance and moisture resistance to glass and plastic substrates, particularly polyethylene terephthalate (hereinafter abbreviated as PET) films. UV curable resin composition useful as an adhesive in the fields of various printed materials, display materials, electrical and electronic component materials, electro-optical component materials for communication, optical component materials, liquid crystal materials, etc. that give cured products and require long-term reliability Related to things.
紫外線硬化樹脂の歴史は意外と古く、変性アクリレート等のビニルモノマーに紫外線を照射するとラジカル重合を起こしポリマーになることはかなり前から知られていた。西ドイツでは１９５０年代には印刷用版材樹脂が、１９６０年代後半には木工用コーティング材が開発され、汎用樹脂としての口火を切り、また、アメリカでは印刷用樹脂などが開発され、それぞれがポティング材、コーティング材、インキ材、接着剤等として発展し、現在の様々なエレクトロニクスの分野への応用に繋がっている。
特に、接着剤の分野にあっては、従来の溶剤揮発硬化樹脂タイプや二液反応硬化樹脂タイプ等に代わり、紫外線硬化樹脂タイプの接着性や速硬化性による生産性の向上、その硬化物の耐熱性等による品質の向上等、紫外線硬化樹脂本来の特性を活かしながら広く用いられるようになってきている。
しかし、各種印刷材料、表示材料、電気電子部品材料、通信用電子光学部品材料、光学部品材料、液晶材料等の分野に多用されるプラスチック基板、特に、ＰＥＴフィルムに対する十分な接着性、耐熱性、耐湿性を有する紫外線硬化物を与える紫外線硬化樹脂組成物は未だ存在していないのが実情である。
The history of ultraviolet curable resins is surprisingly old, and it has been known for a long time that radical polymerization occurs when a vinyl monomer such as a modified acrylate is irradiated with ultraviolet rays to form a polymer. In West Germany, printing plate resins were developed in the 1950s, and wood coating materials were developed in the late 1960s. In the United States, printing resins were developed. It has been developed as a coating material, ink material, adhesive, etc., and has led to applications in various fields of electronics today.
In particular, in the field of adhesives, instead of conventional solvent volatile curable resin types and two-component reaction curable resin types, etc., improved productivity due to UV curable resin type adhesive properties and fast curability, It has been widely used while taking advantage of the inherent properties of ultraviolet curable resins, such as improvement in quality due to heat resistance and the like.
However, plastic substrates that are frequently used in the fields of various printing materials, display materials, electrical and electronic component materials, electro-optical component materials for communication, optical component materials, liquid crystal materials, etc., in particular, sufficient adhesion to PET films, heat resistance, In fact, there is no ultraviolet curable resin composition that provides an ultraviolet cured product having moisture resistance.
特開２００４−１１５７５７号公報（特許文献１）には、（Ａ）数平均分子量が１０，０００〜４０，０００であるウレタン（メタ）アクリレート３０〜７０重量％、（Ｂ）ホモポリマーのガラス転移温度が６０℃以上であるエチレン性不飽和ポリマー３０〜６０重量％を含有する液状硬化性樹脂組成物がＰＥＴ等に対する優れた接着性を示すことが報告されている。
しかし、当該組成物はＰＥＴに対する十分な接着性、耐熱性、耐湿性を有する紫外線硬化物を与えるものではなかった。
JP-A-2004-115757 (Patent Document 1) discloses (A) 30 to 70% by weight of urethane (meth) acrylate having a number average molecular weight of 10,000 to 40,000, and (B) a glass transition of a homopolymer. It has been reported that a liquid curable resin composition containing 30 to 60% by weight of an ethylenically unsaturated polymer having a temperature of 60 ° C. or higher exhibits excellent adhesion to PET or the like.
However, the composition did not give an ultraviolet cured product having sufficient adhesion to PET, heat resistance and moisture resistance.
本発明は、上記事情に鑑みなされたもので、特に、ＰＥＴフィルムに対する優れた接着性、耐熱性、耐湿性を有する紫外線樹脂硬化物を与え、長期信頼性が要求される各種印刷材料、表示材料、電気電子部品材料、通信用電子光学部品材料、光学部品材料、液晶材料等の分野における接着剤として有用な紫外線硬化樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and in particular, provides various cured printing materials and display materials that provide an ultraviolet resin cured product having excellent adhesion, heat resistance, and moisture resistance to a PET film and that require long-term reliability. An object of the present invention is to provide an ultraviolet curable resin composition useful as an adhesive in the fields of electrical and electronic component materials, communication electro-optical component materials, optical component materials, liquid crystal materials and the like.
