JP2014034652A - Thermally conductive tacky-adhesive tape - Google Patents
Thermally conductive tacky-adhesive tape Download PDFInfo
- Publication number
- JP2014034652A JP2014034652A JP2012177061A JP2012177061A JP2014034652A JP 2014034652 A JP2014034652 A JP 2014034652A JP 2012177061 A JP2012177061 A JP 2012177061A JP 2012177061 A JP2012177061 A JP 2012177061A JP 2014034652 A JP2014034652 A JP 2014034652A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive tape
- sensitive adhesive
- pressure
- heat conductive
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Abstract
Description
本発明は、良好な熱伝導性を有し、柔軟性や絶縁性に優れた熱伝導性両面粘着テープに関し、電子部品、ＯＡ機器部品、家電部品等の各種分野での部材の固定用途、特に発熱性のＬＥＤの固定用途に有用である熱伝導性両面粘着テープに関する。 The present invention relates to a heat conductive double-sided pressure-sensitive adhesive tape having good heat conductivity and excellent flexibility and insulation, and for fixing members in various fields such as electronic parts, OA equipment parts, home appliance parts, etc. The present invention relates to a heat conductive double-sided pressure-sensitive adhesive tape useful for fixing heat-generating LEDs.
近年、エレクトロニクス技術の格段なる進歩により電気、電子、ＯＡ機器の高集積化・高性能化が進み、内部の高温化や蓄熱による不具合が生じやすくなっており、内部部品の固定に使用する接着部材にも高温化や蓄熱を防止するための高い熱伝導性が求められている。従来は内部部品の接合には、接着剤やビス止めが使用されてきたが、貼付の簡便さから基材を有しない厚さ１００〜３００μｍ程度の熱伝導性の粘着テープが使われることが多くなっている。 In recent years, remarkable progress in electronics technology has led to higher integration and higher performance of electrical, electronic, and OA equipment, which has been prone to problems caused by internal high temperatures and heat storage. Adhesive members used for fixing internal components In addition, high thermal conductivity is required to prevent high temperature and heat storage. Conventionally, adhesives and screws have been used to join internal parts, but thermal conductive adhesive tapes with a thickness of about 100 to 300 μm, which do not have a base material, are often used for ease of sticking. It has become.
熱伝導性を有する粘着性の組成物としては、例えば、アクリル系ポリマーに熱伝導性フィラーを含有する熱伝導性感圧接着剤（特許文献１参照）や、（メタ）アクリレート系ポリマーと金属水酸化物とを有し、（メタ）アクリレート系ポリマーのトルエン不溶分の割合とトルエン可溶分の分子量とを特定の範囲とし、（メタ）アクリレート系ポリマー１００質量部に対する金属水酸化物の配合割合が８０〜１６０質量部である感圧接着剤組成物が開示されている（特許文献２参照）。 Examples of the adhesive composition having thermal conductivity include a thermally conductive pressure-sensitive adhesive (see Patent Document 1) containing a thermally conductive filler in an acrylic polymer, and a (meth) acrylate polymer and metal hydroxide. The ratio of the toluene-insoluble part of the (meth) acrylate polymer and the molecular weight of the toluene-soluble part are in a specific range, and the blending ratio of the metal hydroxide with respect to 100 parts by mass of the (meth) acrylate polymer is The pressure sensitive adhesive composition which is 80-160 mass parts is disclosed (refer patent document 2).
基材を有しない熱伝導性の粘着テープは、所定サイズへ断裁加工する際に粘着剤層が伸びて変形したり、部材への貼付作業で貼り直しをする際、粘着剤層が伸びたり切れたりする不具合が発生する。ポリエステル等のフィルム基材の両面に粘着剤層を積層した両面粘着テープの場合は、所定サイズへの断裁加工や部品への貼付作業の際、粘着剤層および粘着テープの伸びが抑制されるが、粘着剤層間にあるフィルム基材によって熱伝導のパスラインが隔離され、熱伝導性が悪化する。また、アルミ箔等の金属箔や熱伝導性フィラーを練り込んだ熱伝導性のある基材を使用した場合、絶縁性が不十分であったり、高価でかつ薄膜化が困難であるといった問題が発生する。 A heat-conductive adhesive tape that does not have a base material has a pressure-sensitive adhesive layer that stretches and deforms when it is cut into a predetermined size, or when it is re-applied during application to a member, the adhesive layer stretches or breaks. Malfunction occurs. In the case of double-sided pressure-sensitive adhesive tapes in which a pressure-sensitive adhesive layer is laminated on both sides of a film base material such as polyester, the elongation of the pressure-sensitive adhesive layer and the pressure-sensitive adhesive tape is suppressed during the cutting process to a predetermined size and the attaching operation to a part. The heat conductive pass line is isolated by the film substrate between the adhesive layers, and the thermal conductivity is deteriorated. In addition, when using a heat conductive base material kneaded with a metal foil such as aluminum foil or a heat conductive filler, there are problems such as insufficient insulation and high cost and difficulty in thinning. Occur.
一方、画像表示のバックライトやＬＥＤ照明等に使用される、ＬＥＤチップがアルミ基板上に直列配列された長尺のＬＥＤ光源ユニットは、作成工程等によってＬＥＤチップ側へ凹状に湾曲している場合がある。湾曲した状態のままでＬＥＤチップが配列されたアルミ基板裏面へ両面粘着テープが貼付され、アルミ基板を直線状へ曲げ戻されて画像表示本体へ貼付される際、熱伝導性粘着テープが波ジワになり、ＬＥＤ部品や画像表示本体と熱伝導性粘着テープの間が接触不十分となり、熱伝導性が悪化する。 On the other hand, when a long LED light source unit in which LED chips are arrayed in series on an aluminum substrate, used for image display backlighting, LED lighting, etc., is bent concavely toward the LED chip side due to the production process, etc. There is. When the double-sided adhesive tape is affixed to the back of the aluminum substrate on which the LED chips are arranged in a curved state, and the aluminum substrate is bent back into a linear shape and affixed to the image display body, the heat conductive adhesive tape is The contact between the LED component or the image display main body and the heat conductive adhesive tape becomes insufficient, and the heat conductivity deteriorates.
本発明が解決ようとする課題は、貼付後に被着体が変形した際にも波ジワが生じにくく、かつ断裁加工や粘着テープを貼り直す際、伸びや切れが生じにくい熱伝導性粘着テープを提供することにある。 The problem to be solved by the present invention is to provide a heat conductive adhesive tape that is less likely to be wrinkled even when the adherend is deformed after being applied, and that is less likely to be stretched or cut when being cut or reapplied. It is to provide.
本発明においては、１０枚積層して、ＪＩＳＰ８１１７に準拠して測定されるガーレ式透気度が０．３５ｓｅｃ／１００ｍｌ以下、引張弾性率が３ＧＰａ以下、かつ厚さが１０〜５０μｍの基材の少なくとも一面に、熱伝導性粘着剤層を有する熱伝導性粘着テープにより上記課題を解決する。当該熱伝導性粘着テープによれば、抜き加工や部材への貼り直しの際、粘着テープの伸びや切れが生じにくく、また貼付後に被着体が変形した際の波ジワが生じにくく良好な熱伝導性を実現できる。 In the present invention, ten substrates are laminated, and a Gurley type air permeability measured in accordance with JISP 8117 is 0.35 sec / 100 ml or less, a tensile elastic modulus is 3 GPa or less, and a thickness is 10 to 50 μm. The said subject is solved by the heat conductive adhesive tape which has a heat conductive adhesive layer in at least one surface. According to the heat conductive pressure-sensitive adhesive tape, when punching or reapplying to a member, the pressure-sensitive adhesive tape hardly stretches or breaks, and the wrinkle when the adherend deforms after sticking is excellent. Conductivity can be realized.
本発明の熱伝導性粘着テープは、貼付後に被着体が変形した際にも波ジワが生じにくいことから、粘着テープの浮きや剥がれにより被着体と粘着テープの接触が不十となることを抑制でき、被着体の変形による熱伝導性の低下を抑制できる。また、当該浮剥がれの抑制に加えて、加工時や貼り直しの際に伸びや切れが生じにくいことから、所望の形状、特に細幅や長尺状への加工に際しても、好適に抜き加工や切断加工が可能であり、また、貼り直しの際にも好適に剥離できる。このため、本発明の熱伝導性粘着テープは、高い信頼性が求められる各種の電子機器やＯＡ機器等の電子部品の固定に好適に適用できる。なかでも、発熱量が大きく、画像表示部の輝度を確保するために高い実装密度が求められる画像表示のバックライト等に使用されるＬＥＤ光源ユニットの固定に好適に使用でき、ＬＥＤ光源側へ凹み状に湾曲したＬＥＤ部品を直線状に戻して画像表示装置へ貼付した場合にも波ジワが発生せず好適な熱伝導性を保持できる。 Since the heat conductive adhesive tape of the present invention is less likely to generate wrinkles even when the adherend is deformed after being applied, the contact between the adherend and the adhesive tape becomes inadequate due to the floating or peeling of the adhesive tape. And a decrease in thermal conductivity due to deformation of the adherend can be suppressed. Moreover, in addition to the suppression of the detachment, it is difficult to stretch or break during processing or reattachment. It can be cut and can be suitably peeled off when it is reattached. For this reason, the heat conductive adhesive tape of this invention can be applied suitably for fixation of electronic components, such as various electronic devices and OA apparatus by which high reliability is calculated | required. Among them, it can be used suitably for fixing LED light source units used for image display backlights, etc., which generate a large amount of heat and require high mounting density in order to ensure the brightness of the image display unit. When the LED component curved in a straight line is returned to a straight line and attached to the image display device, wrinkles are not generated, and suitable thermal conductivity can be maintained.
本発明の熱伝導性粘着テープは、基材の少なくとも一面に熱伝導性粘着剤層を有する熱伝導性粘着テープであり、前記基材が、２３℃５０％ＲＨ下にて前記基材を１０枚積層して、ＪＩＳＰ８１１７に準拠して測定されるガーレ式透気度が０．３５ｓｅｃ／１００ｍｌ以下であり、引張弾性率が３ＧＰａ以下であり、厚さが１０〜５０μｍの熱伝導性粘着テープである。本発明の熱伝導性粘着テープは、当該構成により粘着テープの抜き加工や部材への貼り直しの際、粘着テープが伸びたり切れたりせず、ＬＥＤ光源チップ側へ凹み状に湾曲したＬＥＤ基板を直線状に曲げ戻して画像表示装置へ貼付した際に波ジワが発生せず、浮きが発生しない熱伝導性に優れる。 The heat conductive pressure-sensitive adhesive tape of the present invention is a heat conductive pressure-sensitive adhesive tape having a heat conductive pressure-sensitive adhesive layer on at least one surface of a base material, and the base material is 10 at 23 ° C. and 50% RH. A heat conductive adhesive tape having a Gurley air permeability measured in accordance with JISP 8117 of 0.35 sec / 100 ml or less, a tensile elastic modulus of 3 GPa or less, and a thickness of 10 to 50 μm. is there. The heat conductive pressure-sensitive adhesive tape of the present invention is an LED substrate that is curved in a concave shape toward the LED light source chip side without being stretched or cut when the pressure-sensitive adhesive tape is removed or re-applied to a member. When it is bent back into a straight line and pasted to an image display device, no wrinkle is generated, and heat conductivity that does not cause floating is excellent.
