JP2015071716A - Flame-retardant adhesive composition - Google Patents
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本発明は，湿気硬化型の難燃性接着剤組成物に関し，特に難燃性を有しながら低粘度で作業性が良好であって、且つ高い凝集力と接着性を有する難燃性接着剤組成物に関する。 The present invention relates to a moisture curable flame retardant adhesive composition, and in particular, flame retardant adhesive having low cohesiveness, good workability, and high cohesive strength and adhesiveness. Relates to the composition.
従来、（Ａ）架橋可能な加水分解性シリル基を２個以上含有する有機重合体、（Ｂ）平均粒径０．１〜２００μｍの金属水酸化物、（Ｃ）架橋可能な加水分解性シリル基を片末端のみに有するポリエーテル化合物を必須成分として含有することを特徴とする難燃性湿気硬化型樹脂組成物が提案されている（特許文献１）。該難燃性湿気硬化型樹脂組成物は、ハロゲン系難燃剤や酸化アンチモンなどを使用せず、難燃性の規格であるＵＬ９４垂直燃焼性試験でＶ−０に合格し、低粘度で作業性が良好でありながら接着性も良好で、また低揮発性と低ブリードアウト性を有し、硬化物も強靭であるとされている。 Conventionally, (A) an organic polymer containing two or more crosslinkable hydrolyzable silyl groups, (B) a metal hydroxide having an average particle size of 0.1 to 200 μm, and (C) a crosslinkable hydrolyzable silyl group. A flame-retardant moisture-curable resin composition characterized by containing a polyether compound having a group only at one end as an essential component has been proposed (Patent Document 1). The flame retardant moisture curable resin composition does not use a halogen flame retardant or antimony oxide, and passes V-0 in the UL 94 vertical flammability test, which is a flame retardant standard, and has low viscosity and workability. It is said that it has good adhesiveness while being good, has low volatility and low bleed-out property, and is hardened.
また、難燃性を要求される電気製品もしくは精密機器の組立用等の接着剤、固着剤として優れた性能を有する接着剤組成物として、（Ａ）反応性珪素基含有有機重合体、（Ｂ）平均粒径０．１〜２００μｍの金属水酸化物、及び（Ｃ）２３℃における粘度が５００ｍＰａ・ｓ以下である液状化合物であって、誘電率が５以上及び／又は沸点が１７０℃以下の液状化合物、を必須成分として含有する難燃性湿気硬化型接着剤組成物が提案されている（特許文献２）。 In addition, as an adhesive composition having excellent performance as an adhesive or fixing agent for assembly of electrical products or precision instruments that require flame retardancy, (A) a reactive silicon group-containing organic polymer, (B ) A metal hydroxide having an average particle size of 0.1 to 200 μm, and (C) a liquid compound having a viscosity at 23 ° C. of 500 mPa · s or less, having a dielectric constant of 5 or more and / or a boiling point of 170 ° C. or less. A flame retardant moisture curable adhesive composition containing a liquid compound as an essential component has been proposed (Patent Document 2).
さらには、同様に難燃性を要求される電気製品もしくは精密機器の組立用等の接着剤、固着剤として優れた性能を有する接着剤組成物として、（Ａ）反応性珪素基含有有機重合体、（Ｂ）平均粒径０．１〜２００μｍの金属水酸化物、（Ｃ）親水性シリカ、及び（Ｄ）平均粒径０．０１〜１０μｍの表面処理された炭酸カルシウムを必須成分として含有し、前記重合体（Ａ）１００質量部に対して、前記金属水酸化物（Ｂ）１５０〜３５０質量部、前記親水性シリカ（Ｃ）０．１〜１５質量部、前記炭酸カルシウム（Ｄ）１〜５０質量部を配合することを特徴とする難燃性湿気硬化型組成物が提案されている（特許文献３）。 Furthermore, as an adhesive composition having excellent performance as an adhesive or as an adhesive for assembling an electrical product or precision instrument that similarly requires flame retardancy, (A) a reactive silicon group-containing organic polymer And (B) a metal hydroxide having an average particle size of 0.1 to 200 μm, (C) hydrophilic silica, and (D) a surface-treated calcium carbonate having an average particle size of 0.01 to 10 μm as essential components. The metal hydroxide (B) 150 to 350 parts by mass, the hydrophilic silica (C) 0.1 to 15 parts by mass, and the calcium carbonate (D) 1 with respect to 100 parts by mass of the polymer (A). A flame-retardant moisture-curable composition characterized by blending ˜50 parts by mass has been proposed (Patent Document 3).