本発明者等は、上記目的を達成するため、鋭意検討を行なった結果、重量平均分子量１５，０００〜４０，０００のウレタン（メタ）アクリレートオリゴマーと（メタ）アクリレートモノマーと光開始剤とを含む紫外線硬化樹脂組成物が有効であり、さらに上記各成分の配合が、ウレタン（メタ）アクリレートオリゴマー：（メタ）アクリレートモノマー＝７５：２５〜５５：４５（質量部）であり、これらの合計１００質量部に対して、光開始剤が０．１〜１０質量部である紫外線硬化樹脂組成物を用いることによって、特に、ＰＥＴフィルムに対する優れた接着性、耐熱性、耐湿性を有する紫外線樹脂硬化物を与え、長期信頼性が要求される各種印刷材料、表示材料、電気電子部品材料、通信用電子光学部品材料、光学部品材料、液晶材料等の分野における接着剤として有用な紫外線硬化樹脂組成物を提供できることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventors include a urethane (meth) acrylate oligomer having a weight average molecular weight of 15,000 to 40,000, a (meth) acrylate monomer, and a photoinitiator. The ultraviolet curable resin composition is effective, and the blending of the above components is urethane (meth) acrylate oligomer: (meth) acrylate monomer = 75: 25 to 55:45 (parts by mass), and the total of these is 100 masses. By using an ultraviolet curable resin composition having a photoinitiator of 0.1 to 10 parts by mass with respect to parts, particularly, an ultraviolet resin cured product having excellent adhesion, heat resistance and moisture resistance to a PET film. Various printing materials, display materials, electrical and electronic component materials, electro-optical component materials for communication, optical component materials, liquid crystal materials that require long-term reliability It found to be able to provide a useful UV-curable resin composition as an adhesive in the field of equal, leading to the completion of the present invention.
即ち、本発明は、下記紫外線硬化樹脂組成物を提供する。
請求項１：
重量平均分子量１５，０００〜４０，０００のウレタン（メタ）アクリレートオリゴマーと（メタ）アクリレートモノマーと光開始剤とを含む紫外線硬化樹脂組成物。
請求項２：
上記各成分の配合が、ウレタン（メタ）アクリレートオリゴマー：（メタ）アクリレートモノマー＝７５：２５〜５５：４５（質量部）であり、これらの合計１００質量部に対して、光開始剤が０．１〜１０質量部である請求項１記載の紫外線硬化樹脂組成物。
That is, the present invention provides the following ultraviolet curable resin composition.
Claim 1:
An ultraviolet curable resin composition comprising a urethane (meth) acrylate oligomer having a weight average molecular weight of 15,000 to 40,000, a (meth) acrylate monomer, and a photoinitiator.
Claim 2:
The blending of each of the above components is urethane (meth) acrylate oligomer: (meth) acrylate monomer = 75: 25 to 55:45 (parts by mass). The ultraviolet curable resin composition according to claim 1, which is 1 to 10 parts by mass.
本発明によれば、特に、ＰＥＴフィルムに対する優れた接着性、耐熱性、耐湿性を有する紫外線樹脂硬化物を与え、長期信頼性が要求される各種印刷材料、表示材料、電気電子部品材料、通信用電子光学部品材料、光学部品材料、液晶材料等の分野における接着剤として有用な紫外線硬化樹脂組成物を提供することができる。 According to the present invention, in particular, a UV resin cured product having excellent adhesion, heat resistance, and moisture resistance to a PET film is provided, and various printing materials, display materials, electrical and electronic component materials, communication that require long-term reliability are provided. It is possible to provide an ultraviolet curable resin composition useful as an adhesive in fields such as electro-optical component materials, optical component materials, and liquid crystal materials.
以下、本発明についてより詳細に説明する。
本発明は、重量平均分子量１５，０００〜４０，０００のウレタン（メタ）アクリレートオリゴマーと（メタ）アクリレートモノマーと光開始剤とを含む紫外線硬化樹脂組成物であり、さらに上記各成分の配合が、ウレタン（メタ）アクリレートオリゴマー：（メタ）アクリレートモノマー＝７５：２５〜５５：４５（質量部）であり、これらの合計１００質量部に対して、光開始剤が０．１〜１０質量部である紫外線硬化樹脂組成物である。
Hereinafter, the present invention will be described in more detail.
The present invention is an ultraviolet curable resin composition comprising a urethane (meth) acrylate oligomer having a weight average molecular weight of 15,000 to 40,000, a (meth) acrylate monomer, and a photoinitiator, and further, the blending of each of the above components is Urethane (meth) acrylate oligomer: (meth) acrylate monomer = 75: 25 to 55:45 (parts by mass), and the photoinitiator is 0.1 to 10 parts by mass with respect to 100 parts by mass in total. It is an ultraviolet curable resin composition.
ここで上記ウレタン（メタ）アクリレートオリゴマーは本発明の紫外線硬化樹脂組成物のベース成分となるもので、例えば、ジイソシアネートとエチレン性不飽和基を有する化合物とを反応させることにより得られる。 Here, the urethane (meth) acrylate oligomer is a base component of the ultraviolet curable resin composition of the present invention, and can be obtained, for example, by reacting a diisocyanate with a compound having an ethylenically unsaturated group.
