JP2005320418A - Ultraviolet curing-type organopolysiloxane composition - Google Patents
Ultraviolet curing-type organopolysiloxane composition Download PDFInfo
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Abstract
Description
本発明は、接着剤として好適に用いられる紫外線硬化型オルガノポリシロキサン組成物に関するものである。 The present invention relates to an ultraviolet curable organopolysiloxane composition suitably used as an adhesive.
シリコーン材料は、その優れた耐熱性・耐候性・電気特性等から電気・電子部品用途や自動車部品に広く使用されている。更に最近、硬化時間が早いことなどから紫外線により硬化する官能基（アクリル基・メタクリル基等）をシリコーンに導入し、接着剤として使用される材料が開発されている（特許文献１：特開昭６１−１２７７１８号公報参照）。
しかしながら、その材料はオルガノポリシロキサンの末端に導入するため、シリコーン材料としての性質が強く、一般アクリル系接着剤に見られるような高硬度で接着強度の強い材料を開発することができなかった。
Silicone materials are widely used in electrical / electronic parts applications and automotive parts because of their excellent heat resistance, weather resistance, electrical properties, and the like. In recent years, materials that can be used as adhesives have been developed by introducing functional groups (acrylic groups, methacrylic groups, etc.) that are cured by ultraviolet rays into silicones due to their fast curing time (Patent Document 1: Japanese Patent Application Laid-Open (JP-A)). 61-127718).
However, since the material is introduced at the end of the organopolysiloxane, it has strong properties as a silicone material, and it has not been possible to develop a material having high hardness and high adhesive strength as found in general acrylic adhesives.
従って、本発明の目的は、高硬度で接着強度が高く、接着剤として好適な紫外線硬化型オルガノポリシロキサン組成物を提供することにある。 Accordingly, an object of the present invention is to provide an ultraviolet curable organopolysiloxane composition that has high hardness and high adhesive strength and is suitable as an adhesive.
本発明者は、上記目的を達成するため鋭意検討を行った結果、下記一般式（１）のように側鎖にアクリル基やメタクリル基等の官能基を導入し、接着用添加剤としてウレタンアクリレート化合物を添加することで、シリコーンの耐熱性を保持したまま、高硬度で接着性のある材料が得られることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventor introduced a functional group such as an acryl group or a methacryl group into the side chain as shown in the following general formula (1), and urethane acrylate as an adhesive additive. By adding the compound, it was found that a material having high hardness and adhesiveness can be obtained while maintaining the heat resistance of silicone, and the present invention has been made.
従って、本発明は、
（Ａ）下記一般式（１）
Therefore, the present invention
(A) The following general formula (1)
で示される構造からなる環状又は鎖状のオルガノポリシロキサン（但し、各シロキサン単位の配列はランダムである）であって、鎖状の場合、末端がトリメチルシロキシ基、アクリロキシジメチルシロキシ基又はメタクリロキシジメチルシロキシ基により封鎖されたオルガノポリシロキサン １００質量部
（Ｂ）下記一般式（２）
で示される構造を持つウレタンアクリレート化合物 ０．１質量部以上
（Ｃ）光開始剤 ０．０１〜１０質量部
を必須成分とすることを特徴とする紫外線硬化型オルガノポリシロキサン組成物
を提供する。
A cyclic or chain organopolysiloxane having a structure represented by the formula (wherein the arrangement of each siloxane unit is random), and in the case of a chain, the terminal is a trimethylsiloxy group, an acryloxydimethylsiloxy group or a methacryloxy group. Organopolysiloxane blocked with dimethylsiloxy group 100 parts by mass (B) The following general formula (2)
An ultraviolet curable organopolysiloxane composition characterized by comprising 0.1 to 10 parts by mass of a urethane acrylate compound having a structure represented by the formula (C) 0.01 to 10 parts by mass of a photoinitiator as an essential component.
本発明の紫外線硬化型オルガノポリシロキサン組成物によれば、シリコーンの耐熱性を保持したまま、高硬度で接着性のある硬化物を形成することができる。 According to the ultraviolet curable organopolysiloxane composition of the present invention, a cured product having high hardness and adhesion can be formed while maintaining the heat resistance of silicone.