しかしながら、これらの組成物は、十分に低粘度であると言えない場合があり、また接着強さは最大でも３．６Ｎ／ｍｍ２が示されるに留まり、より高い接着強さと組成物自体に高い凝集力を要求される場合は、十分に満足するものでない場合があるという課題がある。 However, these compositions may not be said to be sufficiently low in viscosity and the bond strength remains at most 3.6 N / mm 2 , with higher bond strength and higher composition itself When the cohesive force is required, there is a problem that it may not be fully satisfied.
本発明が解決しようとする課題は、十分に低粘度に設計しても高い接着強さを有し、且つ組成物自体に高い凝集力を有しながら、ＵＬ９４垂直燃焼性試験でＶ−０に合格する難燃性を有する難燃性接着剤組成物を提供することにある。 The problem to be solved by the present invention is to achieve V-0 in the UL94 vertical flammability test while having high adhesive strength even when designed to have a sufficiently low viscosity and having high cohesive strength in the composition itself. It is providing the flame-retardant adhesive composition which has the flame retardance which passes.
請求項１記載の発明は、加水分解により架橋可能なシリル基を有する湿気硬化性樹脂（Ａ）と、金属水酸化物から成る難燃性フィラー（Ｂ）と、少なくともテトラアルコキシシラン又はテトラアルコキシシランの縮合物から成る（Ｃ）と、硬化触媒（Ｄ）とを含み、少なくともテトラアルコキシシラン又はテトラアルコキシシランの縮合物から成る（Ｃ）は、加水分解により架橋可能なシリル基を有する湿気硬化性樹脂（Ａ）１００重量部に対して、０．５〜２０重量部であることを特徴とする難燃性接着剤組成物である。 The invention according to claim 1 is a moisture curable resin (A) having a silyl group that can be crosslinked by hydrolysis, a flame retardant filler (B) comprising a metal hydroxide, and at least tetraalkoxysilane or tetraalkoxysilane. (C) comprising a condensate of (1) and a curing catalyst (D), and (C) comprising at least a tetraalkoxysilane or a tetraalkoxysilane condensate has a moisture-curing property having a silyl group capable of crosslinking by hydrolysis. The flame retardant adhesive composition is 0.5 to 20 parts by weight relative to 100 parts by weight of the resin (A).
請求項２記載の発明は、加水分解により架橋可能なシリル基を有する湿気硬化性樹脂（Ａ）１００重量部に対して、金属水酸化物から成る難燃性フィラー（Ｂ）は１００〜３００重量部であることを特徴とする請求項１記載の難燃性接着剤組成物である。 The invention according to claim 2 is based on 100 parts by weight of the moisture curable resin (A) having a silyl group that can be crosslinked by hydrolysis, and the flame retardant filler (B) made of a metal hydroxide is 100 to 300 parts by weight. It is a flame retardant adhesive composition of Claim 1 characterized by the above-mentioned.
請求項３記載の発明は、テトラアルコキシシランはテトラエトキシシランであることを特徴とする請求項１又は請求項２記載の難燃性接着剤組成物である。 The invention described in claim 3 is the flame retardant adhesive composition according to claim 1 or 2, wherein the tetraalkoxysilane is tetraethoxysilane.
本発明に係る難燃性接着剤組成物は、ＵＬ９４垂直燃焼性試験でＶ−０に合格する難燃性を有すると共に、十分に低粘度に設計しても高い接着強さを有するという効果があり、結果として優れた接着作業性を有するという効果がある。また、硬化後の組成物の凝集力が高く、使用環境温度が高い場合であっても接着強さが維持され、優れた接着信頼性を有するという効果がある。 The flame retardant adhesive composition according to the present invention has flame retardancy that passes V-0 in the UL94 vertical flammability test, and also has the effect of having high adhesive strength even when designed to have a sufficiently low viscosity. As a result, there is an effect of having an excellent bonding workability. In addition, the cohesive strength of the cured composition is high, and even when the use environment temperature is high, the adhesive strength is maintained, and there is an effect of having excellent adhesion reliability.
以下本発明について詳細に説明する。 The present invention will be described in detail below.