ジイソシアネートとしては、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、１，３−キシレンジイソシアネート、１，４−キシレンジイソシアネート、１，５−ナフタレンジイソシアネート、ｍ−フェニレンジイソシアネート、ｐ−フェニ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、イソホロンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネートなどが挙げられる。これらの中でもヘキサメチレンジイソシアネート、イソホロンジイソシアネートなどが黄変し難いため更に好ましい。これらのジイソシアネートは１種を用いても良いし、２種以上を併用することもできる。 Diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate. , Hexamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and the like. Among these, hexamethylene diisocyanate, isophorone diisocyanate, and the like are more preferable because they are hardly yellowed. These diisocyanates may be used alone or in combination of two or more.
エチレン性不飽和基を有する化合物としては、例えば、水酸基、酸ハライド基、エポキシ基を有する（メタ）アクリレートを挙げることができる。
水酸基を有する（メタ）アクリレートは、例えば、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、ペンタエリスリトールトリ（メタ）アクリレート、グリセリンジ（メタ）アクリレートなどやアルキルグリシジルエーテル、グリシジル（メタ）アクリレートなどのグリシジル基含有化合物と（メタ）アクリル酸の付加物などが挙げられる。
Examples of the compound having an ethylenically unsaturated group include (meth) acrylates having a hydroxyl group, an acid halide group, and an epoxy group.
Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin di (meth) acrylate, alkyl glycidyl ether, and glycidyl. Examples include adducts of glycidyl group-containing compounds such as (meth) acrylate and (meth) acrylic acid.
酸ハライド基を有する（メタ）アクリレートとしては、（メタ）アクリル酸クロライド、（メタ）アクリル酸ブロマイドなどを挙げることができる。 Examples of the (meth) acrylate having an acid halide group include (meth) acrylic acid chloride and (meth) acrylic acid bromide.
エポキシ基を有する（メタ）アクリレートとしては、（メタ）アクリル酸のグリシジルエステルなどが挙げられる。 Examples of the (meth) acrylate having an epoxy group include glycidyl ester of (meth) acrylic acid.
また、ウレタン（メタ）アクリレートオリゴマーは、市販品としても入手することができ、例えば、日本合成化学社製ＵＶ３０００Ｂ、ＵＶ３７００Ｂ、ＵＶ２０００Ｂ、ＵＶ３２００等を挙げることができる。 Moreover, a urethane (meth) acrylate oligomer can be obtained also as a commercial item, for example, Nippon Synthetic Chemical Co., Ltd. UV3000B, UV3700B, UV2000B, UV3200 etc. can be mentioned.
このようにようにして得られるウレタン（メタ）アクリレートオリゴマーの重量平均分子量は、１５，０００〜４０，０００、より好ましくは１８，０００〜３８，０００のものを採用できる。重量平均分子量が１５，０００よりも小さいと接着性、耐熱性、耐湿性が劣る恐れがあり、逆に、４０，０００よりも大きいと紫外線硬化樹脂組成物の粘度が高くなりすぎ、塗工性や加工性が低下する恐れがあるため好ましくない。 The urethane (meth) acrylate oligomer thus obtained can have a weight average molecular weight of 15,000 to 40,000, more preferably 18,000 to 38,000. If the weight average molecular weight is less than 15,000, the adhesiveness, heat resistance, and moisture resistance may be inferior. On the other hand, if the weight average molecular weight is greater than 40,000, the viscosity of the UV curable resin composition becomes too high, and the coatability is high. And workability may be reduced, which is not preferable.
ここで、一般に、重量平均分子量は数平均分子量に重量の重みを付けて算出されるもので、本発明の重量平均分子量１５，０００〜４０，０００のウレタン（メタ）アクリレートオリゴマーは、数平均分子量に換算すると、５，０００〜８，０００程度に相当するものである。従って、本発明のウレタン（メタ）アクリレートオリゴマーは特許文献１と明確に異なる分子量を有するものである。また、このウレタン（メタ）アクリレートオリゴマーの回転粘度計による６０℃下での粘度は、２０，０００〜８０，０００ｍＰａ・ｓとするのが好ましく、より好ましくは２５，０００〜７０，０００ｍＰａ・ｓとするのがよい。このような当該分子量（当該粘度）を有するウレタン（メタ）アクリレートオリゴマーは、後述する（メタ）アクリレートモノマーと光開始剤との組み合わせによって、より効果的に、特に、ＰＥＴフィルムに対する優れた接着性、耐熱性、耐高温高湿性を有する紫外線樹脂硬化物を与えることが可能となるものである。 Here, in general, the weight average molecular weight is calculated by weighting the number average molecular weight, and the urethane (meth) acrylate oligomer having a weight average molecular weight of 15,000 to 40,000 of the present invention has a number average molecular weight. Is equivalent to about 5,000 to 8,000. Therefore, the urethane (meth) acrylate oligomer of the present invention has a molecular weight clearly different from that of Patent Document 1. Moreover, it is preferable that the viscosity under 60 degreeC of this urethane (meth) acrylate oligomer by a rotational viscometer shall be 20,000-80,000 mPa * s, More preferably, it is 25,000-70,000 mPa * s. It is good to do. The urethane (meth) acrylate oligomer having the molecular weight (viscosity) as described above is more effectively combined with a (meth) acrylate monomer and a photoinitiator, which will be described later, in particular, excellent adhesion to a PET film, An ultraviolet resin cured product having heat resistance and high temperature and high humidity resistance can be provided.