［基材］
本発明の熱伝導性粘着テープに使用する基材は、当該基材を１０枚積層した際のガーレ式透気度が０．３５ｓｅｃ／１００μｍ以下、好ましくは０．０５〜０．２ｓｅｃ／１００μｍ、より好ましくは、０．０５〜０．１ｓｅｃ／１００μｍの基材である。ガーレ式透気度を当該範囲とすることで、粘着剤の含浸が良好となり、加工時や貼り直しの際の粘着テープの伸びや切れを好適に抑制できる。また、基材に熱伝導性粘着剤が含浸しやすいことから、良好に熱伝導性を発現しやすい。特に、粘着テープを両面粘着テープとする場合には、基材の両面に積層される熱伝導性粘着剤層同士が好適に接近、接触し、好適な熱伝導性を得やすくなる。
[Base material]
The base material used for the heat conductive adhesive tape of the present invention has a Gurley air permeability of 0.35 sec / 100 μm or less, preferably 0.05 to 0.2 sec / 100 μm, when 10 base materials are laminated. More preferably, the substrate is 0.05 to 0.1 sec / 100 μm. By making the Gurley air permeability within the above range, the pressure-sensitive adhesive is satisfactorily impregnated, and the expansion or breakage of the pressure-sensitive adhesive tape at the time of processing or reattachment can be suitably suppressed. Moreover, since it is easy to impregnate a base material with a heat conductive adhesive, it is easy to express heat conductivity favorably. In particular, when the pressure-sensitive adhesive tape is a double-sided pressure-sensitive adhesive tape, the heat conductive pressure-sensitive adhesive layers laminated on both surfaces of the base material are suitably approached and brought into contact with each other, and it becomes easy to obtain suitable heat conductivity.
基材のガーレ式透気度は、基材を１０枚積層し、１０枚重ねの基材を試料として、ＪＩＳ Ｐ８１１７に準拠して測定される透気度である。測定は、２３℃５０％ＲＨ中にて中芯基材を１０枚重ねてセットし、内径２８．６ｍｍ、重さ５６７ｇの内筒が落下して１００ｍｌの空気が通過する時間を測定した場合の通過時間を計測する。 The Gurley type air permeability of the base material is an air permeability measured in accordance with JIS P8117 using 10 base materials stacked and a 10-layer base material as a sample. Measurement is performed when 10 core substrates are stacked and set in 23 ° C. and 50% RH, and an inner tube with an inner diameter of 28.6 mm and a weight of 567 g is dropped and 100 ml of air is measured. Measure the transit time.
本発明に使用する基材は、引張弾性率が３ＧＰａ以下、好ましくは０．５〜２．０ＧＰａの基材を使用する。当該基材を使用することで、粘着テープに良好な柔軟性を付与でき、被着体への貼付後に被着体が変形した場合にも波ジワが生じにくい。当該引張弾性率は、ＭＤ（流れ方向）、ＴＤ（幅方向）共に、上記範囲とすることで、好適に波ジワを抑制でき、かつ熱伝導性両面粘着テープを断裁加工や被着体へ貼り直す際、粘着テープの伸びや切れを抑制できる。 The base material used in the present invention is a base material having a tensile elastic modulus of 3 GPa or less, preferably 0.5 to 2.0 GPa. By using the base material, good flexibility can be imparted to the adhesive tape, and even when the adherend is deformed after being attached to the adherend, wrinkles are hardly generated. By setting the tensile modulus to be in the above range for both MD (flow direction) and TD (width direction), wave wrinkles can be suitably suppressed, and a heat conductive double-sided adhesive tape is applied to a cut or adherend. When repairing, the elongation and breakage of the adhesive tape can be suppressed.
基材の引張弾性率は、幅２０ｍｍ、長さ１５０ｍｍの試験片を２３℃５０％ＲＨの環境で、ＪＩＳ Ｋ７１６１に規定の方法にて１ｍｍ／ｍｉｎの速度で引っ張り、５０ｍｍ標線間の引張初期０．２％伸度時の引張伸度と引張強度の関係曲線の傾斜接線を、伸度１００％まで外挿して求めた引張強度［Ｐａ］である。 The tensile elastic modulus of the base material is that a test piece having a width of 20 mm and a length of 150 mm is pulled at a speed of 1 mm / min by a method defined in JIS K7161 in an environment of 23 ° C. and 50% RH, and the initial tension between 50 mm marked lines is This is the tensile strength [Pa] obtained by extrapolating the sloped tangent of the relationship curve between tensile elongation and tensile strength at 0.2% elongation to 100% elongation.
本発明に使用する基材は、厚さが１０〜５０μｍ、好ましくは２０〜４５μｍである。基材厚さを当該厚さとすることで、好適に波ジワを抑制できる。また、熱伝導性粘着剤層のアンカリング性が良好となる。このため両面粘着テープとした際の両面からの粘着剤層の接触が生じやすくなり、好適な熱伝導性を実現でき、かつ断裁加工時や粘着テープの貼り直しの際、粘着テープの伸びや切れを抑制できる。 The base material used in the present invention has a thickness of 10 to 50 μm, preferably 20 to 45 μm. Wave wrinkles can be suitably suppressed by setting the substrate thickness to the thickness. Moreover, the anchoring property of a heat conductive adhesive layer becomes favorable. For this reason, when the double-sided pressure-sensitive adhesive tape is used, contact of the pressure-sensitive adhesive layer from both sides is likely to occur, suitable thermal conductivity can be realized, and the adhesive tape can be stretched or cut during cutting or when re-attaching the pressure-sensitive adhesive tape. Can be suppressed.
本発明に使用する基材は、上記透気度、引張弾性率及び厚さの基材であれば特に制限されないが、多孔質な基材を使用することで、これら透気度等を実現しやすいため好ましい。なかでも、不織布、織布、モノフィラメント糸で構成された繊維織物（メッシュ基材）等が挙げられる。なかでも、薄い厚さでも高い引張弾性率を得やすい不織布や、高いガーレ式透気度を得やすいメッシュ基材を好ましく使用できる。 The substrate used in the present invention is not particularly limited as long as it has the above-mentioned air permeability, tensile elastic modulus and thickness. However, by using a porous substrate, these air permeability and the like are realized. It is preferable because it is easy. Among these, a nonwoven fabric, a woven fabric, a fiber woven fabric (mesh base material) composed of monofilament yarn, and the like can be given. Especially, the nonwoven fabric which is easy to obtain a high tensile elasticity even if it is thin thickness, and the mesh base material which is easy to obtain a high Gurley type air permeability can be used preferably.
不織布の材質としては、粘着テープの不織布として用いられる公知慣用の不織布を用いることができる。代表的な例としては、マニラ麻等の麻、レーヨン、再生セルロース、木材パルプ等のセルロース系繊維、アセテート繊維、ポリエステル繊維、ポリビニルアルコール繊維、ポリアミド繊維等の化学繊維及びこれらの混合物等が挙げられる。さらに、必要に応じて、ビスコース含浸や熱可塑性樹脂をバインダーとした含浸処理を施しても良い。 As a material of the nonwoven fabric, a known and conventional nonwoven fabric used as a nonwoven fabric for an adhesive tape can be used. Typical examples include hemp such as Manila hemp, cellulosic fibers such as rayon, regenerated cellulose, and wood pulp, chemical fibers such as acetate fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, and mixtures thereof. Furthermore, you may perform the impregnation process which used the viscose impregnation and the thermoplastic resin as a binder as needed.
なかでも、麻を含有する不織布が、薄い厚さでも高い引張破断強度を得やすいため好ましい。麻としては、強度の点からマニラ麻が好ましい。また、マニラ麻の含有率は３０質量％以上であることが好ましく、４０〜６０質量％であることがさらに好ましい。マニラ麻を含有する不織布としては、マニラ麻単独、またはマニラ麻と、ビニロン、レーヨン繊維、ポリエステル繊維、パルプ、再生セルロース等の一種以上を混抄したものを好ましく使用できる。なかでも１０〜５０μｍの厚さで高い引張破断強度が得られる、ポリエステル繊維、または、レーヨン繊維、再生セルロース、木材パルプ等のセルロース系繊維を２０〜４０質量％含有するものを好ましく使用できる。 Among these, a nonwoven fabric containing hemp is preferable because it is easy to obtain a high tensile breaking strength even with a thin thickness. As the hemp, Manila hemp is preferable from the viewpoint of strength. Moreover, it is preferable that the content rate of a Manila hemp is 30 mass% or more, and it is more preferable that it is 40-60 mass%. As the nonwoven fabric containing Manila hemp, it is preferable to use Manila hemp alone or a mixture of Manila hemp and one or more of vinylon, rayon fiber, polyester fiber, pulp, regenerated cellulose and the like. Especially, what contains 20-40 mass% of polyester fiber or cellulose fibers, such as rayon fiber, a regenerated cellulose, and a wood pulp from which high tensile breaking strength is obtained with the thickness of 10-50 micrometers can be used preferably.
また、不織布の強度を向上させる目的で、不織布製造工程で公知慣用の強化剤を添加することが好ましい。強化剤は、内添強化剤或いは外添強化剤を、単独または併用しても良い。内添強化剤としては、ポリアクリルアミド系樹脂、尿素−ホルムアルデヒド系樹脂、メラミン−ホルムアルデヒド系樹脂、エポキシ−ポリアミド系樹脂等が使用できる。特に、エポキシ−ポリアミド系樹脂であるポリアミドアミン・エピクロルヒドリン樹脂が著しく不織布の層間強度を上げるため好ましい。内添強化剤の添加量としては、好ましくは不織布に対して０．２〜１質量％、さらに好ましくは０．３〜０．５質量％である。一方、外添強化剤としては、でんぷん；ビスコース、カルボキシメチルセルロース、ポリビニルアルコール、ポリアクリルアミド等の熱可塑性樹脂が使用できる。中でも、不織布基材の層間強度を上げるために、上述の内添強化剤を使用することが好ましい。 For the purpose of improving the strength of the nonwoven fabric, it is preferable to add a known and usual reinforcing agent in the nonwoven fabric manufacturing process. As the reinforcing agent, an internal additive reinforcing agent or an external additive reinforcing agent may be used alone or in combination. As the internal reinforcement, polyacrylamide resins, urea-formaldehyde resins, melamine-formaldehyde resins, epoxy-polyamide resins, and the like can be used. In particular, a polyamidoamine / epichlorohydrin resin which is an epoxy-polyamide resin is preferable because it significantly increases the interlayer strength of the nonwoven fabric. The amount of the internally added reinforcing agent is preferably 0.2 to 1% by mass, more preferably 0.3 to 0.5% by mass, based on the nonwoven fabric. On the other hand, as the external additive reinforcing agent, a thermoplastic resin such as starch; viscose, carboxymethylcellulose, polyvinyl alcohol, polyacrylamide or the like can be used. Especially, in order to raise the interlayer strength of a nonwoven fabric base material, it is preferable to use the above-mentioned internal additive reinforcement agent.
前述の不織布の坪量は５〜１５ｇ／ｍ２であることが好ましく、７〜１２ｇ／ｍ２であることが一層好ましい。また、密度は０．１５〜０．３５ｇ／ｍ２であることが好ましく、０．２〜０．３ｇ／ｍ２であることがより好ましい。本範囲の場合、熱伝導性両面粘着テープの貼り直しの際の不織布の切断し難さ、湾曲したＬＥＤ部品を直線状へ戻す場合の曲げへの追従性、不織布への粘着剤の含浸性をバランスよく向上させることができ、熱伝導性を一層向上させることができる。 Preferably the basis weight of the aforementioned non-woven fabric is 5 to 15 g / m 2, and still more preferably 7~12g / m 2. Moreover, it is preferable that a density is 0.15-0.35 g / m < 2 >, and it is more preferable that it is 0.2-0.3 g / m < 2 >. In the case of this range, it is difficult to cut the nonwoven fabric when re-attaching the heat-conductive double-sided adhesive tape, the ability to follow bending when returning a curved LED component to a straight line, and the impregnation property of the adhesive to the nonwoven fabric. The balance can be improved, and the thermal conductivity can be further improved.