本発明の請求項１記載の難燃性接着剤組成物は、加水分解により架橋可能なシリル基を有する湿気硬化性樹脂（Ａ）と、金属水酸化物から成る難燃性フィラー（Ｂ）と、少なくともテトラアルコキシシラン又はテトラアルコキシシランの縮合物から成る（Ｃ）と、硬化触媒（Ｄ）とを含むことを特徴とする難燃性接着剤組成物であり、この他に必要に応じて脱水剤、接着性付与剤、充填剤等を配合することが出来る。 The flame retardant adhesive composition according to claim 1 of the present invention comprises a moisture curable resin (A) having a silyl group capable of crosslinking by hydrolysis, a flame retardant filler (B) comprising a metal hydroxide, and A flame retardant adhesive composition comprising (C) comprising at least tetraalkoxysilane or a tetraalkoxysilane condensate and a curing catalyst (D), and in addition, dehydration as necessary An agent, an adhesion-imparting agent, a filler and the like can be blended.
加水分解により架橋可能なシリル基を有する湿気硬化性樹脂（Ａ）
本発明に係る加水分解により架橋可能なシリル基を有する湿気硬化性樹脂（Ａ）は、例えば水等の活性水素基含有化合物と反応することによりシラノール基を生成できるシリル基を有する樹脂であり、脱離する保護基の種類によって、脱アルコール型、脱オキシム型、脱酢酸型、脱アミド型、脱アセトン型などがある。該湿気硬化性樹脂（Ａ）としては、主鎖としてポリシロキサン構造を有するシリコーン樹脂やポリオキシアルキレン構造を有する変性シリコーン樹脂を使用することが出来る。
Moisture curable resin having a silyl group that can be crosslinked by hydrolysis (A)
The moisture curable resin (A) having a silyl group crosslinkable by hydrolysis according to the present invention is a resin having a silyl group capable of generating a silanol group by reacting with an active hydrogen group-containing compound such as water, for example. Depending on the type of protecting group to be eliminated, there are dealcohol-type, deoxime-type, deacetate-type, deamid-type, and deacetone-type. As the moisture curable resin (A), a silicone resin having a polysiloxane structure as a main chain or a modified silicone resin having a polyoxyalkylene structure can be used.
加水分解により架橋可能なシリル基を有する湿気硬化性樹脂（Ａ）を硬化させる際は、硬化触媒（Ｄ）が用いられ、該硬化触媒（Ｄ）としては、有機錫、無機錫、チタン触媒、ビスマス触媒、金属錯体、白金触媒、塩基性物質及び有機燐酸化物などが使用される。有機錫の具体例としては、ジブチル錫ジラウリレート、ジオクチル錫ジマレート、ジブチル錫フタレート、オクチル酸第一錫、ジブチル錫ジアセテート、ジブチル錫塩と正珪酸エチルとの反応生成物等が挙げられる。金属錯体としては、テトラブチルチタネート、テトライソプロピルチタネート、トリエタノールアミンチタネート等のチタネート化合物類、オクチル酸鉛、ナフテン酸鉛、ナフテン酸ニッケル、ナフテン酸コバルト等のカルボン酸金属塩、アルミニウムアセチルアセテート錯体等の金属アセチルアセテート錯体、バナジウムアセチルアセトナート錯体等の金属アセチルアセトナート錯体などが挙げられる。硬化触媒（Ｄ）は加水分解により架橋可能なシリル基を有する湿気硬化性樹脂（Ａ）１００重量部に対して０．０１〜２０重量部が適当である。０．０１重量部未満では硬化が不十分となり、２０重量部超では反応が速くなりすぎて増粘が顕著になり、接着作業性が不良となる。 When curing the moisture curable resin (A) having a silyl group that can be cross-linked by hydrolysis, a curing catalyst (D) is used. As the curing catalyst (D), organic tin, inorganic tin, titanium catalyst, Bismuth catalyst, metal complex, platinum catalyst, basic substance and organic phosphorous oxide are used. Specific examples of the organic tin include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin diacetate, a reaction product of dibutyltin salt and normal ethyl silicate, and the like. Examples of metal complexes include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, triethanolamine titanate, carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate, cobalt naphthenate, aluminum acetyl acetate complex, etc. And metal acetylacetonate complexes such as metal acetylacetate complexes and vanadium acetylacetonate complexes. The curing catalyst (D) is suitably 0.01 to 20 parts by weight with respect to 100 parts by weight of the moisture curable resin (A) having a silyl group that can be crosslinked by hydrolysis. If it is less than 0.01 part by weight, curing is insufficient, and if it exceeds 20 parts by weight, the reaction becomes too fast and the thickening becomes remarkable, resulting in poor adhesion workability.