また、（メタ）アクリレートモノマーは上記ウレタン（メタ）アクリレート（ベース成分）の低粘度化や架橋、また後述する光開始剤の溶媒となる成分で、例えば、アクリロイルモルフォリン、ジメチルアクリルアミド、ジエチルアクリルアミド、ジイソプロピルアクリルアミド、イソボルニル（メタ）アクリレート、ジシクロペンテニルアクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、メチル（メタ）アクリレート、エチル（メタ）アクリレート、シクロヘキシルメタクリレート、ジシクロペンタジエニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、ジアセトンアクリルアミド、イソブトキシメチル（メタ）アクリルアミド、３−ヒドロキシシクロヘキシルアクリレート、２−アクリロイルシクロヘキシルコハク酸、Ｎ−ビニルピロリドン等を挙げることができる。これらの中でも、特に、アクリロイルモルフォリン、ジメチルアクリルアミド、Ｎ−ビニルピロリドンが接着性に優れた紫外線硬化樹脂組成物を与えることから好ましい。（メタ）アクリレートモノマーは１種を用いても良いし、２種以上を併用することもできる。 Further, the (meth) acrylate monomer is a component that serves as a solvent for the photoinitiator described below, such as acryloylmorpholine, dimethylacrylamide, diethylacrylamide, low viscosity and crosslinking of the urethane (meth) acrylate (base component). Diisopropylacrylamide, isobornyl (meth) acrylate, dicyclopentenyl acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl methacrylate, dicyclo Pentadienyl (meth) acrylate, tricyclodecanyl (meth) acrylate, diacetone acrylamide, isobutoxymethyl (meth) acrylamide, 3-hydroxy Hexyl acrylate, 2-acryloyl-cyclohexyl succinic acid, and N- vinylpyrrolidone. Among these, acryloylmorpholine, dimethylacrylamide, and N-vinylpyrrolidone are particularly preferable because they give an ultraviolet curable resin composition excellent in adhesiveness. One (meth) acrylate monomer may be used, or two or more may be used in combination.
また、（メタ）アクリレートモノマーは、市販品としても入手することができ、例えば共栄社化学社製ＡＭＯ（アクリロイルモルフォリン）、ライトアクリレートＩＢ−ＸＡ（イソボロニルアクリレート）、ライトアクリレートＩＭＡ（イソミリスチルアクリレート）等を挙げることができる。 The (meth) acrylate monomer can also be obtained as a commercial product. For example, AMO (acryloylmorpholine), light acrylate IB-XA (isoboronyl acrylate), light acrylate IMA (isomyristyl acrylate) manufactured by Kyoeisha Chemical Co., Ltd. And the like.
光開始剤は、紫外線照射により分解活性化して、前述のウレタン（メタ）アクリレート同士又はウレタン（メタ）アクリレートと（メタ）アクリレートモノマーとの共重合、架橋などの反応促進を行なう成分で公知の光開始剤を使用することができる。具体的な光開始剤として、例えば、１−ヒドロキシシクロヘキシルフェニルケトン、２，２−ジメトキシ−２−フェニルアセトフェノン、フェニルアセトフェノンジエチルケタール、アルコキシアセトフェノン、ベンジルメチルケタール、ベンゾフェノン及び３，３−ジメチル−４−メトキシベンゾフェノン、４，４−ジメトキシベンゾフェノン、４，４−ジアミノベンゾフェノン等のベンゾフェノン誘導体、ベンゾイル安息香酸アルキル、ビス（４−ジアルキルアミノフェニル）ケトン、ベンジル及びベンジルメチルケタール等のベンジル誘導体、ベンゾイル及びベンゾインブチルメチルケタール等のベンゾイン誘導体、ベンゾインイソプロピルエーテル、２−ヒドロキシ−２−メチルプロピオフェノン、２，４−ジエチルチオキサントン及び２，４−ジクロロチオキサントン等のチオキサントン誘導体、フルオレン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノプロパン−１、２−ベンジル−２−ジメチルアミノ−１−（モルホリノフェニル）−ブタノン−１、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルホスフィンオキシド等のホスフィンオキシド誘導体が挙げられる。これらの中でも、特に、ベンゾフェノン、ベンゾインイソプロピルエーテル、１−ヒドロキシシクロヘキシルフェニルケトンは分子吸光係数が大きいことから好ましい。 A photoinitiator is a component that is activated by decomposing by irradiation with ultraviolet rays and promotes reactions such as copolymerization and crosslinking of the aforementioned urethane (meth) acrylates or urethane (meth) acrylate and (meth) acrylate monomer. Initiators can be used. Specific photoinitiators include, for example, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, phenylacetophenone diethyl ketal, alkoxyacetophenone, benzylmethyl ketal, benzophenone and 3,3-dimethyl-4- Benzophenone derivatives such as methoxybenzophenone, 4,4-dimethoxybenzophenone and 4,4-diaminobenzophenone, benzoylalkyl benzoate, bis (4-dialkylaminophenyl) ketone, benzyl derivatives such as benzyl and benzylmethyl ketal, benzoyl and benzoinbutyl Benzoin derivatives such as methyl ketal, benzoin isopropyl ether, 2-hydroxy-2-methylpropiophenone, 2,4-diethylthioxanthone And thioxanthone derivatives such as 2,4-dichlorothioxanthone, fluorene, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, 2-benzyl-2-dimethylamino-1- (morpholinophenyl) ) -Butanone-1,2,4,6-trimethylbenzoyldiphenylphosphine oxide, and phosphine oxide derivatives such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. Among these, benzophenone, benzoin isopropyl ether, and 1-hydroxycyclohexyl phenyl ketone are particularly preferable because of their large molecular extinction coefficients.