本発明の紫外線硬化型オルガノポリシロキサン組成物の（Ａ）成分は、紫外線で硬化させるために使用されるベースポリマーであり、下記一般式（１）
で示される構造からなる環状又は鎖状のオルガノポリシロキサン（但し、各シロキサン単位の配列はランダムである）であって、鎖状の場合、末端がトリメチルシロキシ基、アクリロキシジメチルシロキシ基又はメタクリロキシジメチルシロキシ基により封鎖されたオルガノポリシロキサンである。
The component (A) of the ultraviolet curable organopolysiloxane composition of the present invention is a base polymer used for curing with ultraviolet rays, and the following general formula (1)
A cyclic or chain organopolysiloxane having a structure represented by the formula (wherein the arrangement of each siloxane unit is random), and in the case of a chain, the terminal is a trimethylsiloxy group, an acryloxydimethylsiloxy group or a methacryloxy group. An organopolysiloxane blocked with dimethylsiloxy groups.
即ち、（Ａ）成分のオルガノポリシロキサンは、Ｒ1Ｒ2ＳｉＯ2/2単位とＲ2 2ＳｉＯ2/2単位とからなる環状のオルガノポリシロキサンであるか、又は主鎖がＲ1Ｒ2ＳｉＯ2/2単位及びＲ2 2ＳｉＯ2/2単位からなり、分子鎖両末端がＲ2 3ＳｉＯ1/2単位又はＲ1（ＣＨ3）2ＳｉＯ1/2単位で封鎖された鎖状のオルガノポリシロキサンである。 That is, the organopolysiloxane of component (A) is a cyclic organopolysiloxane composed of R 1 R 2 SiO 2/2 units and R 2 2 SiO 2/2 units, or the main chain is R 1 R 2. It is composed of a SiO 2/2 unit and a R 2 2 SiO 2/2 unit, and both ends of the molecular chain are blocked with R 2 3 SiO 1/2 units or R 1 (CH 3 ) 2 SiO 1/2 units. Organopolysiloxane.
ここで、Ｒ1はアクリロキシプロピル基又はメタクリロキシプロピル基で、同一でも異なっていてもよく、この官能基が光開始剤と共存下で紫外線を照射されるとラジカル反応を起こし、重合していくものである。 Here, R 1 is an acryloxypropyl group or a methacryloxypropyl group, which may be the same or different. When this functional group is irradiated with ultraviolet rays in the presence of a photoinitiator, it undergoes a radical reaction and polymerizes. It is going.
Ｒ2はＲ1以外の一価炭化水素基であり、好ましくは炭素数１〜１０、特に１〜８のものである。具体的にはメチル基、エチル基、プロピル基、イソプロピル基、イソブチル基、ｔｅｒｔ−ブチル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、フェニル基、トリル基、キシリル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基、ビニル基、アリル基、ブテニル基、ペンテル基、ヘキセニル基等のアルケニル基が挙げられ、好ましくは、アルキル基であり、特に好ましくはメチル基である。 R 2 is a monovalent hydrocarbon group other than R 1 , and preferably has 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms. Specifically, methyl groups, ethyl groups, propyl groups, isopropyl groups, isobutyl groups, tert-butyl groups, butyl groups, pentyl groups, hexyl groups and other alkyl groups, cyclopentyl groups, cyclohexyl groups and other cycloalkyl groups, phenyl groups Aryl groups such as tolyl group and xylyl group, aralkyl groups such as benzyl group and phenethyl group, alkenyl groups such as vinyl group, allyl group, butenyl group, pentyl group and hexenyl group, preferably an alkyl group. Particularly preferred is a methyl group.
また、式（１）において、ｋは１〜１，０００、好ましくは３〜１５０の整数、ｍは０〜５００、好ましくは０〜１００の整数であり、ｋ、ｍは、ｋ／（ｋ＋ｍ）＝０．５〜１、好ましくは０．８〜１を満足する０又は正の整数である。この場合、ｋの単位は紫外線により重合する官能基（アクリロキシプロピル基又はメタアクリロキシプロピル基）を有する単位であり、ｋ／（ｋ＋ｍ）＜０．５では、要求される接着強度を得ることができない。 In the formula (1), k is an integer of 1 to 1,000, preferably 3 to 150, m is an integer of 0 to 500, preferably 0 to 100, and k and m are k / (k + m). = 0.5 to 1, preferably 0 or a positive integer satisfying 0.8 to 1. In this case, the unit of k is a unit having a functional group (acryloxypropyl group or methacryloxypropyl group) that is polymerized by ultraviolet rays. When k / (k + m) <0.5, the required adhesive strength is obtained. I can't.
なお、ｋ＋ｍは３〜１，０００、好ましくは３〜２５０、特に３〜１５０であることが好ましい。 K + m is 3 to 1,000, preferably 3 to 250, and particularly preferably 3 to 150.
以下に、（Ａ）成分として用いられる化合物の具体例を示す。 Below, the specific example of the compound used as (A) component is shown.