金属水酸化物から成る難燃性フィラー（Ｂ）
本発明に係る難燃性接着剤組成物に配合される難燃性フィラーは金属水酸化物であり、特には、水酸化アルミニウム、水酸化マグネシウム又はこれらの混合物を使用することができる。水酸化アルミニウム又は水酸化マグネシウムは一般的にプラスチックの難燃化剤として使用されているが、通常、ＵＬ９４垂直燃焼性試験でＶ−０に合格する難燃性を付与するためには該水酸化アルミニウム又は水酸化マグネシウムを多量に配合しなければならず、そうすると組成物が高粘度となって作業性が不良となる。これを解決するために上記特許文献１及び特許文献２のように架橋可能な加水分解性シリル基を片末端のみに有するポリエーテル化合物や液状化合物を配合すると、組成物の粘度は低下しても同時に硬化物の凝集力が低下して接着力が低下するという相矛盾する傾向にあった。このような従来の技術に対して、本発明は難燃性フィラーとしてこれらの金属水酸化物を多量に配合しても、従来のようなポリエーテル化合物や液状化合物を配合することなく、以下に詳述する少なくともテトラアルコキシシラン又はテトラアルコキシシランの縮合物から成る（Ｃ）を配合する処方をとっている。このため、硬化前は該少なくともテトラアルコキシシラン又はテトラアルコキシシランの縮合物から成る（Ｃ）の希釈効果により組成物は低粘度となり、次に硬化触媒（Ｄ）により硬化反応が開始すると、該少なくともテトラアルコキシシラン又はテトラアルコキシシランの縮合物から成る（Ｃ）によって湿気硬化性樹脂（Ａ）の架橋度が高められて硬化物の凝集力が高くなるものである。結果的には本発明により、難燃性接着剤組成物の低粘度化と硬化物の高凝集力化が初めて実現されている。
Flame retardant filler made of metal hydroxide (B)
The flame retardant filler blended in the flame retardant adhesive composition according to the present invention is a metal hydroxide, and in particular, aluminum hydroxide, magnesium hydroxide or a mixture thereof can be used. Aluminum hydroxide or magnesium hydroxide is generally used as a flame retardant for plastics. However, in order to impart flame retardancy that passes V-0 in the UL94 vertical flammability test, the hydroxide is usually used. A large amount of aluminum or magnesium hydroxide must be blended, and the composition becomes highly viscous and the workability becomes poor. In order to solve this, when a polyether compound or liquid compound having a crosslinkable hydrolyzable silyl group only at one end is blended as in Patent Document 1 and Patent Document 2, the viscosity of the composition is lowered. At the same time, there was a tendency to contradict that the cohesive strength of the cured product was reduced and the adhesive strength was reduced. In contrast to such conventional techniques, the present invention can be used in the following without blending a large amount of these metal hydroxides as a flame retardant filler without blending a conventional polyether compound or liquid compound. The formulation which mix | blends (C) which consists of the condensate of at least tetraalkoxysilane or tetraalkoxysilane explained in full detail is taken. Therefore, before curing, the composition has a low viscosity due to the dilution effect of (C) comprising at least tetraalkoxysilane or a tetraalkoxysilane condensate, and then when the curing reaction is initiated by the curing catalyst (D), the at least The degree of cross-linking of the moisture curable resin (A) is increased by (C) comprising tetraalkoxysilane or a tetraalkoxysilane condensate, and the cohesive strength of the cured product is increased. As a result, the present invention achieves for the first time a low-viscosity adhesive composition and a high cohesive strength of the cured product.
金属水酸化物から成る難燃性フィラー（Ｂ）の配合量は湿気硬化性樹脂（Ａ）１００重量部に対して１００〜３００重量部であり、１００重量部未満では難燃性が不十分となり、３００重量部超では組成物の粘度が高くなり、作業性が不良となる。 The blending amount of the flame retardant filler (B) made of a metal hydroxide is 100 to 300 parts by weight with respect to 100 parts by weight of the moisture curable resin (A). If it exceeds 300 parts by weight, the viscosity of the composition becomes high and workability becomes poor.