不織布の抄紙方法としては、特に限定されるものではないが、公知の湿式法により得られ、円網抄紙機、短網抄紙機、長網抄紙機、傾斜短網抄紙機等を使用した各種抄紙法が用いられる。 The paper making method of the nonwoven fabric is not particularly limited, but can be obtained by a known wet method, and various paper machines using a circular net paper machine, a short net paper machine, a long net paper machine, an inclined short net paper machine, etc. The method is used.
メッシュ基材の材質としては、ポリエステル樹脂、アミド樹脂、ポリアリレート樹脂等の公知のモノフィラメント繊維をスクリーン状に織ったメッシュ基材を用いることができる。中でも、モノフィラメントとして、引張弾性率や引張強度が高いポリエステル樹脂の使用が好ましい。メッシュ基材の形態としては、繊維径５〜２５μｍのモノフィラメント糸がＭＤおよびＴＤで１インチ当たり８０〜３００本交互に織り込まれた厚さ１０〜５０μｍのメッシュ基材を用いる。好ましくは繊維径１０〜２０μｍのモノフィラメント糸がＭＤおよびＴＤで１インチ当たり１００〜２００本交互に織り込まれた厚さ２０〜４０μｍのメッシュ基材である。この範囲にあるメッシュ基材を用いると、熱伝導性両面粘着テープの貼り直しの際の不織布の切断し難さ、湾曲したＬＥＤ部品を直線状へ曲げ戻した場合のＬＥＤ基板への追従性、不織布への粘着剤の含浸性をバランスよく向上させることができ、熱伝導性を向上させることができる。 As a material of the mesh base material, a mesh base material in which known monofilament fibers such as polyester resin, amide resin, polyarylate resin or the like are woven in a screen shape can be used. Among them, it is preferable to use a polyester resin having a high tensile elastic modulus and high tensile strength as a monofilament. As a form of the mesh substrate, a mesh substrate having a thickness of 10 to 50 μm in which 80 to 300 monofilament yarns having a fiber diameter of 5 to 25 μm are alternately woven by MD and TD per inch is used. Preferably, it is a mesh base material having a thickness of 20 to 40 μm in which 100 to 200 monofilament yarns having a fiber diameter of 10 to 20 μm are alternately woven in MD and TD per inch. When using a mesh base material in this range, it is difficult to cut the nonwoven fabric when re-attaching the heat conductive double-sided pressure-sensitive adhesive tape, the followability to the LED substrate when the curved LED component is bent back into a straight line, The impregnation property of the adhesive to the nonwoven fabric can be improved in a well-balanced manner, and the thermal conductivity can be improved.
前述の不織布、メッシュ基材は、熱伝導性両面粘着テープの構成にした際に、引張速度３００ｍｍ／ｍｉｎの９０°ピール粘着力より高い引張破断強度であり、２３℃５０％ＲＨ中での３００ｍｍ／ｍｉｎの引張速度において、５〜５０Ｎ／２０ｍｍ幅の引張破断強度が好ましい。とくに粘着テープは流れ方向（ＭＤ）へ貼付されていくことが多く、粘着テープの貼り直しの際に流れ方向（ＭＤ）へ応力がかかるため、流れ方向（ＭＤ）の引張破断強度は１０〜５０Ｎ／２０ｍｍ幅が好ましい。 The above-mentioned nonwoven fabric and mesh base material have a tensile breaking strength higher than a 90 ° peel adhesive strength at a tensile speed of 300 mm / min when it is configured as a heat conductive double-sided adhesive tape, and 300 mm in 23 ° C. and 50% RH. A tensile breaking strength of 5 to 50 N / 20 mm width is preferred at a tensile speed of / min. In particular, the adhesive tape is often applied in the flow direction (MD), and stress is applied to the flow direction (MD) when the adhesive tape is applied again. Therefore, the tensile breaking strength in the flow direction (MD) is 10 to 50 N. A width of 20 mm is preferred.
［熱伝導性粘着剤層］
本発明の熱伝導性粘着テープにおいては、粘着剤層として熱伝導性の粘着剤層を使用する。当該熱伝導性粘着剤層としては、通常の熱伝導性粘着テープに使用される熱伝導性の粘着剤層を使用でき、アクリル系粘着剤組成物、ゴム系粘着剤組成物、シリコーン系粘着剤組成物等の粘着剤組成物に、導電性フィラーを含有する粘着剤組成物からなる粘着剤層を好ましく使用できる。
[Thermal conductive adhesive layer]
In the heat conductive adhesive tape of this invention, a heat conductive adhesive layer is used as an adhesive layer. As the heat conductive pressure-sensitive adhesive layer, a heat conductive pressure-sensitive adhesive layer used for a normal heat conductive pressure-sensitive adhesive tape can be used, and an acrylic pressure-sensitive adhesive composition, a rubber-based pressure-sensitive adhesive composition, a silicone-based pressure-sensitive adhesive layer. A pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition containing a conductive filler can be preferably used for a pressure-sensitive adhesive composition such as a composition.
なかでも、（メタ）アクリレートを主たるモノマー成分とするアクリル系共重合体と、熱伝導性の無機フィラーとを含有するアクリル系粘着剤組成物を好ましく使用できる。 Among these, an acrylic pressure-sensitive adhesive composition containing an acrylic copolymer containing (meth) acrylate as a main monomer component and a thermally conductive inorganic filler can be preferably used.
（アクリル系共重合体）
アクリル系粘着剤組成物に使用するアクリル系共重合体は、（メタ）アクリレートモノマーを主たるモノマー成分とするアクリル系共重合体である。主たるモノマー成分として使用する（メタ）アクリレートとしては、粘着剤に使用する各種（メタ）アクリレートを使用でき、なかでもアルキル基の炭素数１〜１２のアルキル（メタ）アクリレートを好ましく使用できる。炭素数１〜１２のアルキル（メタ）アクリレートとしては、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、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート等のモノマーがあげられ、これらの１種または２種以上が用いられる。なかでも、アルキル基の炭素数が４〜８のアルキル（メタ）アクリレート、特にｎ−ブチルアクリレート及び２−エチルヘキシルアクリレートはフィラーを添加しても粘着性を確保しやすいため好ましい。
(Acrylic copolymer)
The acrylic copolymer used for the acrylic pressure-sensitive adhesive composition is an acrylic copolymer having a (meth) acrylate monomer as a main monomer component. As the (meth) acrylate used as the main monomer component, various (meth) acrylates used for the pressure-sensitive adhesive can be used, and among them, alkyl (meth) acrylates having 1 to 12 carbon atoms in the alkyl group can be preferably used. Examples of the alkyl (meth) acrylate having 1 to 12 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, Examples include monomers such as n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and one or more of these are used. It is done. Of these, alkyl (meth) acrylates having 4 to 8 carbon atoms in the alkyl group, particularly n-butyl acrylate and 2-ethylhexyl acrylate, are preferable because they can easily secure adhesiveness even when a filler is added.
炭素数１〜１２のアルキル（メタ）アクリレートの含有量は、アクリル系共重合体を構成するモノマー成分中の５０質量％以上とすることが好ましく、６０〜９８質量％であることが好ましく、８０質量％〜９８質量％以上であることが更に好ましい。 The content of the alkyl (meth) acrylate having 1 to 12 carbon atoms is preferably 50% by mass or more, preferably 60 to 98% by mass in the monomer component constituting the acrylic copolymer, 80 It is still more preferable that it is mass%-98 mass% or more.
また、本発明に使用する粘着剤組成物においては、上記主たる（メタ）アクリレートモノマーに、架橋剤と架橋反応するビニルモノマーとして炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーを併用することも好ましい。当該炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーを使用することでアクリル系共重合体に無機フィラーを多量に含有しても凝集性と流動性とを特に好適に兼備できる。炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーは、側鎖が長いため架橋点の流動性に優れる。また、炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーは、ガラス転移温度が低いため、粘着剤層の損失正接のピークを示す温度が低くなり、流動性に優れる粘着剤組成物を実現できる。さらに、炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーは立体障害が少ないため末端のカルボキシ基と架橋剤が反応しやすく粘着剤組成物の凝集力を得ることができる。このように、当該（メタ）アクリレートモノマーを使用することで、樹脂の凝集力を低下させずに粘着剤の凝集性と流動性を両立でき、得られる粘着剤組成物は多量のフィラーを含有しても特に優れた粘着物性を示す。 In the pressure-sensitive adhesive composition used in the present invention, the main (meth) acrylate monomer has a molecular chain formed of a carboxy group as a vinyl monomer that undergoes a crosslinking reaction with a crosslinking agent via a saturated hydrocarbon group having 2 or more carbon atoms. It is also preferable to use a (meth) acrylate monomer at the terminal in combination. By using a (meth) acrylate monomer having a carboxy group at the molecular chain end through a saturated hydrocarbon group having 2 or more carbon atoms, the acrylic copolymer can be cohesive even if it contains a large amount of an inorganic filler. The fluidity can be particularly suitably combined. A (meth) acrylate monomer having a carboxy group at the end of a molecular chain via a saturated hydrocarbon group having 2 or more carbon atoms is excellent in fluidity at a crosslinking point because of a long side chain. In addition, since the (meth) acrylate monomer having a carboxy group at the molecular chain terminal via a saturated hydrocarbon group having 2 or more carbon atoms has a low glass transition temperature, the temperature at which the loss tangent peak of the pressure-sensitive adhesive layer is low is low. Thus, an adhesive composition having excellent fluidity can be realized. Furthermore, since the (meth) acrylate monomer having a carboxy group at the molecular chain end via a saturated hydrocarbon group having 2 or more carbon atoms has little steric hindrance, the terminal carboxy group and the crosslinking agent can easily react with each other. Cohesive force can be obtained. Thus, by using the (meth) acrylate monomer, it is possible to achieve both cohesiveness and fluidity of the adhesive without reducing the cohesive strength of the resin, and the resulting adhesive composition contains a large amount of filler. However, it exhibits particularly excellent adhesive properties.
炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーとしては、例えば、下式（１）にて表わされる（メタ）アクリレートモノマーを例示できる。 Examples of the (meth) acrylate monomer having a carboxy group at the molecular chain end through a saturated hydrocarbon group having 2 or more carbon atoms include a (meth) acrylate monomer represented by the following formula (1).
なお、上記ジカルボン酸残基とは、分子鎖末端にジカルボン酸の一方のカルボキシ基が結合した構造におけるジカルボン酸の残基を表し、例えば、ＨＯＯＣ−Ｒ−ＣＯＯＨとして表わされるジカルボン酸により形成されるジカルボン酸残基は−ＯＯＣ−Ｒ−ＣＯＯＨである。当該ジカルボン酸残基を構成するジカルボン酸としては、上記Ｒが直接結合したジカルボン酸や、上記Ｒとして二価の脂肪族炭化水素基や芳香族炭化水素基を有するジカルボン酸を適宜使用でき、なかでも脂肪族炭化水素基、特に鎖状脂肪族炭化水素基を有するジカルボン酸は立体障害が生じにくいため好ましい。好適なジカルボン酸としては、具体的には、シュウ酸、マロン酸、コハク酸、マレイン酸、フマル酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸等を例示できる。 In addition, the said dicarboxylic acid residue represents the residue of the dicarboxylic acid in the structure which one carboxy group of dicarboxylic acid couple | bonded with the molecular chain terminal, For example, it forms with the dicarboxylic acid represented as HOOC-R-COOH. The dicarboxylic acid residue is -OOC-R-COOH. As the dicarboxylic acid constituting the dicarboxylic acid residue, a dicarboxylic acid in which R is directly bonded, or a dicarboxylic acid having a divalent aliphatic hydrocarbon group or an aromatic hydrocarbon group as R can be appropriately used. However, dicarboxylic acids having an aliphatic hydrocarbon group, particularly a chain aliphatic hydrocarbon group, are preferred because steric hindrance is unlikely to occur. Specific examples of suitable dicarboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. It can be illustrated.