また、光開始剤は、市販品としても入手することができ、例えば、チバスペシャルティーケミカルズ社製イルガキュア１８４Ｄ（１−ヒドロキシシクロヘキシルフェニルケトン）、ダロキュア１１７３（２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン）、イルガキュア９０７（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ン−１−オン）等を挙げることができる。 Photoinitiators can also be obtained as commercial products, such as Irgacure 184D (1-hydroxycyclohexyl phenyl ketone), Darocur 1173 (2-hydroxy-2-methyl-1-phenyl) manufactured by Ciba Specialty Chemicals. -Propan-1-one), Irgacure 907 (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one) and the like.
このような紫外線硬化樹脂組成物の上記各成分の配合は、ウレタン（メタ）アクリレートオリゴマー：（メタ）アクリレートモノマー＝７５：２５〜５５：４５（質量部）とし、これらの合計１００質量部に対して、光開始剤を０．１〜１０質量部とすることができる。 The composition of each of the above components of the ultraviolet curable resin composition is urethane (meth) acrylate oligomer: (meth) acrylate monomer = 75: 25 to 55:45 (parts by mass), and the total of these is 100 parts by mass. Thus, the photoinitiator can be 0.1 to 10 parts by mass.
前述の通り、ウレタン（メタ）アクリレートオリゴマーは、ベース成分として機能し、（メタ）アクリレートモノマーは該ウレタン（メタ）アクリレートオリゴマーの低粘度化や架橋、また、光開始剤の溶媒となる成分として機能するため、ウレタン（メタ）アクリレートオリゴマーが５５質量部未満（（メタ）アクリレートモノマーが４５質量部超過）ではウレタン（メタ）アクリレートオリゴマーが不足し、ＰＥＴフィルムに対する優れた接着性、耐熱性、耐高温高湿性を有する紫外線樹脂硬化物を与えることができなくなる恐れがあり、ウレタン（メタ）アクリレートオリゴマーが７５質量部超過（（メタ）アクリレートモノマーが２５質量部未満）では（ウレタン（メタ）アクリレートオリゴマーと（メタ）アクリレートモノマーの合計を１００質量部としているので）相対的に（メタ）アクリレートモノマーが不足し、紫外線硬化樹脂組成物の粘度が高くなりすぎる恐れがあり好ましくない。 As described above, the urethane (meth) acrylate oligomer functions as a base component, and the (meth) acrylate monomer functions as a component that serves as a solvent for reducing the viscosity and crosslinking of the urethane (meth) acrylate oligomer and as a solvent for the photoinitiator. Therefore, when the urethane (meth) acrylate oligomer is less than 55 parts by mass (the (meth) acrylate monomer exceeds 45 parts by mass), the urethane (meth) acrylate oligomer is insufficient, and excellent adhesion to PET film, heat resistance, and high temperature resistance. There is a possibility that a UV resin cured product having high humidity cannot be provided, and when the urethane (meth) acrylate oligomer exceeds 75 parts by mass (the (meth) acrylate monomer is less than 25 parts by mass) (urethane (meth) acrylate oligomer and Of (meth) acrylate monomer Since the total is 100 parts by mass) relative (meth) acrylate monomer is insufficient, there is a possibility that the viscosity of the ultraviolet curable resin composition is too high is not preferable.
また、紫外線硬化に際し、ウレタン（メタ）アクリレートオリゴマーと（メタ）アクリレートモノマーの合計１００質量部に対し、光開始剤０．１質量部未満の添加では十分な重合開始能がなく、光開始剤１０質量部を超えると重合開始能が頭打ちとなるため好ましくない。 Further, in the case of ultraviolet curing, the addition of less than 0.1 part by weight of the photoinitiator with respect to a total of 100 parts by weight of the urethane (meth) acrylate oligomer and the (meth) acrylate monomer does not provide sufficient polymerization initiation ability, and the photoinitiator 10 Exceeding parts by mass is not preferable because the polymerization initiating ability reaches a peak.