少なくともテトラアルコキシシラン又はテトラアルコキシシランの縮合物から成る（Ｃ）
本発明に係る難燃性接着剤組成物に配合される少なくともテトラアルコキシシラン又はテトラアルコキシシランの縮合物から成る（Ｃ）は、上述の目的で配合されるが、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、及びこれらの縮合物を使用することができる。その中でも、好ましいものとしては、テトラエトキシシラン及びテトラエトキシシランの縮合物（５量体）及び同縮合物（１０量体）である。
(C) comprising at least tetraalkoxysilane or a condensate of tetraalkoxysilane
(C) comprising at least tetraalkoxysilane or a condensate of tetraalkoxysilane blended in the flame retardant adhesive composition according to the present invention is blended for the above-mentioned purpose. For example, tetramethoxysilane, tetraethoxy Silane, tetrapropoxysilane, tetrabutoxysilane, and condensates thereof can be used. Among these, tetraethoxysilane, tetraethoxysilane condensate (pentamer) and the same condensate (decamer) are preferable.
少なくともテトラアルコキシシラン又はテトラアルコキシシランの縮合物から成る（Ｃ）の配合量は、湿気硬化性樹脂（Ａ）１００重量部に対して０．５〜２０重量部であり、０．５重量部未満では組成物の粘度が高くなり、作業性が不良となり、２０重量部超では難燃性が不十分となる。配合量が１．０重量部未満では組成物の粘度が高くなる傾向があるが、難燃性に影響を与えない範囲で他の希釈剤を併用することにより作業性を良好とすることができる。 The blending amount of (C) comprising at least tetraalkoxysilane or a tetraalkoxysilane condensate is 0.5 to 20 parts by weight with respect to 100 parts by weight of the moisture curable resin (A), and less than 0.5 parts by weight. Then, the viscosity of the composition becomes high, workability becomes poor, and if it exceeds 20 parts by weight, the flame retardancy becomes insufficient. If the blending amount is less than 1.0 part by weight, the viscosity of the composition tends to be high, but workability can be improved by using another diluent in a range that does not affect the flame retardancy. .
また、本発明に係る難燃性接着剤組成物には脱水剤を添加することができ、該脱水剤の添加により貯蔵中に湿気と反応して増粘または硬化することを抑制することができる。脱水剤には、ビニルトリメトキシシラン、オルソギ酸エチルなどを使用することができ、湿気硬化性樹脂（Ａ）１００重量部に対して０．１〜１０重量部の範囲で添加される。 Moreover, a dehydrating agent can be added to the flame retardant adhesive composition according to the present invention, and the addition of the dehydrating agent can suppress the increase in viscosity or curing by reacting with moisture during storage. . As the dehydrating agent, vinyltrimethoxysilane, ethyl orthoformate or the like can be used, and it is added in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the moisture curable resin (A).
また、本発明に係る難燃性接着剤組成物には、使用される被着体に対する接着性を向上させるために接着性付与剤を添加することができる。具体的にはシラン系カップリング剤、チタネート系カップリング剤、シラン系又はチタネート系カップリング剤とポリイソシアネート系化合物との反応生成物などを用いることができる。これらは単独で使用、または２種以上を併用することができる。 Moreover, in order to improve the adhesiveness with respect to the to-be-adhered body used, the adhesiveness imparting agent can be added to the flame-retardant adhesive composition which concerns on this invention. Specifically, a silane coupling agent, a titanate coupling agent, a reaction product of a silane or titanate coupling agent and a polyisocyanate compound, or the like can be used. These can be used alone or in combination of two or more.
また、本発明に係る難燃性接着剤組成物には充填剤を配合することができる。該充填剤は、粘度調整、粘性調整、固形分調整などの目的で配合され、具体例として、炭酸カルシウム、硅砂、タルク、カーボンブラック、酸化チタン、カオリンなどの無機充填材、硬化樹脂の補強のためにガラス繊維などの補強材、軽量化及び粘度調整などのためにシラスバルーン、ガラスバルーンなどの中空体などを使用することができる。 Moreover, a filler can be mix | blended with the flame-retardant adhesive composition which concerns on this invention. The filler is blended for the purpose of adjusting the viscosity, adjusting the viscosity, adjusting the solid content, and as specific examples, inorganic fillers such as calcium carbonate, cinnabar, talc, carbon black, titanium oxide, and kaolin, and reinforcing resin reinforcement. Therefore, reinforcing materials such as glass fibers, hollow bodies such as shirasu balloons and glass balloons can be used for weight reduction and viscosity adjustment.