上記式（１）で表わされる（メタ）アクリレートのなかでも、Ｒ２が炭素数２〜１８のアルキレン基であることが好ましく、炭素数が２〜５のアルキレン基であることが特に好ましい。また、Ｘ１がカルボキシ基であることが好ましい。具体的には、例えば、β−カルボキシアルキル（メタ）アクリレート、エチレンオキサイド（ＥＯ）変性コハク酸（メタ）アクリレート、プロピレンオキサイド（ＰＯ）変性コハク酸（メタ）アクリレート等が例示できる。これらのなかでも、β−カルボキシエチルアクリレートを特に好ましく使用できる。 Among the (meth) acrylates represented by the above formula (1), R 2 is preferably an alkylene group having 2 to 18 carbon atoms, and particularly preferably an alkylene group having 2 to 5 carbon atoms. X 1 is preferably a carboxy group. Specifically, for example, β-carboxyalkyl (meth) acrylate, ethylene oxide (EO) modified succinic acid (meth) acrylate, propylene oxide (PO) modified succinic acid (meth) acrylate and the like can be exemplified. Among these, β-carboxyethyl acrylate can be particularly preferably used.
炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーの含有量は、アクリル系共重合体を構成するモノマー成分中の０．５〜１０質量％であることが好ましく、１〜５質量％であることがより好ましい。炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーの含有量を当該範囲とすることで、架橋点を好適に形成しやすくなり、粘着剤の凝集力や初期接着性を向上させやすくなる。 The content of the (meth) acrylate monomer having a carboxy group at the molecular chain end through a saturated hydrocarbon group having 2 or more carbon atoms is 0.5 to 10% by mass in the monomer component constituting the acrylic copolymer. It is preferable that it is 1-5 mass%. By setting the content of the (meth) acrylate monomer having a carboxy group at the end of the molecular chain through a saturated hydrocarbon group having 2 or more carbon atoms within the above range, a crosslinking point can be easily formed, It becomes easy to improve cohesion force and initial adhesiveness.
アクリル系共重合体を構成するモノマー成分としては、上記以外のモノマー成分として、各種ビニルモノマーを使用できる。このようなビニルモノマーとしては、カルボキシ基含有モノマーを好ましく使用でき、当該カルボキシ基含有ビニルモノマーとしては、例えば、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、無水マレイン酸、フタル酸、無水フタル酸、クロトン酸等の１種又は２種以上を使用できる。なかでもアクリル酸、メタクリル酸は、アクリル系共重合体の凝集性を好適に調整しやすいため好ましく使用できる。 As the monomer component constituting the acrylic copolymer, various vinyl monomers can be used as monomer components other than those described above. As such a vinyl monomer, a carboxy group-containing monomer can be preferably used. Examples of the carboxy group-containing vinyl monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, phthalic acid, and phthalic anhydride. 1 type, or 2 or more types, such as crotonic acid, can be used. Of these, acrylic acid and methacrylic acid can be preferably used because they easily adjust the cohesiveness of the acrylic copolymer.
当該カルボキシ基含有ビニルモノマーの含有量は、アクリル系共重合体を構成するモノマー成分中の１０質量％以下であることが好ましく、０．５〜１０質量％であることがさらに好ましく、１〜５質量％であることがより好ましい。当該範囲で含有することにより、粘着剤の凝集力や保持力、接着性を、向上させやすい。 The content of the carboxy group-containing vinyl monomer is preferably 10% by mass or less, more preferably 0.5 to 10% by mass, and more preferably 1 to 5% in the monomer component constituting the acrylic copolymer. More preferably, it is mass%. By containing in the said range, it is easy to improve the cohesive force, holding force, and adhesiveness of an adhesive.
また、その他のビニルモノマーとして、酢酸ビニル、２−アクリルアミド−２−メチルプロパンスルフォン酸等のスルホン酸基含有モノマー、炭素数１〜３の（メタ）アクリレート、炭素数１３以上の（メタ）アクリレート、イソボルニル（メタ）アクリレート、スチレン等、公知のビニルモノマーを使用してもよい。 Other vinyl monomers include vinyl acetate, sulfonic acid group-containing monomers such as 2-acrylamido-2-methylpropanesulfonic acid, (meth) acrylates having 1 to 3 carbon atoms, (meth) acrylates having 13 or more carbon atoms, Known vinyl monomers such as isobornyl (meth) acrylate and styrene may be used.
その他のビニルモノマーを使用する場合の含有量は、アクリル系共重合体を構成するモノマー成分中の１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。当該範囲で含有することにより、粘着剤の凝集力や保持力、接着性を好適な範囲に調整しやすい。 The content in the case of using other vinyl monomers is preferably 10% by mass or less, more preferably 5% by mass or less, in the monomer component constituting the acrylic copolymer. By containing in the said range, it is easy to adjust the cohesive force, holding force, and adhesiveness of an adhesive to a suitable range.
上記アクリル系共重合は、溶液重合法、塊状重合法などの公知の重合方法により共重合させることにより得ることができる。重合開始方法も過酸化ベンゾイルや過酸化ラウリロイルなどの過酸化物系、アゾビスイソブチルニトリルなどのアゾ系の熱重合開始剤を用いた熱による開始方法や、アセトフェノン系、ベンゾインエーテル系、ベンジルケタール系、アシルフォスフィンオキシド系、ベンゾイン系、ベンゾフェノン系の光重合開始剤を用いた紫外線照射による開始方法や、電子線照射による方法を任意に選択できる。 The acrylic copolymer can be obtained by copolymerization by a known polymerization method such as a solution polymerization method or a bulk polymerization method. Polymerization is initiated by peroxides such as benzoyl peroxide and lauryl peroxide, thermal initiation methods using azo-based thermal polymerization initiators such as azobisisobutylnitrile, acetophenone, benzoin ether, benzyl ketal In addition, an initiation method by ultraviolet irradiation using an acylphosphine oxide-based, benzoin-based or benzophenone-based photopolymerization initiator, or a method by electron beam irradiation can be arbitrarily selected.
上記範囲内で重合したアクリル系共重合体は、ゲルパーミエーションクロマトグラフィのポリスチレン換算による重量平均分子量が３０万〜８０万、より好ましくは４０万〜７０万である。重量平均分子量が３０万以上とすることで粘着剤の凝集力を確保しやすくなり、高温下での接着性を向上させやすい。また重量平均分子量が８０万以下とすることで、熱伝導性フィラーの分散性や、粘着剤の塗工性、初期接着性を向上させやすい。 The acrylic copolymer polymerized within the above range has a weight average molecular weight in terms of polystyrene of gel permeation chromatography of 300,000 to 800,000, more preferably 400,000 to 700,000. When the weight average molecular weight is 300,000 or more, the cohesive force of the pressure-sensitive adhesive is easily secured, and the adhesiveness at high temperature is easily improved. Moreover, it is easy to improve the dispersibility of a heat conductive filler, the applicability | paintability of an adhesive, and initial stage adhesiveness because a weight average molecular weight shall be 800,000 or less.
（無機フィラー）
本発明に使用する無機フィラーは、熱伝導性を有する無機フィラーを使用でき、例えば、金属水酸化物、金属酸化物、金属、セラミックス等を使用できる。具体的には、熱伝導性のフィラーとして、例えば、水酸化アルミニウム、水酸化マグネシウム、酸化アルミニウム、酸化ケイ素、酸化マグネシウム、酸化亜鉛、酸化チタン、酸化ジルコニウム、酸化鉄、炭化ケイ素、窒化ホウ素、窒化アルミニウム、窒化チタン、窒化ケイ素、ホウ素化チタン、カーボン、ニッケル、銅、アルミニウム、チタン、金、銀等が挙げられる。これら無機フィラーは、アクリル系共重合体への分散性向上のため、シランカップリング処理、ステアリン酸処理などの表面処理を施してもよい。
(Inorganic filler)
As the inorganic filler used in the present invention, an inorganic filler having thermal conductivity can be used. For example, a metal hydroxide, a metal oxide, a metal, a ceramic, or the like can be used. Specifically, as the thermally conductive filler, for example, aluminum hydroxide, magnesium hydroxide, aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, titanium oxide, zirconium oxide, iron oxide, silicon carbide, boron nitride, nitriding Examples thereof include aluminum, titanium nitride, silicon nitride, titanium boride, carbon, nickel, copper, aluminum, titanium, gold, and silver. These inorganic fillers may be subjected to surface treatment such as silane coupling treatment or stearic acid treatment in order to improve dispersibility in the acrylic copolymer.
これら無機フィラーは、必要に応じて適宜選択して使用すればよいが、ＬＥＤの固定等の電子機器部品の固定に際しては、熱伝導性とともに難燃性も有する無機フィラーを使用することが好ましい。特に、ＬＥＤ固定用途においては、熱伝導に加えて難燃性を有するフィラーとして、水酸化アルミニウム、水酸化マグネシウムなどの金属水酸化物を使用することが特に好ましい。これらの金属水酸化物は熱伝導性を付与することができる。特に金属水酸化物の中で水酸化アルミニウムは、２５０℃程度から熱分解反応が起こり、難燃効果を発現するため使用することが好ましい。 These inorganic fillers may be appropriately selected and used as necessary, but it is preferable to use an inorganic filler that has both heat conductivity and flame retardancy when fixing electronic equipment components such as fixing LEDs. In particular, in LED fixing applications, it is particularly preferable to use a metal hydroxide such as aluminum hydroxide or magnesium hydroxide as a filler having flame retardancy in addition to heat conduction. These metal hydroxides can impart thermal conductivity. In particular, among the metal hydroxides, aluminum hydroxide is preferably used because it undergoes a thermal decomposition reaction from about 250 ° C. and exhibits a flame retardant effect.
無機フィラーの形状は、規則的な形状又は不規則な形状のいずれであってもよく、例えば、多角形状、立方体状、楕円状、球状、針状、平板状、鱗片状又はこれらを組み合わせた形状等が挙げられ、これらが凝集したフィラーであってもよい。無機フィラーの大きさは、最大となる幅や長さの平均、例えば粒子状の場合にはその平均粒径が、０．５〜５０μｍであることが好ましい。より好ましくは１〜３０μｍである。なお、フィラーの大きさ、形状は、得られる粘着テープの厚さにより適宜選択される。粘着テープの厚さよりも無機フィラーの最大の幅や長さが小さい方が望ましい。 The shape of the inorganic filler may be either a regular shape or an irregular shape, such as a polygonal shape, a cubic shape, an elliptical shape, a spherical shape, a needle shape, a flat plate shape, a scale shape, or a combination thereof. Etc., and these may be agglomerated fillers. As for the size of the inorganic filler, it is preferable that the average of the maximum width and length, for example, in the case of particles, the average particle size is 0.5 to 50 μm. More preferably, it is 1-30 micrometers. In addition, the magnitude | size and shape of a filler are suitably selected by the thickness of the adhesive tape obtained. It is desirable that the maximum width and length of the inorganic filler be smaller than the thickness of the adhesive tape.