本発明の（Ｂ）成分は、紫外線で硬化した材料を接着させるために添加する化合物であり、下記一般式（２）に示すようなウレタンアクリレート基を持つことで各種被着体に対する接着性が向上する。 (B) component of this invention is a compound added in order to adhere | attach the material hardened | cured with the ultraviolet-ray, and it has adhesiveness with respect to various adherends by having a urethane acrylate group as shown in the following general formula (2). improves.
ここで、Ｒ3はｎ価（ｎ＝１〜４）の有機基であり、炭素数１〜１３、特に１〜８のものが好ましく、メチル基、エチル基、プロピル基、イソプロピル基、イソブチル基、ｔｅｒｔ−ブチル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、フェニル基、トリル基、キシリル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基、ビニル基、アリル基、ブテニル基、ペンテル基、ヘキセニル基等のアルケニル基が挙げられ、更にメチレン基、エチレン基、ペンタメチレン基、ヘキサメチレン基等のアルキレン基、また以下の構造を持った有機基が挙げられ、特に好ましくは、アルキレン基である。 Here, R 3 is an n-valent (n = 1 to 4) organic group, preferably having 1 to 13 carbon atoms, particularly 1 to 8 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, isobutyl group. Tert-butyl group, butyl group, pentyl group, hexyl group and other alkyl groups, cyclopentyl group, cyclohexyl group and other cycloalkyl groups, phenyl group, tolyl group, xylyl group and other aryl groups, benzyl group, phenethyl group, etc. Examples include alkenyl groups such as aralkyl groups, vinyl groups, allyl groups, butenyl groups, pentyl groups, hexenyl groups, and alkylene groups such as methylene groups, ethylene groups, pentamethylene groups, hexamethylene groups, and the following structures. And particularly preferably an alkylene group.
Ｒ4は一価の有機基であり、炭素数１〜１３、特に１〜８の一価炭化水素基が好ましく、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、フェニル基、トリル基、キシリル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基、ビニル基、アリル基、ブテニル基、ペンテル基、ヘキセニル基等のアルケニル基が挙げられ、好ましくは、アルキル基であり、特に好ましくは、メチル基である。また炭化水素基だけでなく、ウレイド結合、アミド結合、尿素結合等の窒素・酸素含有結合、エーテル結合を有した官能基でも接着性の向上となりやすく、有用性が高い。
また、Ｒ5は水素原子、メチル基又はフェニル基である。
R 4 is a monovalent organic group, preferably a monovalent hydrocarbon group having 1 to 13 carbon atoms, particularly 1 to 8, and alkyl such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group. Group, cycloalkyl group such as cyclopentyl group and cyclohexyl group, aryl group such as phenyl group, tolyl group and xylyl group, aralkyl group such as benzyl group and phenethyl group, vinyl group, allyl group, butenyl group, pentyl group, hexenyl group And an alkenyl group such as an alkyl group, and a methyl group is particularly preferable. Also, not only hydrocarbon groups but also functional groups having nitrogen / oxygen-containing bonds such as ureido bonds, amide bonds, urea bonds, and ether bonds, and the functional groups having ether bonds, are likely to improve the adhesiveness and are highly useful.
R 5 is a hydrogen atom, a methyl group or a phenyl group.
下記に（Ｂ）成分の具体例を示す。 Specific examples of the component (B) are shown below.
上記（Ｂ）成分の配合量は、（Ａ）成分の１００質量部に対して０．１質量部以上であり、好ましくは０．１〜６０質量部、更に好ましくは０．２〜４０質量部である。 The blending amount of the component (B) is 0.1 parts by mass or more, preferably 0.1 to 60 parts by mass, more preferably 0.2 to 40 parts by mass with respect to 100 parts by mass of the component (A). It is.
本発明の（Ｃ）成分は、（Ａ），（Ｂ）成分を紫外線で硬化させるために必要な光開始剤であり、光開始剤としては、例えばベンゾインとその誘導体、ベンゾインアクリルエーテルなどのベンゾインエーテル類、ベンジルとその誘導体、芳香族ジアゾニウム塩、アントラキノンとその誘導体、アセトフェノンとその誘導体、ジフェニルジスルフイドなどのイオウ化合物、ベンゾフェノンとその誘導体等、従来知られた適宜の光開始剤を用いうる。光開始剤の添加量は、（Ａ）成分１００質量部に対し０．０１〜１０質量部であり、特に０．１〜５質量部が好ましいが、光開始剤の種類や性質によっては上記範囲外でも用いうる。 The component (C) of the present invention is a photoinitiator necessary for curing the components (A) and (B) with ultraviolet rays. Examples of the photoinitiator include benzoin and its derivatives, and benzoin such as benzoin acrylic ether. Ether, benzyl and its derivatives, aromatic diazonium salts, anthraquinone and its derivatives, acetophenone and its derivatives, sulfur compounds such as diphenyldisulfide, benzophenone and its derivatives, etc. . The addition amount of the photoinitiator is 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A), and particularly preferably 0.1 to 5 parts by mass. Can be used outside.