以下，実施例及び比較例にて本発明に係る難燃性接着剤組成物について具体的に説明する。 Hereinafter, the flame retardant adhesive composition according to the present invention will be specifically described with reference to Examples and Comparative Examples.
実施例１乃至実施例７
表１に示す配合にて、加水分解により架橋可能なシリル基を有する湿気硬化性樹脂（Ａ）として変性シリコーン樹脂であるＥＳＴ２５０（商品名、ＰＰＧ骨格変性シリコーン樹脂、粘度：２０Ｐａ・ｓ／２３℃、株式会社カネカ製）を、金属水酸化物から成る難燃性フィラー（Ｂ）として、水酸化アルミニウムであるハイジライトＨ−３２（商品名、昭和電工株式会社製、平均粒子径８μｍ）を、充填剤として重質炭酸カルシウム ホワイトンＳＢ（商品名、白石カルシウム株式会社製、平均粒子径４μｍ）を、少なくともテトラアルコキシシラン又はテトラアルコキシシランの縮合物から成る（Ｃ）として、テトラエトキシランであるエチルシリケート２８(商品名、コルコート株式会社製）、又はテトラエトキシシラン（５量体）であるエチルシリケート４０(商品名、コルコート株式会社製）、又はテトラエトキシシラン（１０量体）であるエチルシリケート４８(商品名、コルコート株式会社製）を、脱水剤としてＡ−１７１（ビニルトリメトキシシラン、商品名、モメンティブ・パフォーマンス・マテリアルズ社製）を、接着性付与剤としてＳＨ−６０２０（３−（２−アミノエチル)アミノプロピルトリメトキシシラン、商品名、東レ・ダウコーニング社製）を、硬化触媒（Ｂ）としてジブチル錫化合物であるネオスタンＵ−２２０Ｈ（商品名、日東化成株式会社製）を使用し、減圧下で撹拌・混合し、実施例１乃至実施例７の難燃性接着剤組成物を得た。
Example 1 to Example 7
EST250 (trade name, PPG skeleton modified silicone resin, viscosity: 20 Pa · s / 23 ° C.) which is a modified silicone resin as a moisture curable resin (A) having a silyl group that can be cross-linked by hydrolysis in the formulation shown in Table 1. , Manufactured by Kaneka Corporation) as a flame retardant filler (B) made of a metal hydroxide, Hydrite H-32 (trade name, manufactured by Showa Denko KK, average particle size 8 μm), which is aluminum hydroxide, Heavy calcium carbonate Whiteon SB (trade name, manufactured by Shiraishi Calcium Co., Ltd., average particle size of 4 μm) as a filler, tetraethoxylane as at least tetraalkoxysilane or a tetraalkoxysilane condensate (C) Ethyl which is ethyl silicate 28 (trade name, manufactured by Colcoat Co., Ltd.) or tetraethoxysilane (pentamer) Silicate 40 (trade name, manufactured by Colcoat Co., Ltd.) or ethyl silicate 48 (trade name, manufactured by Colcoat Co., Ltd.), which is tetraethoxysilane (10-mer), was used as a dehydrating agent, and A-171 (vinyltrimethoxysilane, commercial product). Name, manufactured by Momentive Performance Materials), and SH-6020 (3- (2-aminoethyl) aminopropyltrimethoxysilane, product name, manufactured by Toray Dow Corning) as an adhesion-imparting agent. The flame retardant adhesive composition of Examples 1 to 7 was prepared by using Neostan U-220H (trade name, manufactured by Nitto Kasei Co., Ltd.) which is a dibutyltin compound as (B) and stirring and mixing under reduced pressure. Got.
比較例１乃至比較例５
表１に示す配合にて、実施例１乃至実施例７で使用した材料の他、希釈剤としてポリエチレングリコール Ｐ−１０００（重量平均分子量Ｍｗ；１０００、商品名、株式会社ＡＤＥＫＡ製）、フタル酸ジイソノニル、及びイソパラフィン系希釈剤としてＩＰソルベント１６２０（商品名、密度０．７６１／１５℃、出光興産株式会社製）を使用し、減圧下で撹拌・混合し、比較例１乃至比較例５の難燃性接着剤組成物を得た。
Comparative Examples 1 to 5
In addition to the materials used in Examples 1 to 7 in the formulation shown in Table 1, polyethylene glycol P-1000 (weight average molecular weight Mw; 1000, trade name, manufactured by ADEKA Corporation), diisononyl phthalate as a diluent And IP solvent 1620 (trade name, density 0.761 / 15 ° C., manufactured by Idemitsu Kosan Co., Ltd.) as an isoparaffin-based diluent, stirred and mixed under reduced pressure, and flame retardant of Comparative Examples 1 to 5 An adhesive composition was obtained.