粘着剤組成物への無機フィラーの添加量としては、良好な熱伝導性や難燃性を実現するために、アクリル系共重合体１００質量部に対し２００質量部以上とすることが好ましく、より好ましくは２２０質量部〜２８０質量部、さらに好ましくは２４０〜２６０質量部である。上記粘着剤組成物のなかでも、架橋剤と架橋反応するビニルモノマーとして炭素数が２以上の飽和炭化水素基を介してカルボキシ基を分子鎖末端に有する（メタ）アクリレートモノマーを使用した粘着剤組成物は、多量の無機フィラーを含有しても好適な接着性を実現できるため好ましい。 The amount of the inorganic filler added to the pressure-sensitive adhesive composition is preferably 200 parts by mass or more with respect to 100 parts by mass of the acrylic copolymer in order to achieve good thermal conductivity and flame retardancy. Preferably it is 220 mass parts-280 mass parts, More preferably, it is 240-260 mass parts. Among the above-mentioned pressure-sensitive adhesive compositions, a pressure-sensitive adhesive composition using a (meth) acrylate monomer having a carboxy group at the end of a molecular chain via a saturated hydrocarbon group having 2 or more carbon atoms as a vinyl monomer that undergoes a crosslinking reaction with a crosslinking agent. The product is preferable because it can realize suitable adhesiveness even if it contains a large amount of inorganic filler.
（粘着付与樹脂）
本発明の熱伝導性粘着剤には粘着物性を向上する目的で粘着付与樹脂を使用してもよい。粘着付与樹脂としては公知の脂肪族系石油樹脂、芳香族系石油樹脂、脂環族系石油樹脂などの石油樹脂、ロジン樹脂、ロジンエステル樹脂、不均化ロジン樹脂、重合ロジン樹脂、重合ロジンエステル樹脂、ロジンフェノールなどのロジン系樹脂、テルペン樹脂、テルペンフェノール樹脂などが使用できる。また粘着付与樹脂は２種類以上の樹脂を併用することができる。
(Tackifying resin)
A tackifier resin may be used in the heat conductive adhesive of the present invention for the purpose of improving adhesive properties. As tackifying resins, known aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, etc., rosin resins, rosin ester resins, disproportionated rosin resins, polymerized rosin resins, polymerized rosin esters Resins, rosin resins such as rosin phenol, terpene resins, terpene phenol resins and the like can be used. Further, two or more kinds of tackifying resins can be used in combination.
粘着付与樹脂の添加量としては、アクリル系共重合体１００質量部に対し２０質量部以下が好ましい。より好ましくは１０質量部以下である。当該範囲とすることで、良好な粘着付与効果や初期接着性を得られやすくなる。また、特に高い難燃性、例えばＵＬ９４Ｖ−０やＶＴＭ−０等の高い難燃性を要求される用途については、粘着付与樹脂を使用しないことも好ましい。 As addition amount of tackifying resin, 20 mass parts or less are preferable with respect to 100 mass parts of acrylic copolymers. More preferably, it is 10 parts by mass or less. By setting it as the said range, it will become easy to acquire a favorable tackifying effect and initial stage adhesiveness. Moreover, it is also preferable not to use a tackifying resin for applications that require particularly high flame retardancy, for example, high flame retardancy such as UL94V-0 and VTM-0.
また、粘着付与樹脂は、引火点が高い粘着付与樹脂を使用することが好ましく、引火点が２００度以上の樹脂を使用することが特に好ましい。引火点が２００度以上の粘着付与樹脂を使用すると、難燃性フィラーが燃焼時に熱分解して生じる難燃効果を特に効率的に発揮しやすくなる。 Moreover, it is preferable to use tackifying resin with a high flash point, and it is especially preferable to use resin with a flash point of 200 degree | times or more as tackifying resin. When a tackifying resin having a flash point of 200 degrees or more is used, it becomes easy to particularly effectively exhibit a flame retardant effect produced by thermal decomposition of the flame retardant filler during combustion.
（架橋剤）
本発明の粘着剤組成物にはエポキシ系架橋剤を使用することで、凝集力及び耐熱性を向上できる。エポキシ系架橋剤としては、１．３−ビス（Ｎ，Ｎ―グリシジルアミノメチル）シクロヘキサン（三菱ガス化学社製テトラッドＣ）、１．３−ビス（Ｎ，Ｎ−グリシジルアミノメチル）ベンゼン（三菱ガス化学社製テトラッドＸ）など公知のエポキシ系架橋剤を使用できる。
(Crosslinking agent)
The cohesive force and heat resistance can be improved by using an epoxy-based crosslinking agent in the pressure-sensitive adhesive composition of the present invention. Examples of the epoxy crosslinking agent include 1.3-bis (N, N-glycidylaminomethyl) cyclohexane (Tetrad C manufactured by Mitsubishi Gas Chemical Company), 1.3-bis (N, N-glycidylaminomethyl) benzene (Mitsubishi Gas). Known epoxy crosslinking agents such as Tetrad X) manufactured by Kagaku Co., Ltd. can be used.
架橋度合いの指標として、粘着剤層をトルエンに２４時間浸漬した後の不溶分を測定するゲル分率の値が用いられる。本発明の粘着剤組成物の架橋後のゲル分率は、３０質量％〜６５質量％が好ましい。またより好ましくは４０質量％〜５５質量％である。尚、ゲル分率の値は、無機フィラーの添加量を差し引いた樹脂の不溶分をさす。当該範囲とすることで、架橋後の粘着剤層に応力が加わった際にも、アクリル系共重合体と無機フィラーとの間の剥離が生じにくく、良好な粘着物性を得やすく、また、好適な初期接着性を得やすくなる。 As an index of the degree of cross-linking, the value of the gel fraction for measuring the insoluble content after the pressure-sensitive adhesive layer is immersed in toluene for 24 hours is used. As for the gel fraction after bridge | crosslinking of the adhesive composition of this invention, 30 mass%-65 mass% are preferable. More preferably, it is 40 mass%-55 mass%. In addition, the value of a gel fraction refers to the insoluble part of resin which deducted the addition amount of the inorganic filler. By adopting the range, even when stress is applied to the pressure-sensitive adhesive layer after crosslinking, peeling between the acrylic copolymer and the inorganic filler hardly occurs, and it is easy to obtain good pressure-sensitive adhesive properties. Easy initial adhesion.
（分散剤）
本発明の粘着剤組成物には、分散性を向上させるため各種分散剤を使用してもよい。特に、アミン系の分散剤は、エポキシ系架橋剤の架橋阻害を生じることなく好適な接着性を有する粘着剤層を形成できるため好ましい。また、アクリル系の粘着剤組成物中に多量の無機フィラーを使用した場合にも、好適に無機フィラーを分散でき、かつ、保管時に無機フィラーが沈降した場合にも、凝集して再分散できないケーキング状態の発生を好適に防止できる。なかでも、アミン化が５以上のアミン系分散剤を好ましく使用でき、１０〜１５０がより好ましく、２０〜８０がさらに好ましい。アミン系の分散剤としては、例えば、ビックケミージャパン社製ＢＹＫ−１１２、ＢＹＫ−２００８等が挙げられる。
(Dispersant)
Various dispersants may be used in the pressure-sensitive adhesive composition of the present invention in order to improve dispersibility. In particular, an amine-based dispersant is preferable because a pressure-sensitive adhesive layer having suitable adhesiveness can be formed without causing crosslinking inhibition of the epoxy-based crosslinking agent. In addition, even when a large amount of inorganic filler is used in the acrylic pressure-sensitive adhesive composition, the inorganic filler can be suitably dispersed, and even when the inorganic filler settles during storage, caking that cannot be aggregated and redispersed. The occurrence of the state can be suitably prevented. Among these, an amine dispersant having an amination of 5 or more can be preferably used, more preferably 10 to 150, and still more preferably 20 to 80. Examples of amine-based dispersants include BYK-112 and BYK-2008 manufactured by BYK Japan.
粘着剤組成物への分散剤の添加量としては、エポキシ系架橋剤の架橋阻害が無く、良好なケーキング防止効果や接着性を実現するために、アクリル系共重合体１００質量部に対し固形分で３〜５質量部が好ましい。アミン系分散剤の添加量を当該範囲とすることで、得られる粘着剤層の凝集力を確保しやすく、また、無機フィラーの良好な分散性や耐ケーキング性を得やすいことから、特に好適な保持力や接着性を実現できる。 The amount of the dispersant added to the pressure-sensitive adhesive composition is such that there is no cross-linking inhibition of the epoxy-based cross-linking agent, and in order to realize a good anti-caking effect and adhesiveness, the solid content with respect to 100 parts by mass of the acrylic copolymer. 3 to 5 parts by mass is preferable. By making the addition amount of the amine dispersant within this range, it is easy to ensure the cohesive strength of the resulting pressure-sensitive adhesive layer, and it is easy to obtain good dispersibility and caking resistance of the inorganic filler, which is particularly preferable. Holding power and adhesion can be realized.
また、本発明の粘着剤組成物は、熱伝導性、難燃性、粘着物性を大きく阻害しない範囲内で、老化防止剤、着色剤などの添加剤を適宜使用してもよい。 In addition, the pressure-sensitive adhesive composition of the present invention may appropriately use additives such as an anti-aging agent and a colorant as long as the thermal conductivity, flame retardancy, and pressure-sensitive adhesive properties are not significantly impaired.
本発明の粘着剤組成物からなる粘着剤層は損失正接のピークを示す温度が−４０℃以上、−１０℃以下であることが好ましい。当該範囲とすることで、無機フィラーを多く配合しても粘着剤の流動性と凝集性を両立しやすくなる。なお、損失正接のピーク温度は、５ｍｍ厚にまで重ね合わせた粘着剤層を試験片とし、レオメトリックス社製粘弾性試験機アレス２ｋＳＴＤに直径７．９ｍｍのパラレルプレートを装着し、試験片を挟み込み周波数１Ｈｚ、温度分散法で測定した値である。 The pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition of the present invention preferably has a temperature at which the loss tangent peak is -40 ° C or higher and -10 ° C or lower. By setting it as the said range, even if it mix | blends many inorganic fillers, it will become easy to make the fluidity | liquidity and cohesion of an adhesive compatible. The peak temperature of loss tangent is 5 mm thick. The test piece is an adhesive layer, a rheometer viscoelasticity tester Ares 2kSTD is attached to a parallel plate with a diameter of 7.9 mm, and the test piece is sandwiched. This is a value measured by a frequency 1 Hz frequency dispersion method.
（粘着剤製造方法）
本発明の粘着剤組成物の製造方法として、前述の製造方法でアクリル系共重合体を製造した後に、必要に応じて粘着付与樹脂及び粘度調整用に酢酸エチル、ヘキサン、ＭＥＫなどの有機溶剤を添加し、粘着付与樹脂を溶解させながら混合し、得られた樹脂組成物を取り出す。次に得られた樹脂組成物と無機フィラー及びその他添加剤とを、プラネタリーミキサーなどの低速攪拌機を用い、樹脂組成物、無機フィラー及びその他添加剤が均一になるまで混合し、粘着剤組成物を得る。
(Adhesive manufacturing method)
As a manufacturing method of the pressure-sensitive adhesive composition of the present invention, after manufacturing an acrylic copolymer by the above-described manufacturing method, an organic solvent such as ethyl acetate, hexane, or MEK is used for adjusting the tackifier resin and viscosity as necessary. Add and mix while dissolving the tackifying resin and take out the resulting resin composition. Next, the obtained resin composition and the inorganic filler and other additives are mixed using a low-speed stirrer such as a planetary mixer until the resin composition, the inorganic filler and other additives are uniform, and an adhesive composition Get.