更に、本発明の紫外線硬化樹脂組成物には、接着促進剤としてシランカップリング剤を添加することができる。このシランカップリング剤としては、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−メタクリロキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−クロロプロピルメトキシシラン、ビニルトリクロロシラン、γ−メルカプトプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルトリメトキシシランなどがあり、これらの１種を単独で又は２種以上を混合して用いることができる。これらシランカップリング剤の添加量は、上記ウレタンアクリレートオリゴマー及び（メタ）アクリレートモノマーの合計１００質量部に対して、通常０．１〜５質量部で十分である。 Furthermore, a silane coupling agent can be added as an adhesion promoter to the ultraviolet curable resin composition of the present invention. As this silane coupling agent, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Xylpropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropylmethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- There are β (aminoethyl) -γ-aminopropyltrimethoxysilane and the like, and one of these can be used alone or two or more of them can be used in combination. As for the addition amount of these silane coupling agents, 0.1-5 mass parts is enough normally with respect to a total of 100 mass parts of the said urethane acrylate oligomer and a (meth) acrylate monomer.
また、本発明の紫外線硬化樹脂組成物には、同様に接着性を向上させる目的でエポキシ基含有化合物を添加することができる。エポキシ基含有化合物としては、トリグリシジルトリス（２−ヒドロキシエチル）イソシアヌレート；ネオペンチルグリコールジグリシジルエーテル；１，６−ヘキサンジオールジグリシジルエーテル；アクリルグリシジルエーテル；２−エチルヘキシルグリシジルエーテル；フェニルグリシジルエーテル；フェノールグリシジルエーテル；ｐ−ｔ−ブチルフェニルグリシジルエーテル；アジピン酸ジグリシジルエステル；ｏ−フタル酸ジグリシジルエステル；グリシジルメタクリレート；ブチルグリシジルエーテル等が挙げられる。また、エポキシ基を含有した分子量が数百から数千のオリゴマーや重量平均分子量が数千から数十万のポリマーを添加することによっても同様の効果が得られる。これらエポキシ基含有化合物の添加量は、上記ウレタンアクリレートオリゴマー及び（メタ）アクリレートモノマーの合計１００質量部に対して、１０〜３０質量部で十分で、上記エポキシ基含有化合物の少なくとも１種を単独で、又は混合して添加することができる。 Similarly, an epoxy group-containing compound can be added to the ultraviolet curable resin composition of the present invention for the purpose of improving adhesiveness. Examples of the epoxy group-containing compound include triglycidyl tris (2-hydroxyethyl) isocyanurate; neopentyl glycol diglycidyl ether; 1,6-hexanediol diglycidyl ether; acrylic glycidyl ether; 2-ethylhexyl glycidyl ether; Examples thereof include phenol glycidyl ether; pt-butylphenyl glycidyl ether; adipic acid diglycidyl ester; o-phthalic acid diglycidyl ester; glycidyl methacrylate; Further, the same effect can be obtained by adding an oligomer containing an epoxy group having a molecular weight of several hundred to several thousand or a polymer having a weight average molecular weight of several thousand to several hundred thousand. As for the addition amount of these epoxy group-containing compounds, 10 to 30 parts by mass is sufficient for a total of 100 parts by mass of the urethane acrylate oligomer and the (meth) acrylate monomer, and at least one of the epoxy group-containing compounds is used alone. Or can be mixed and added.
以上の添加剤の他、本発明の光硬化性接着剤は、紫外線吸収剤、老化防止剤、染料等を少量含んでいてもよい。また、場合によってはシリカゲル、炭酸カルシウム、シリコン共重合体の微粒子等の充填剤を少量含んでもよい。 In addition to the above additives, the photocurable adhesive of the present invention may contain a small amount of an ultraviolet absorber, an anti-aging agent, a dye and the like. In some cases, a small amount of fillers such as silica gel, calcium carbonate, silicon copolymer fine particles and the like may be contained.
このようにして形成される紫外線硬化樹脂組成物によるＰＥＴフィルムへの接着層の厚みは、１０〜１５０μｍ、特に２０〜１００μｍの範囲が好ましい。１０μｍ未満では接着性が不十分であり、１５０μｍを超えると硬化が不十分となる恐れがあり好ましくない。 Thus, the thickness of the contact bonding layer to the PET film by the ultraviolet curable resin composition formed is 10-150 micrometers, Especially the range of 20-100 micrometers is preferable. If it is less than 10 μm, the adhesion is insufficient, and if it exceeds 150 μm, curing may be insufficient, which is not preferable.
上記の接着層をＰＥＴフィルム上に塗布する方法としては、均一な厚さの層が形成できる方法を選択すればよく、スクリーン印刷、スプレー塗布、ディッピング塗布等の公知の方法が使用できる。 As a method for applying the adhesive layer on the PET film, a method capable of forming a layer having a uniform thickness may be selected, and known methods such as screen printing, spray coating, and dipping coating can be used.