評価項目および評価方法Evaluation items and evaluation methods
粘度
実施例及び比較例の難燃性接着剤組成物を２３℃雰囲気下に４時間以上静置した後、ＢＳ型粘度計（ローターＮｏ．６またはＮｏ．７、１０ｒｐｍ）にて粘度を測定した。５００Ｐａ・ｓ／２３℃以下を○と評価し、これを超えるものを×と評価した。
Viscosity After the flame retardant adhesive compositions of Examples and Comparative Examples were allowed to stand at 23 ° C. for 4 hours or longer, the viscosity was measured with a BS type viscometer (rotor No. 6 or No. 7, 10 rpm). . A value of 500 Pa · s / 23 ° C. or lower was evaluated as “good”, and a value exceeding this was evaluated as “poor”.
難燃性
実施例及び比較例の難燃性接着剤組成物を、シリコーン離型紙間で１．５ｍｍのスペーサを用いてシートを作製する。２３℃７日後、離型紙から剥がし、１．５×１３×１３０ｍｍの硬化シートを作製した。得られた硬化シートに対し、ＵＬ９４Ｖ−０規格に基づき試験を行い、難燃性を評価した。具体的には以下の各項目を全て満たすものを合格、一つでも満たさないものを不合格とした。
ａ）各試料の残炎時間ｔ１またはｔ２が「１０秒以下」
ｂ）全ての処理による各組の残炎時間の合計（５枚の試料のｔ１＋ｔ２）が「５０秒以下」
ｃ）第２回接炎の各試料の残炎時間と残じん時間の合計（ｔ２＋ｔ３）が「３０秒以下」
ｄ）各試料の保持クランプまでの残炎または残じんが「無いこと」
ｅ）発炎物質または滴下物による標識用綿の着火が「無いこと」
なお、ｔ１〜ｔ３は以下の通りである。
ｔ１：第１回接炎の試料の残炎時間（秒）
ｔ２：第２回接炎の試料の残炎時間（秒）
ｔ３：第２回接炎の試料の残じん時間（秒）
A sheet is produced using the flame retardant adhesive compositions of the flame retardant Examples and Comparative Examples using a 1.5 mm spacer between silicone release papers. After 23 days at 23 ° C., the film was peeled off from the release paper to prepare a cured sheet of 1.5 × 13 × 130 mm. The obtained cured sheet was tested based on the UL94V-0 standard to evaluate flame retardancy. Specifically, those that satisfy all the following items were accepted, and those that did not meet even one were rejected.
a) After flame time t1 or t2 of each sample is “10 seconds or less”
b) The total after flame time of each set by all treatments (t1 + t2 of 5 samples) is “50 seconds or less”
c) The total after flame time and residual time (t2 + t3) of each sample of the second flame contact is “30 seconds or less”
d) “No residual flame or dust” up to the holding clamp of each sample.
e) There shall be no ignition of labeling cotton by flame retardants or drops.
T1 to t3 are as follows.
t1: Afterflame time of the first flame contact sample (seconds)
t2: Afterflame time of the second flame contact sample (seconds)
t3: Residual time of the second flame contact sample (seconds)
被膜強さ（凝集力）
実施例及び比較例の難燃性接着剤組成物を、シリコーン離型紙上にて２ｍｍ厚のスペーサを用いて厚さ２ｍｍのシート状となるよう塗布する。２３℃５０％ＲＨにて７日間養生させて厚さ２ｍｍのシート状硬化皮膜とした後、離型紙から剥がし、打抜き刃形等を用いてＪＩＳ Ｋ６２５１に規定するダンベル状３号形試験片を作成する。該試験片を引張速度１００ｍｍ／分にて引張り、破断強度を測定し、該測定値を皮膜強さ（単位：Ｎ／ｍｍ２）とした。皮膜強さが３．４Ｎ／ｍｍ２以上を○と評価し、３．４Ｎ／ｍｍ２未満を×と評価した。
Film strength (cohesive force)
The flame retardant adhesive compositions of Examples and Comparative Examples are applied to a 2 mm thick sheet using a 2 mm thick spacer on a silicone release paper. After curing for 7 days at 23 ° C. and 50% RH to form a sheet-like cured film with a thickness of 2 mm, it is peeled off from the release paper, and a dumbbell-shaped No. 3 test piece defined in JIS K6251 is prepared using a punching blade shape or the like. To do. The test piece was pulled at a pulling speed of 100 mm / min, the breaking strength was measured, and the measured value was defined as the film strength (unit: N / mm 2 ). When the film strength was 3.4 N / mm 2 or more, it was evaluated as “good”, and less than 3.4 N / mm 2 was evaluated as “x”.