［熱伝導性両面粘着テープ］
本発明の熱伝導性両面粘着テープは、基材の少なくとも一面に前述の粘着剤組成物からなる粘着剤層を有する粘着テープである。粘着剤層の厚さは、１回の乾燥後塗工厚さで１０μｍ〜１５０μｍであることが好ましい。当該範囲とすることで、粘着物性を好適に確保しやすく、また、製造時の粘着剤中の希釈溶剤の乾燥が容易となり生産性を向上させやすくなる。
[Heat conductive double-sided adhesive tape]
The heat conductive double-sided adhesive tape of this invention is an adhesive tape which has an adhesive layer which consists of an above-mentioned adhesive composition in at least one surface of a base material. The thickness of the pressure-sensitive adhesive layer is preferably 10 μm to 150 μm as a coating thickness after drying once. By setting it as the said range, it is easy to ensure adhesive physical property suitably, and it becomes easy to dry the dilution solvent in the adhesive at the time of manufacture, and it becomes easy to improve productivity.
粘着テープの厚さは、特に両面粘着テープの場合、５０μｍ〜３００μｍであることが好ましい。接合させる部品と熱伝導性両面粘着テープ間に空隙を発生させないため、より好ましくは１００μｍ〜２８０μｍである。 The thickness of the pressure-sensitive adhesive tape is preferably 50 μm to 300 μm, particularly in the case of a double-sided pressure-sensitive adhesive tape. In order not to generate a gap between the parts to be joined and the heat conductive double-sided pressure-sensitive adhesive tape, it is more preferably 100 μm to 280 μm.
熱伝導性両面粘着テープの製造方法は、剥離ライナーなどの支持体に前記粘着剤組成物をロールコーターやダイコーターなどで一定の厚さで塗布し、ドライヤーで希釈溶剤を乾燥させ、基材の片側に貼合することで片面粘着テープが製造できる。更に別の剥離ライナーに前記粘着剤組成物を塗布、乾燥したものを基材のもう一方の側に貼合することで両面粘着テープが製造できる。 The method for producing a heat conductive double-sided pressure-sensitive adhesive tape is as follows. The pressure-sensitive adhesive composition is applied to a support such as a release liner at a constant thickness using a roll coater or a die coater, and the diluted solvent is dried using a dryer. A single-sided adhesive tape can be manufactured by laminating on one side. Furthermore, a double-sided pressure-sensitive adhesive tape can be produced by applying the pressure-sensitive adhesive composition to another release liner and bonding the dried composition to the other side of the substrate.
粘着剤組成物中の無機フィラーとして、熱伝導性フィラーを使用した熱伝導性粘着剤組成物を使用した本発明の両面粘着テープは、特に液晶画像表示のバックライト等に使用されるＬＥＤ光源の固定に特に好適に使用できる。具体的な使用態様の例としては、以下のような態様を例示できる。液晶画像表示のバックライトに使用されるＬＥＤ光源ユニットとして、３〜２０ｍｍ幅の細長いアルミ製などの板の上にＬＥＤチップが多数実装されたＬＥＤ基板を使用し、ＬＥＤ基板を画面の端の一辺または二辺に設置し、導光板と拡散板でＬＥＤの光を画面全体に導き発光させる。ＬＥＤ基板はバックライト背面筐体にＬ字アングルで固定される。ＬＥＤ前述のＬＥＤ基板とＬ字アングルの固定に本発明の熱伝導性両面粘着テープを使用することができる。ＬＥＤが発光することにより発生した熱は、熱伝導性両面粘着テープを介してＬ字アングル及び液晶バックライト背面筐体に放熱される。 As the inorganic filler in the pressure-sensitive adhesive composition, the double-sided pressure-sensitive adhesive tape of the present invention using a heat-conductive pressure-sensitive adhesive composition using a heat-conductive filler is an LED light source particularly used for a backlight for liquid crystal image display. It can be particularly suitably used for fixing. Specific examples of usage modes include the following modes. As an LED light source unit used in a backlight for liquid crystal image display, an LED substrate on which a large number of LED chips are mounted on a 3-20 mm wide strip of aluminum or the like is used, and the LED substrate is one side of the edge of the screen. Alternatively, it is installed on two sides, and the light of the LED is guided to the entire screen by the light guide plate and the diffusion plate to emit light. The LED substrate is fixed to the backlight rear case at an L-shaped angle. LED The heat conductive double-sided pressure-sensitive adhesive tape of the present invention can be used for fixing the LED substrate and the L-shaped angle. The heat generated when the LED emits light is dissipated to the L-shaped angle and the liquid crystal backlight back casing through the heat conductive double-sided adhesive tape.
従来はＬＥＤ光源ユニットの固定には、基材無しの熱伝導性粘着テープが使用されていたが、ＬＥＤ光源ユニットを本発明の粘着テープで固定する場合、基材無しの熱伝導性粘着テープに比べ粘着テープが伸びたり切断しにくく、貼り作業性に優れる。また、ＬＥＤ基板は製造工程および搬送工程等において、ＬＥＤチップ側へ凹み状に湾曲することがある。湾曲の程度としては、３〜２０ｍｍ幅で１００〜５００ｍｍ長さのＬＥＤ基板において、ＬＥＤチップ側を天面側にして平坦な場所へ置いた際、長手方向の両端が３〜３０ｍｍ浮く状態となる。ＬＥＤ基板への熱伝導性両面粘着テープの貼付は、ＬＥＤ基板が湾曲した状態で貼付された後、バックライト背面筐体へ貼付される際、ＬＥＤ基板を直線状へ曲げ戻され貼付される。この際、熱伝導性両面粘着テープは長手方向へ圧縮され、ＬＥＤ基板の長さに対して基材が余りやすくなる。熱伝導性両面粘着テープの基材の弾性が不十分であると、ＬＥＤ基板への両面粘着テープの追従性が劣り、波ジワが発生する。波ジワが発生すると、ＬＥＤ基板あるいはバックライト背面筐体の間に空隙が発生し、熱伝導性が悪化する。本発明の熱伝導性両面粘着テープを使用することにより、ＬＥＤチップ側の長手方向へ凹み状に湾曲したＬＥＤ基板を直線状へ曲げ戻されてバックライト背面筐体へ貼付される際、熱伝導性両面粘着テープに波ジワが発生しにくく、ＬＥＤ基板とバックライト背面筐体に密着し、熱伝導性が良好となる。 Conventionally, a heat conductive adhesive tape without a substrate has been used for fixing the LED light source unit. However, when fixing an LED light source unit with the adhesive tape of the present invention, the heat conductive adhesive tape without a substrate is used. Compared with adhesive tape, it is hard to stretch or cut, and it is excellent in workability. In addition, the LED substrate may be bent in a concave shape toward the LED chip in the manufacturing process, the transport process, and the like. As for the degree of bending, in an LED substrate having a width of 3 to 20 mm and a length of 100 to 500 mm, when placed on a flat place with the LED chip side as the top surface side, both ends in the longitudinal direction float 3 to 30 mm. . The sticking of the heat conductive double-sided pressure-sensitive adhesive tape to the LED substrate is performed by sticking the LED substrate back to a straight line when the LED substrate is attached in a curved state and then attached to the backlight rear housing. At this time, the heat-conductive double-sided pressure-sensitive adhesive tape is compressed in the longitudinal direction, and the base material becomes much easier than the length of the LED substrate. When the elasticity of the base material of the heat conductive double-sided pressure-sensitive adhesive tape is insufficient, the followability of the double-sided pressure-sensitive adhesive tape to the LED substrate is inferior, and wrinkles are generated. When wave wrinkles are generated, a gap is generated between the LED substrate or the backlight rear case, and the thermal conductivity is deteriorated. By using the heat conductive double-sided pressure-sensitive adhesive tape of the present invention, the LED substrate bent in a concave shape in the longitudinal direction on the LED chip side is bent back into a linear shape and adhered to the backlight rear case. The wavy double-sided pressure-sensitive adhesive tape is less likely to wrinkle, adheres closely to the LED substrate and the backlight rear case, and has good thermal conductivity.
熱伝導性フィラーを使用した粘着テープをＬＥＤ光源の固定に使用する場合には、粘着テープの熱伝導率は０．６Ｗ／ｍ・ｋ以上であることが好ましい。また、難燃性はＵｎｄｅｒｗｒｉｔｅｒｓ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｃ．社の規格において、ＵＬ９４Ｖ−２またはＶＴＭ−２以上の性能であることが好ましい。さらに粘着物性として、２３℃５０％ＲＨ下でのアルミへの貼付１時間後の引張速度３００ｍｍ／ｍｉｎの９０°ピール粘着力が５〜１０Ｎ／２０ｍｍ幅、保持力は、５ｍｍ幅×３０ｍｍ長の面積で１００ｇの荷重をせん断方向にかけた際に２４時間保持する性能であることが好ましい。 When an adhesive tape using a thermally conductive filler is used for fixing the LED light source, the thermal conductivity of the adhesive tape is preferably 0.6 W / m · k or more. In addition, flame retardancy is reported by Underwriters Laboratories Inc. It is preferable that the performance is UL94V-2 or VTM-2 or higher in the company standard. Furthermore, as adhesive physical properties, 90 ° peel adhesive strength at a tensile speed of 300 mm / min after 1 hour sticking to aluminum at 23 ° C. and 50% RH is 5 to 10 N / 20 mm width, and holding force is 5 mm width × 30 mm length. It is preferable to have a performance of holding for 24 hours when a load of 100 g in area is applied in the shear direction.
以下に実施例について具体的に説明をするが、本発明はこれに限定されるものではない。 Examples will be specifically described below, but the present invention is not limited thereto.
［実施例１］
（１−１）アクリル系共重合体の調整
攪拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に、２−エチルヘキシルアクリレート９６．４質量部、β−カルボキシエチルアクリレート２．４質量部、アクリル酸１．２質量部、酢酸エチル９８質量部を仕込み、攪拌下、窒素を吹き込みながら７５℃まで昇温した。その後、予め酢酸エチルにて溶解したアゾビスイソブチロニトリル溶液２質量部（固形分５質量％）を添加した。その後、攪拌下７５℃にて８時間ホールドした後、内容物を冷却し２００メッシュ金網にて濾過した。不揮発分５０質量％、粘度８０００ｍＰａ・ｓの粘着剤組成物を得た。得られた粘着剤組成物中のアクリル重合体の重量平均分子量は５０万であった。
[Example 1]
(1-1) Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, and a thermometer, 96.4 parts by mass of 2-ethylhexyl acrylate, 2.4 parts by mass of β-carboxyethyl acrylate Part, 1.2 parts by mass of acrylic acid and 98 parts by mass of ethyl acetate were added, and the temperature was raised to 75 ° C. while blowing nitrogen under stirring. Thereafter, 2 parts by mass (solid content 5% by mass) of an azobisisobutyronitrile solution previously dissolved in ethyl acetate was added. Then, after holding for 8 hours at 75 ° C. with stirring, the contents were cooled and filtered through a 200 mesh wire mesh. A pressure-sensitive adhesive composition having a nonvolatile content of 50% by mass and a viscosity of 8000 mPa · s was obtained. The weight average molecular weight of the acrylic polymer in the obtained pressure-sensitive adhesive composition was 500,000.