本発明の紫外線硬化樹脂組成物を硬化する場合は、光源として紫外〜可視領域に発光する多くのものが採用でき、例えば、超高圧、高圧、低圧水銀灯、ケミカルランプ、キセノンランプ、ハロゲンランプ、マーキュリーハロゲンランプ、カーボンアーク灯、白熱灯、レーザー光等が挙げられる。照射時間は、ランプの種類、光源の強さによって一概には決められないが、数十秒〜数十分程度である。 When the ultraviolet curable resin composition of the present invention is cured, many light sources that emit light in the ultraviolet to visible region can be used as the light source, for example, ultrahigh pressure, high pressure, low pressure mercury lamp, chemical lamp, xenon lamp, halogen lamp, mercury A halogen lamp, a carbon arc lamp, an incandescent lamp, a laser beam, etc. are mentioned. The irradiation time cannot be determined unconditionally depending on the type of lamp and the intensity of the light source, but it is about several tens of seconds to several tens of minutes.
また、硬化促進のために、予め積層体を３０〜８０℃に加温し、これに紫外線を照射してもよい。 In order to accelerate curing, the laminate may be preheated to 30 to 80 ° C. and irradiated with ultraviolet rays.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において部は質量部を示す。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part.
［実施例１〜５，比較例１〜５］
下記表１に示す各実施例及び比較例の配合で市販のウレタンアクリレートオリゴマー、アクリレートモノマー、光開始剤の各成分を均一になるまで攪拌し、各紫外線硬化樹脂組成物を調製した。
[Examples 1-5, Comparative Examples 1-5]
Each component of a commercially available urethane acrylate oligomer, acrylate monomer, and photoinitiator was agitated with the formulation of each Example and Comparative Example shown in Table 1 below to prepare each ultraviolet curable resin composition.
一方、幅１５０ｍｍ×長さ１５０ｍｍ×厚さ１８８μｍのＰＥＴフィルムを用意し、該ＰＥＴフィルム上に端から幅１５０ｍｍ×長さ２５ｍｍ×厚さ４５μｍの離型マスクを載置し、該ＰＥＴフィルムの１／６の面積を被覆すると共に、該離型マスク被覆部及び離型マスク非被覆部（離型マスクで覆われていない部分であって、該ＰＥＴフィルムの残りの５／６の面積を有する部分）の両方の上から、上記任意の配合の紫外線硬化樹脂組成物を全面的にスプレー塗布し、該離型マスク非被覆部に幅１５０ｍｍ×長さ１２５ｍｍ×厚さ１００μｍ（上記ＰＥＴフィルム上に直接厚さ１００μｍの紫外線硬化樹脂組成物を塗布）、該離型マスク被覆部に幅１５０ｍｍ×長さ２５ｍｍ×厚さ５５μｍ（上記ＰＥＴフィルム上に載置した厚さ４５μｍの離型マスク上に厚さ５５μｍの紫外線硬化樹脂組成物を塗布）の紫外線硬化樹脂組成物を形成し、これらに紫外線照射装置（ウシオ電機株式会社製，型番ＳＰ−７）を用いて１５ｃｍの位置から５秒間３６５ｎｍの紫外線を照射し、該紫外線硬化樹脂組成物を硬化させた後、該離型マスクを外し、ＰＥＴフィルムへの紫外線樹脂硬化物の接着部分：幅１５０ｍｍ×長さ１２５ｍｍ×厚さ約１００μｍと未接着部分：幅１５０ｍｍ×長さ２５ｍｍ×厚さ約５５μｍとを有する試料を得た。 On the other hand, a PET film having a width of 150 mm × a length of 150 mm × a thickness of 188 μm was prepared, and a release mask having a width of 150 mm × a length of 25 mm × a thickness of 45 μm from the end was placed on the PET film. / 6 area, and the release mask coating portion and the release mask non-cover portion (the portion not covered by the release mask and having the remaining 5/6 area of the PET film) The UV curable resin composition of the above-mentioned arbitrary composition is spray-coated all over from above, and the width of the release mask non-covered part is 150 mm wide × 125 mm long × 100 μm thick (directly on the PET film). 100 μm thick UV curable resin composition is applied), and the release mask coating part is 150 mm wide × 25 mm long × 55 μm thick (a 45 μm thick release mass placed on the PET film) A UV curable resin composition having a thickness of 55 μm is applied onto the film, and an ultraviolet irradiation device (model number SP-7, manufactured by USHIO INC.) Is used to form 5 UV curable resin compositions. After irradiating 365 nm of ultraviolet rays for 2 seconds to cure the ultraviolet curable resin composition, the release mask was removed, and the adhesion part of the ultraviolet resin cured product to the PET film: width 150 mm × length 125 mm × thickness about 100 μm And a non-adhered portion: a sample having a width of 150 mm × a length of 25 mm × a thickness of about 55 μm was obtained.