本発明の紫外線硬化型オルガノポリシロキサン組成物には、紫外線硬化に支障をきたさない限り、他の添加剤を加えることもできる。このような添加剤としては、公知の光増感剤、接着助剤、安定剤、クラウンエーテル類、クリプテートのようなイオントラップ剤、ハイドロキノン、メトキシハイドロキノンのような重合禁止剤等が挙げられる。他にも可撓性・相溶性向上を目的としてアクリル酸ラウリル、アクリル酸イソボルニル、メタクリル酸２−エチルヘキシル等の反応性希釈剤、メタクリロキシプロピルトリメトキシシラン、アクリロキシプロピルジメトキシメチルシラン等のシランカップリング剤等を添加してもよい。 Other additives may be added to the ultraviolet curable organopolysiloxane composition of the present invention as long as the ultraviolet curing is not hindered. Examples of such additives include known photosensitizers, adhesion assistants, stabilizers, crown ethers, ion trapping agents such as cryptate, and polymerization inhibitors such as hydroquinone and methoxyhydroquinone. Other reactive diluents such as lauryl acrylate, isobornyl acrylate, 2-ethylhexyl methacrylate, and silane cups such as methacryloxypropyltrimethoxysilane and acryloxypropyldimethoxymethylsilane for the purpose of improving flexibility and compatibility A ring agent or the like may be added.
また、本発明の紫外線硬化型オルガノポリシロキサン組成物には、必要に応じて各種充填剤を配合することもでき、硬化時における収縮率や硬化物の機械的強度、耐熱性、耐薬品性、難燃性、熱膨張係数、ガス透過率などを適宜調整することができる。このような添加剤としては、煙霧質シリカ、シリカアロゲル、炭酸カルシウム、炭酸マグネシウム、石英粉末、酸化チタン、酸化鉄、ガラス繊維等の無機充填剤等が挙げられる。 Further, the ultraviolet curable organopolysiloxane composition of the present invention can be blended with various fillers as necessary, shrinkage at the time of curing, mechanical strength of the cured product, heat resistance, chemical resistance, Flame retardancy, thermal expansion coefficient, gas permeability and the like can be adjusted as appropriate. Examples of such additives include fumed silica, silica allogel, calcium carbonate, magnesium carbonate, quartz powder, titanium oxide, iron oxide, inorganic fillers such as glass fiber, and the like.
本発明の紫外線硬化型オルガノポリシロキサン組成物を硬化する場合は、常法により高圧水銀灯、キセノンランプ、ハロゲンランプ、蛍光灯等を使用し、例えば波長２５４ｎｍ、３６５ｎｍで通常の条件において紫外線照射すればよい。 When curing the ultraviolet curable organopolysiloxane composition of the present invention, a high pressure mercury lamp, a xenon lamp, a halogen lamp, a fluorescent lamp or the like is used by a conventional method. Good.
また、本発明の紫外線硬化型オルガノポリシロキサン組成物は、接着剤として有用であり、特にガラス同士の貼り合せ、エポキシ基板の保護、ＣＤピックアップ材料と金属との接着に有効に使用することができる。 Moreover, the ultraviolet curable organopolysiloxane composition of the present invention is useful as an adhesive, and can be used effectively particularly for laminating glass, protecting an epoxy substrate, and bonding a CD pickup material and a metal. .
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、下記例で部は質量部を示し、Ｍｅはメチル基を示す。 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 the following examples, “part” represents “part by mass”, and “Me” represents a methyl group.
［実施例１〜８］
以下の構造を持つ化合物を合成した。
[Examples 1 to 8]
A compound having the following structure was synthesized.
また、ウレタンアクリレート化合物として、共栄社化学（株）製のＡＨ−６００（フェニルグリシジルエーテルアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー）とＡＴ−６００（ペンタエリスリトールトリアクリレートヘキサメチレンジイソシアネートウレタンプレポリマー）を使用した。 As urethane acrylate compounds, AH-600 (phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer) and AT-600 (pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer) manufactured by Kyoeisha Chemical Co., Ltd. were used.