（１−２）粘着剤組成物の調整
プラネタリーミキサーの容器に、無機フィラーとして熱伝導の水酸化アルミニウム（昭和電工社製ハイジライトＨ３２、平均粒径８μｍ）を上記（１−１）の粘着剤組成物固形分１００質量部に対し２５０質量部を入れ、その後、上記（１−１）で得られた粘着剤組成物を加える。３０分攪拌させ水酸化アルミニウと粘着剤組成物を均一に混合させた。酢酸エチルを加え固形分６４質量％になるよう調整し、粘度６７００ｍＰａ・ｓの熱伝導粘着剤組成物（Ａ）を得た。
(1-2) Adjustment of pressure-sensitive adhesive composition Into the container of the planetary mixer, heat-conducting aluminum hydroxide (Hijilite H32, Showa Denko Co., Ltd., average particle size: 8 μm) as an inorganic filler is bonded to the above (1-1). 250 parts by mass is added to 100 parts by mass of the solid content of the adhesive composition, and then the pressure-sensitive adhesive composition obtained in (1-1) above is added. The mixture was stirred for 30 minutes to uniformly mix aluminum hydroxide and the pressure-sensitive adhesive composition. Ethyl acetate was added to adjust the solid content to 64% by mass to obtain a heat conductive adhesive composition (A) having a viscosity of 6700 mPa · s.
（１−３）不織布の調整
マニラ麻５０質量％、ポリエステル３０質量％、再生セルロース１９．５質量％、ポリアミドアミン・エピクロルヒドリン樹脂０．５質量％を含む溶液を、傾斜短網抄紙機にて、坪量９．４ｇ／ｍ２、密度０．２５ｇ／ｃｍ３、厚さ３０μｍになるように抄紙し、引張破断強度がＭＤで１１．２Ｎ／２０ｍｍ、ＴＤで５．１Ｎ／２０ｍｍ、弾性率がＭＤで１．７ＧＰａ、ＴＤで０．６ＧＰａを得た。１０枚重ねのガーレ式透気度が０．１０秒であった。
(1-3) Preparation of non-woven fabric A solution containing 50% by mass of Manila hemp, 30% by mass of polyester, 19.5% by mass of regenerated cellulose, and 0.5% by mass of polyamidoamine / epichlorohydrin resin Paper is made so that the amount is 9.4 g / m 2 , the density is 0.25 g / cm 3 , and the thickness is 30 μm. The tensile strength at break is 11.2 N / 20 mm in MD, 5.1 N / 20 mm in TD, and the elastic modulus is MD. 1.7 GPa and TD 0.6 GPa. The 10-layer Gurley air permeability was 0.10 seconds.
（１−４）粘着テープの調整
（１−２）で得られた熱伝導粘着剤組成物（Ａ）へ、エポキシ系架橋剤（三菱ガス化学社製テトラッドＣ）を固形分２質量％になるよう酢酸エチルで溶解した溶液を熱伝導粘着剤組成物中のアクリル共重合体固形分１００部に対して、０．４２部配合し、ディゾルバー攪拌機で３０分間攪拌する。得られた粘着剤組成物Ａを剥離ライナーに乾燥後厚さが９５μｍになるようにロールコーターで塗布し、８０℃ドライヤー中で３分間乾燥させる。同様にして計２枚の粘着シートを得る。（１−３）で得られた厚さ３０μｍの不織布の両側に粘着シートをラミネートし、厚さ２００μｍの両面粘着テープを作成した。架橋剤の架橋反応のため４０℃乾燥機に４８時間養生させ両面粘着テープを得た。
(1-4) Adjustment of pressure-sensitive adhesive tape To the heat conductive pressure-sensitive adhesive composition (A) obtained in (1-2), an epoxy-based crosslinking agent (Tetrad C manufactured by Mitsubishi Gas Chemical Co., Ltd.) has a solid content of 2% by mass. 0.42 parts of the solution dissolved in ethyl acetate is mixed with 100 parts of the acrylic copolymer solid content in the heat conductive adhesive composition, and stirred with a dissolver stirrer for 30 minutes. The obtained pressure-sensitive adhesive composition A is applied to a release liner with a roll coater so as to have a thickness of 95 μm after drying, and dried in an 80 ° C. dryer for 3 minutes. Similarly, a total of two adhesive sheets are obtained. An adhesive sheet was laminated on both sides of the 30 μm-thick nonwoven fabric obtained in (1-3) to prepare a double-sided adhesive tape having a thickness of 200 μm. A double-sided pressure-sensitive adhesive tape was obtained by curing in a 40 ° C. dryer for 48 hours for the crosslinking reaction of the crosslinking agent.
［実施例２］
不織布として、マニラ麻４０質量％、ポリエステル４０質量％、再生セルロース１９．５質量％、ポリアミドアミン・エピクロルヒドリン樹脂０．５質量％を含む溶液を、傾斜短網抄紙機にて、坪量１６．８ｇ／ｍ２、密度０．２８ｇ／ｃｍ３、厚さ４５μｍになるように抄紙し、引張破断強度がＭＤで１７．６Ｎ／２０ｍｍ、ＴＤで７．６Ｎ／２０ｍｍ、弾性率がＭＤで１．８ＧＰａ、ＴＤで０．６ＧＰａを得た。１０枚重ねのガーレ式透気度が０．２０秒であった。得られた不織布を基材として使用し、厚さ２１３μｍにしたこと以外は実施例１と同様にして両面粘着テープを得た。
[Example 2]
As a non-woven fabric, a solution containing 40% by mass of Manila hemp, 40% by mass of polyester, 19.5% by mass of regenerated cellulose, and 0.5% by mass of polyamidoamine / epichlorohydrin resin was measured with an inclined short net paper machine at a basis weight of 16.8 g / The paper was made to m 2 , density 0.28 g / cm 3 and thickness 45 μm, the tensile strength at break was 17.6 N / 20 mm in MD, 7.6 N / 20 mm in TD, and the elastic modulus was 1.8 GPa in MD. 0.6 GPa was obtained by TD. Ten sheets of Gurley air permeability was 0.20 seconds. A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the obtained nonwoven fabric was used as a base material and the thickness was 213 μm.
［実施例３］
不織布として、マニラ麻５０質量％、木材パルプ３０質量％、レーヨン繊維１７．５質量％、ポリビニルアルコール繊維２質量％、ポリアミドアミン・エピクロルヒドリン樹脂０．５質量％を含む溶液を、傾斜短網抄紙機にて、坪量１７．５ｇ／ｍ２、密度０．３４ｇ／ｃｍ３、厚さ４０μｍになるように抄紙し、引張破断強度がＭＤで１２．４Ｎ／２０ｍｍ、ＴＤで１１．２Ｎ／２０ｍｍ、弾性率がＭＤで１．２ＧＰａ、ＴＤ１．２ＧＰａを得た。１０枚重ねのガーレ式透気度が０．３０秒であった。得られた不織布を基材として使用し、厚さ２１２μｍにしたこと以外は実施例１と同様にして両面粘着テープを得た。
[Example 3]
As a non-woven fabric, a solution containing 50% by mass of Manila hemp, 30% by mass of wood pulp, 17.5% by mass of rayon fiber, 2% by mass of polyvinyl alcohol fiber, and 0.5% by mass of polyamidoamine / epichlorohydrin resin Paper with a basis weight of 17.5 g / m 2 , a density of 0.34 g / cm 3 and a thickness of 40 μm, and a tensile breaking strength of 12.4 N / 20 mm in MD, 11.2 N / 20 mm in TD, elasticity The rate was 1.2 GPa and TD 1.2 GPa in MD. Ten sheets of Gurley air permeability was 0.30 seconds. A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the obtained non-woven fabric was used as a substrate and the thickness was 212 μm.
［実施例４］
不織布として、マニラ麻８０質量％、再生セルロース２０質量％を含む溶液を、傾斜短網抄紙機にて、坪量１７．０ｇ／ｍ２、密度０．３０ｇ／ｃｍ３、厚さ４７μｍになるように抄紙し、外添強化剤として尿素リン酸エステル化でんぷん水溶液を不織布に対し、ワイヤーバーにて１００℃で３分間乾燥後、０．５ｇ／ｍ２となるよう塗布し、引張破断強度がＭＤで２１．２Ｎ／２０ｍｍ、ＴＤで２１．２Ｎ／２０ｍｍ、弾性率がＭＤで１．６ＧＰａ、ＴＤ０．９ＧＰａを得た。１０枚重ねのガーレ式透気度が０．２０秒であった。得られた不織布を基材として使用し、厚さ２１３μｍにしたこと以外は実施例１と同様にして両面粘着テープを得た。
[Example 4]
As a non-woven fabric, a solution containing 80% by mass of Manila hemp and 20% by mass of regenerated cellulose is so formed as to have a basis weight of 17.0 g / m 2 , a density of 0.30 g / cm 3 , and a thickness of 47 μm using an inclined short paper machine. Paper is made, and urea phosphate esterified aqueous starch solution is applied to the nonwoven fabric as an external additive strengthening agent after being dried at 100 ° C. for 3 minutes with a wire bar to 0.5 g / m 2, and the tensile strength at break is MD. 21.2 N / 20 mm, 21.2 N / 20 mm in TD, elastic modulus was 1.6 GPa in MD, and TD 0.9 GPa. Ten sheets of Gurley air permeability was 0.20 seconds. A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the obtained nonwoven fabric was used as a base material and the thickness was 213 μm.
［実施例５］
基材として、繊維径２５μｍのポリエステル製モノフィラメント糸を、ＭＤとＴＤへ１インチ当たり１３２本となるよう交互に織り込んだ厚さ５０μｍのメッシュ基材を作成し、引張破断強度がＭＤで４０．６Ｎ／２０ｍｍ、ＴＤで４１．６Ｎ／２０ｍｍ、弾性率がＭＤで０．５ＧＰａ、ＴＤ０．６ＧＰａを得た。１０枚重ねのガーレ式透気度が０．０６秒であった。得られた不織布を使用し、厚さ２０８μｍにしたこと以外は実施例１と同様にして両面粘着テープを得た。
[Example 5]
As a base material, a 50 μm-thick mesh base material in which polyester monofilament yarns having a fiber diameter of 25 μm are alternately woven into MD and TD so as to be 132 pieces per inch is prepared, and the tensile breaking strength is 40.6 N in MD. / 20 mm, 41.6 N / 20 mm in TD, and elastic modulus was 0.5 GPa and TD 0.6 GPa in MD. The 10-layer Gurley air permeability was 0.06 seconds. A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the obtained nonwoven fabric was used and the thickness was 208 μm.
［実施例６］
実施例１における水酸化アルミニウム（昭和電工社製ハイジライトＨ３２、平均粒径８μｍ）の添加量を、粘着剤組成物固形分１００質量部に対し２７０質量部に変更した以外は実施例１と同様にして熱伝導粘着剤組成物（Ｂ）を得た。得られた熱伝導粘着剤組成物（Ｂ）を用いて、実施例１と同様にして両面粘着テープを作成した。
[Example 6]
The same as Example 1 except that the addition amount of aluminum hydroxide (Hijilite H32 manufactured by Showa Denko KK, average particle size 8 μm) in Example 1 was changed to 270 parts by mass relative to 100 parts by mass of the solid content of the pressure-sensitive adhesive composition. Thus, a heat conductive adhesive composition (B) was obtained. A double-sided pressure-sensitive adhesive tape was prepared in the same manner as in Example 1 using the obtained heat conductive pressure-sensitive adhesive composition (B).
［実施例７］
実施例１における水酸化アルミニウム（昭和電工社製ハイジライトＨ３２、平均粒径８μｍ）の添加量を、粘着剤組成物固形分１００質量部に対し２２０質量部に変更した以外は実施例１と同様にして熱伝導粘着剤組成物（Ｃ）を得た。得られた熱伝導粘着剤組成物（Ｃ）を用いて、実施例１と同様にして両面粘着テープを作成した。
[Example 7]
The same as in Example 1 except that the addition amount of aluminum hydroxide (Hijilite H32 manufactured by Showa Denko KK, average particle size of 8 μm) in Example 1 was changed to 220 parts by mass with respect to 100 parts by mass of the solid content of the pressure-sensitive adhesive composition. Thus, a heat conductive adhesive composition (C) was obtained. A double-sided pressure-sensitive adhesive tape was prepared in the same manner as in Example 1 using the obtained heat conductive pressure-sensitive adhesive composition (C).