被膜硬度
上記皮膜強さ（凝集力）の評価において作製した実施例及び比較例の難燃性接着剤組成物のシート状硬化皮膜を３〜４枚程度重ねて、ＪＩＳ Ｋ６２５３−３：２０１２に規定するタイプＡデュロメータにて硬度を測定し、該硬度を皮膜硬度とした。皮膜硬度が７５以上を○と評価し、７５未満を×と評価した。
Film hardness About 3 to 4 sheet-like cured films of the flame-retardant adhesive compositions of Examples and Comparative Examples prepared in the evaluation of the above-mentioned film strength (cohesive force) are specified in JIS K6253-3: 2012. The hardness was measured with a type A durometer, and the hardness was defined as the film hardness. When the film hardness was 75 or more, it was evaluated as ○, and when it was less than 75, it was evaluated as ×.
接着強さ
実施例及び比較例の難燃性接着剤組成物を、ＳＵＳ３０４ステンレス鋼板（１ｍｍ厚×２５ｍｍ×７０ｍｍ）の接着面積２５×２５ｍｍに約１００μｍ厚に塗布し、３分間２３℃５０％ＲＨにて放置後、同様に接着剤組成物を塗布、放置した同形状のＳＵＳ３０４ステンレス鋼板を貼り合わせ２３℃５０％ＲＨにて７日間養生後、引張速度５０ｍｍ／分で引張せん断強さを測定し、該測定値を接着強さ（Ｎ／ｍｍ２）とした。接着強さが３．７Ｎ／ｍｍ２以上を○と評価し、３．７Ｎ／ｍｍ２未満を×と評価した。
Adhesive Strength The flame retardant adhesive compositions of Examples and Comparative Examples were applied to an adhesive area of 25 × 25 mm of a SUS304 stainless steel plate (1 mm thickness × 25 mm × 70 mm) to a thickness of about 100 μm, and 3 minutes at 23 ° C. and 50% RH. Then, the adhesive composition was applied in the same manner, and the SUS304 stainless steel plate with the same shape was pasted together. After curing for 7 days at 23 ° C. and 50% RH, the tensile shear strength was measured at a tensile speed of 50 mm / min. The measured value was defined as the adhesive strength (N / mm 2 ). Bond strength was evaluated as ○ and 3.7 N / mm 2 or more were evaluated as × less than 3.7 N / mm 2.
評価結果
評価結果を表２に示す。実施例１乃至実施例７の難燃性接着剤組成物は、接着強さが３．７０Ｎ/ｍｍ２以上有し、特に実施例７の難燃性接着剤組成物は粘度が７０Ｐａ・ｓ／２３℃と低粘度でありながら被膜強さは５．００Ｎ/ｍｍ２、且つ接着強さは３．９０Ｎ/ｍｍ２と成り、高い接着性と硬化被膜の高い凝集力を示した。これに対して、比較例２乃至比較例４の難燃性接着剤組成物は低粘度ではあるが、皮膜強さ、皮膜硬度、接着強さも低下した。また、比較例５の難燃性接着剤組成物は、難燃性が低下した。
Evaluation results The evaluation results are shown in Table 2. The flame retardant adhesive compositions of Examples 1 to 7 have an adhesive strength of 3.70 N / mm 2 or more, and in particular, the flame retardant adhesive composition of Example 7 has a viscosity of 70 Pa · s / The film strength was 5.00 N / mm 2 and the adhesive strength was 3.90 N / mm 2 while having a low viscosity of 23 ° C., indicating high adhesion and high cohesive strength of the cured film. On the other hand, the flame retardant adhesive compositions of Comparative Examples 2 to 4 had low viscosity, but the film strength, film hardness, and adhesive strength also decreased. Moreover, the flame retardancy of the flame retardant adhesive composition of Comparative Example 5 decreased.
Claims (3)
The flame retardant adhesive composition according to claim 1 or 2, wherein the tetraalkoxysilane is tetraethoxysilane.
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