光重合開始剤として、ジエトキシアセトフェノンを使用した。
以下に配合表を示す。また紫外線照射は高圧水銀灯：コンベアタイプ（８０Ｗ／ｃｍ）、距離１０ｃｍ、速度１ｍ／ｍｉｎの照射×１回で行い（合計エネルギー量５００ｍＪ／ｃｍ2）、硬さは（株）上島製作所製のショアーＤ型硬度計にて測定した。接着性は被着体（ガラスに対して強密着しているか簡易的に確認した（○：強密着、×：剥離）。結果を表１に示す。
Diethoxyacetophenone was used as a photopolymerization initiator.
The recipe is shown below. In addition, UV irradiation is performed with a high-pressure mercury lamp: conveyor type (80 W / cm), distance 10 cm, speed 1 m / min. Irradiation 1 time (total energy 500 mJ / cm 2 ), hardness is Shore manufactured by Ueshima Seisakusho Co., Ltd. It was measured with a D-type hardness meter. The adhesion was confirmed simply (whether it was strongly adhered to the glass (O: strong adhesion, x: peeling). Table 1 shows the results.)
＊１ Ｒ−９７２（表面が疎水化処理されたヒュームドシリカ）：日本アエロジル（株）製
＊２ ブレンマーＣＭＡ（メタクリル酸セチル）：日本油脂（株）製
＊３ ＫＢＭ５１０２（γ−アクリロキシプロピルメチルジメトキシシラン）：信越化学工業（株）製
* 1 R-972 (fumed silica whose surface has been hydrophobized): Nippon Aerosil Co., Ltd. * 2 Blemmer CMA (cetyl methacrylate): Nippon Oil & Fats Co., Ltd. * 3 KBM5102 (γ-acryloxypropylmethyl) Dimethoxysilane): Shin-Etsu Chemical Co., Ltd.
［比較例１〜４］
以下の化合物を合成し、表２に示す配合で紫外線硬化型オルガノポリシロキサン組成物を調製し、上記と同様にして物性を評価した。結果を表２に示す。
[Comparative Examples 1-4]
The following compounds were synthesized, UV curable organopolysiloxane compositions were prepared with the formulation shown in Table 2, and the physical properties were evaluated in the same manner as described above. The results are shown in Table 2.
＊１ Ｒ−９７２（表面が疎水化処理されたヒュームドシリカ）：日本アエロジル（株）製
＊２ ブレンマーＣＭＡ（メタクリル酸セチル）：日本油脂（株）製
＊３ ＫＢＭ５１０２（γ−アクリロキシプロピルメチルジメトキシシラン）：信越化学工業（株）製
* 1 R-972 (fumed silica whose surface has been hydrophobized): Nippon Aerosil Co., Ltd. * 2 Blemmer CMA (cetyl methacrylate): Nippon Oil & Fats Co., Ltd. * 3 KBM5102 (γ-acryloxypropylmethyl) Dimethoxysilane): Shin-Etsu Chemical Co., Ltd.
Claims (1)
で示される構造からなる環状又は鎖状のオルガノポリシロキサン（但し、各シロキサン単位の配列はランダムである）であって、鎖状の場合、末端がトリメチルシロキシ基、アクリロキシジメチルシロキシ基又はメタクリロキシジメチルシロキシ基により封鎖されたオルガノポリシロキサン １００質量部
（Ｂ）下記一般式（２）
で示される構造を持つウレタンアクリレート化合物 ０．１質量部以上
（Ｃ）光開始剤 ０．０１〜１０質量部
を必須成分とすることを特徴とする紫外線硬化型オルガノポリシロキサン組成物。 (A) The following general formula (1)
A cyclic or chain organopolysiloxane having a structure represented by the formula (wherein the arrangement of each siloxane unit is random), and in the case of a chain, the terminal is a trimethylsiloxy group, acryloxydimethylsiloxy group or methacryloxy Organopolysiloxane blocked with dimethylsiloxy group 100 parts by mass (B) The following general formula (2)
A urethane acrylate compound having a structure represented by the formula: 0.1 part by mass or more (C) 0.01 to 10 parts by mass of a photoinitiator as an essential component.
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| JP2004138921A JP2005320418A (en) | 2004-05-07 | 2004-05-07 | Ultraviolet curing-type organopolysiloxane composition |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004138921A JP2005320418A (en) | 2004-05-07 | 2004-05-07 | Ultraviolet curing-type organopolysiloxane composition |
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| JP2005320418A true JP2005320418A (en) | 2005-11-17 |
Family
ID=35467916
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| JP2004138921A Pending JP2005320418A (en) | 2004-05-07 | 2004-05-07 | Ultraviolet curing-type organopolysiloxane composition |
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