さらに、この試料を幅２５ｍｍ、６等分に裁断して得られたＰＥＴフィルムへの紫外線樹脂硬化物の接着部分：幅２５ｍｍ×長さ１２５ｍｍ×厚さ約１００μｍと、未接着部分：幅２５ｍｍ×長さ２５ｍｍ×厚さ約５５μｍとからなる試料片の、未接着部分のＰＥＴフィルムと紫外線樹脂硬化物をそれぞれ引っ張り試験機のクランプで把持し、クロスヘッドスピード５０ｍｍ／ｍｉｎでＴピール試験を行い、該ＰＥＴフィルムと紫外線樹脂硬化物との接着部分の接着強度を調べた。なお、該接着強度は、この初期値の他、８５℃，１００時間放置後、及び６５℃，９０％ＲＨ×１００時間放置後についても調べた。結果を表１に示す。 Furthermore, the adhesive part of the UV resin cured product to the PET film obtained by cutting this sample into 25 mm width and 6 equal parts: width 25 mm × length 125 mm × thickness of about 100 μm, and unadhered part: width 25 mm × A sample piece consisting of 25 mm long x about 55 μm thick, the unbonded part of the PET film and the UV resin cured product are each held by a clamp of a tensile tester, and a T peel test is performed at a crosshead speed of 50 mm / min. The adhesive strength of the adhesive portion between the PET film and the ultraviolet resin cured product was examined. In addition to the initial value, the adhesive strength was also examined after standing at 85 ° C. for 100 hours and after standing at 65 ° C. and 90% RH × 100 hours. The results are shown in Table 1.
注）
（＊１）ＵＶ３７００Ｂ：日本合成化学社製ウレタンアクリレートオリゴマー，重量平均分子量３８０００，数平均分子量８０００，粘度３００００〜６００００ｍＰａ・ｓ／６０℃，ガラス転移点−５９℃。
（＊２）ＵＶ３０００Ｂ：日本合成化学社製ウレタンアクリレートオリゴマー，重量平均分子量１８０００，数平均分子量５０００，粘度４５０００〜６５０００ｍＰａ・ｓ／６０℃，ガラス転移点−５２℃。
（＊３）ＵＸ３２０４：日本化薬社製ウレタンアクリレートオリゴマー，重量平均分子量１１５００，数平均分子量３１００，粘度１８７００ｍＰａ・ｓ／６０℃，ガラス転移点−３９℃。
（＊４）ＵＸ２３０１：日本化薬社製ウレタンアクリレートオリゴマー，重量平均分子量７２００，数平均分子量３３００，粘度２１３０ｍＰａ・ｓ／６０℃，ガラス転移点−３９℃。
（＊５）ＵＦ８００１：共栄社化学社製ウレタンアクリレートオリゴマー，重量平均分子量４５００，数平均分子量２３００，粘度４９８００ｍＰａ・ｓ／６０℃，ガラス転移点＋５６℃。
（＊６）ＡＭＯ：共栄社化学社製アクリロイルモルフォリン。
（＊７）イルガキュア１８４Ｄ：チバスペシャルティーケミカルズ社製１−ヒドロキシ−シクロヘキシル−フェニル−ケトン。光開始剤。
note)
(* 1) UV3700B: urethane acrylate oligomer manufactured by Nippon Synthetic Chemical Co., Ltd., weight average molecular weight 38000, number average molecular weight 8000, viscosity 30000-60000 mPa · s / 60 ° C., glass transition point −59 ° C.
(* 2) UV3000B: Nippon Synthetic Chemical Co., Ltd. urethane acrylate oligomer, weight average molecular weight 18000, number average molecular weight 5000, viscosity 45000-65000 mPa · s / 60 ° C., glass transition point −52 ° C.
(* 3) UX3204: Nippon Kayaku Co., Ltd. urethane acrylate oligomer, weight average molecular weight 11500, number average molecular weight 3100, viscosity 18700 mPa · s / 60 ° C., glass transition point −39 ° C.
(* 4) UX2301: urethane acrylate oligomer manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight 7200, number average molecular weight 3300, viscosity 2130 mPa · s / 60 ° C., glass transition point −39 ° C.
(* 5) UF8001: urethane acrylate oligomer manufactured by Kyoeisha Chemical Co., Ltd., weight average molecular weight 4500, number average molecular weight 2300, viscosity 49800 mPa · s / 60 ° C., glass transition point + 56 ° C.
(* 6) AMO: Acryloyl morpholine manufactured by Kyoeisha Chemical Co., Ltd.
(* 7) Irgacure 184D: 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by Ciba Specialty Chemicals. Photoinitiator.
表１より、実施例１〜５は比較例１〜５に対して、初期値のみならず、８５℃，１００時間放置後、及び６５℃，９０％ＲＨ×１００時間放置後の接着強度についても優れていることが確認された。 From Table 1, Examples 1 to 5 are not only the initial values but also the adhesive strength after being left at 85 ° C. for 100 hours and after being left at 65 ° C. and 90% RH × 100 hours as compared with Comparative Examples 1 to 5. It was confirmed to be excellent.
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| WO2010122768A1 (en) * | 2009-04-20 | 2010-10-28 | 株式会社ブリヂストン | Thiol group-containing adhesive resin composition |
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