［実施例８］
実施例１における水酸化アルミニウム（昭和電工社製ハイジライトＨ３２、平均粒径８μｍ）の添加量を、粘着剤組成物固形分１００質量部に対し２００質量部に変更した以外は実施例１と同様にして熱伝導粘着剤組成物（Ｄ）を得た。得られた熱伝導粘着剤組成物（Ｄ）を用いて、実施例１と同様にして両面粘着テープを作成した。
[Example 8]
The same as Example 1 except that the addition amount of aluminum hydroxide (Hijilite H32 manufactured by Showa Denko KK, average particle size 8 μm) in Example 1 was changed to 200 parts by mass with respect to 100 parts by mass of the solid content of the pressure-sensitive adhesive composition. Thus, a heat conductive adhesive composition (D) was obtained. A double-sided pressure-sensitive adhesive tape was prepared in the same manner as in Example 1 using the obtained heat conductive pressure-sensitive adhesive composition (D).
［実施例９］
粘着付与剤として、テルペン樹脂（ヤスハラケミカル社製ＰＸ１２５０）をアクリル共重合体固形分１００質量部に対し１５質量部、重合ロジンペンタエリスリトール（ハリマ化成社製ハリタックＰＣＪ）をアクリル共重合体固形分１００質量部に対し５質量部を配合させた熱伝導粘着剤組成物（Ｅ）を用いたこと以外は実施例１と同様にして両面粘着テープを得た。なお、粘着付与剤の配合は後述の粘着剤組成物の調整方法により行った。
[Example 9]
As a tackifier, terpene resin (PX1250 manufactured by Yasuhara Chemical Co., Ltd.) is 15 parts by mass with respect to 100 parts by mass of acrylic copolymer solids, and polymerized rosin pentaerythritol (Halitac PCJ manufactured by Harima Chemicals Co., Ltd.) is 100 parts by mass of acrylic copolymer solids. A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the heat conductive pressure-sensitive adhesive composition (E) in which 5 parts by mass was blended with respect to the parts was used. In addition, the compounding of the tackifier was performed by the adjustment method of the below-mentioned adhesive composition.
［実施例１０］
粘着付与剤として、テルペン樹脂（ヤスハラケミカル社製ＰＸ１２５０）の使用量１５質量部を、アクリル共重合体固形分１００質量部に対し５質量部とした熱伝導粘着剤組成物（Ｆ）を用いたこと以外は実施例９と同様に両面粘着テープを得た。
[Example 10]
As a tackifier, the heat conductive adhesive composition (F) which used 15 mass parts of terpene resin (PX1250 by Yashara Chemical Co., Ltd.) as 5 mass parts with respect to 100 mass parts of acrylic copolymer solid content was used. Otherwise, a double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 9.
［実施例１１］
（１１−１）アクリル系共重合体の調整
攪拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に、２−エチルヘキシルアクリレート３０．０質量部、ブチルアクリレート６３．４質量部、アクリル酸３．０質量部、酢酸ビニル３．５質量部、β―ヒドロキシエチルアクリレート０．１質量部、酢酸エチル９８質量部を仕込み、攪拌下、窒素を吹き込みながら７５℃まで昇温した。その後、予め酢酸エチルにて溶解したアゾビスイソブチロニトリル溶液２質量部（固形分５質量％）を添加した。その後、攪拌下７５℃にて８時間ホールドした後、内容物を冷却し２００メッシュ金網にて濾過した。不揮発分５０質量％、粘度８０００ｍＰａ・ｓ、の粘着剤組成物を得た。得られた粘着剤組成物中のアクリル重合体の重量平均分子量は５０万であった。
[Example 11]
(11-1) Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 30.0 parts by mass of 2-ethylhexyl acrylate, 63.4 parts by mass of butyl acrylate, acrylic 3.0 parts by weight of acid, 3.5 parts by weight of vinyl acetate, 0.1 part by weight of β-hydroxyethyl acrylate and 98 parts by weight of ethyl acetate were charged, and the temperature was raised to 75 ° C. while blowing nitrogen under stirring. Thereafter, 2 parts by mass (solid content 5% by mass) of an azobisisobutyronitrile solution previously dissolved in ethyl acetate was added. Then, after holding for 8 hours at 75 ° C. with stirring, the contents were cooled and filtered through a 200 mesh wire mesh. A pressure-sensitive adhesive composition having a nonvolatile content of 50% by mass and a viscosity of 8000 mPa · s was obtained. The weight average molecular weight of the acrylic polymer in the obtained pressure-sensitive adhesive composition was 500,000.
得られたアクリル共重合体溶液を用いて（１−２）粘着剤組成物の調整に記載の方法にて熱伝導粘着剤組成物の調整を行い、熱伝導性粘着剤組成物（Ｇ）を得た。得られた熱伝導粘着剤組成物（Ｇ）を用いて（１−３）粘着テープの調整に記載の方法にて両面粘着テープを得た。 Using the obtained acrylic copolymer solution, the heat conductive pressure-sensitive adhesive composition is adjusted by the method described in (1-2) Preparation of pressure-sensitive adhesive composition, and the heat conductive pressure-sensitive adhesive composition (G) is obtained. Obtained. Using the obtained heat conductive adhesive composition (G), a double-sided adhesive tape was obtained by the method described in (1-3) Preparation of adhesive tape.
［実施例１２］
（１２−１）アクリル系共重合体の調整
攪拌機、還流冷却管、窒素導入管、温度計を備えた反応容器に、ブチルアクリレート９３．４質量部、アクリル酸３．５質量部、酢酸ビニル３．０質量部、β―ヒドロキシエチルアクリレート０．１質量部、酢酸エチル９８質量部を仕込み、攪拌下、窒素を吹き込みながら７５℃まで昇温した。その後、予め酢酸エチルにて溶解したアゾビスイソブチロニトリル溶液２質量部（固形分５質量％）を添加した。その後、攪拌下７５℃にて８時間ホールドした後、内容物を冷却し２００メッシュ金網にて濾過した。不揮発分５０質量％、粘度８０００ｍＰａ・ｓの粘着剤組成物を得た。得られた粘着剤組成物中のアクリル重合体の重量平均分子量は５０万であった。
[Example 12]
(12-1) Preparation of acrylic copolymer In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, and a thermometer, 93.4 parts by mass of butyl acrylate, 3.5 parts by mass of acrylic acid, vinyl acetate 3 0.0 parts by mass, 0.1 parts by mass of β-hydroxyethyl acrylate, and 98 parts by mass of ethyl acetate were charged, and the temperature was raised to 75 ° C. while blowing nitrogen under stirring. Thereafter, 2 parts by mass (solid content 5% by mass) of an azobisisobutyronitrile solution previously dissolved in ethyl acetate was added. Then, after holding for 8 hours at 75 ° C. with stirring, the contents were cooled and filtered through a 200 mesh wire mesh. A pressure-sensitive adhesive composition having a nonvolatile content of 50% by mass and a viscosity of 8000 mPa · s was obtained. The weight average molecular weight of the acrylic polymer in the obtained pressure-sensitive adhesive composition was 500,000.
得られたアクリル共重合体溶液を用いて（１−２）粘着剤組成物の調整に記載の方法にて熱伝導粘着剤組成物の調整を行い熱伝導性粘着剤組成物（Ｈ）を得た。得られた熱伝導粘着剤組成物（Ｈ）を用いて（１−３）粘着テープの調整に記載の方法にて両面粘着テープを得た。 The heat conductive adhesive composition (H) is obtained by adjusting the heat conductive pressure sensitive adhesive composition by the method described in (1-2) Adjustment of pressure sensitive adhesive composition using the obtained acrylic copolymer solution. It was. Using the obtained heat conductive adhesive composition (H), a double-sided adhesive tape was obtained by the method described in (1-3) Preparation of adhesive tape.
［比較例１］
基材を使用しないこと意外は実施例１と同様にして厚さ１９０μｍの基材無し両面粘着テープを得た。
[Comparative Example 1]
A double-sided adhesive tape without a substrate having a thickness of 190 μm was obtained in the same manner as in Example 1 except that the substrate was not used.
［比較例２］
基材として、厚さ６μｍのＰＥＴフィルム（東レ社製ルミラーＳ）を使用し、厚さ１９６μｍにしたこと以外は実施例１と同様にして両面粘着テープを得た。用いた厚さ６μｍのＰＥＴフィルムは、引張破断強度がＭＤで１８．２Ｎ／２０ｍｍ、ＴＤで１９．２Ｎ／２０ｍｍ、弾性率がＭＤで４．３ＧＰａ、ＴＤで４．７ＧＰａを得た。１０枚重ねのガーレ式透気度が１０秒を超える値であった。
[Comparative Example 2]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that a PET film having a thickness of 6 μm (Lumirror S manufactured by Toray Industries, Inc.) was used as the substrate and the thickness was 196 μm. The PET film having a thickness of 6 μm used had a tensile strength at break of 18.2 N / 20 mm in MD, 19.2 N / 20 mm in TD, 4.3 GPa in MD, and 4.7 GPa in TD. The 10-layer Gurley air permeability was a value exceeding 10 seconds.
［比較例３］
基材として、厚さ３０μｍのポリイミドコートＰＥＴフィルム（東レ社製ルミラーＺＶ７０）を使用し、厚さ２２０μｍにしたこと以外は実施例１と同様にして両面粘着テープを得た。厚さ３０μｍのポリイミドコートＰＥＴフィルムは、引張破断強度がＭＤで９０Ｎ／２０ｍｍ、ＴＤで１０２Ｎ／２０ｍｍ、弾性率がＭＤで３．６ＧＰａ、ＴＤで４．２ＧＰａを得た。１０枚重ねのガーレ式透気度が１０秒以上であった。
[Comparative Example 3]
A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that a polyimide-coated PET film having a thickness of 30 μm (Lumirror ZV70 manufactured by Toray Industries, Inc.) was used as the substrate and the thickness was 220 μm. The polyimide-coated PET film having a thickness of 30 μm had a tensile strength at break of 90 N / 20 mm in MD, 102 N / 20 mm in TD, 3.6 GPa in MD, and 4.2 GPa in TD. Ten sheets of Gurley air permeability was 10 seconds or more.
［比較例４］
不織布として、マニラ麻５０質量％、ポリエステル３０質量％、再生セルロース１９．５質量％、ポリアミドアミン・エピクロルヒドリン樹脂０．５質量％を含む溶液を、傾斜短網抄紙機にて、坪量１７．３ｇ／ｍ２、密度０．２５ｇ／ｃｍ３、厚さ５５μｍになるように抄紙し、引張破断強度がＭＤで２６．５Ｎ／２０ｍｍ、ＴＤで２３．６Ｎ／２０ｍｍ、弾性率がＭＤで１．７ＧＰａ、ＴＤで０．６ＧＰａを得た。し、引張破断強度がＭＤで１２．４Ｎ／２０ｍｍ、ＴＤで１１．２Ｎ／２０ｍｍ、弾性率がＭＤで１．２ＧＰａ、ＴＤ１．２ＧＰａを得た。１０枚重ねのガーレ式透気度が０．４２秒であった。得られた不織布を基材として使用し、厚さ２２３μｍにしたこと以外は実施例１と同様にして両面粘着テープを得た。
[Comparative Example 4]
As a nonwoven fabric, a solution containing 50% by mass of Manila hemp, 30% by mass of polyester, 19.5% by mass of regenerated cellulose, and 0.5% by mass of polyamidoamine / epichlorohydrin resin was measured on a slanted short paper machine with a basis weight of 17.3 g / The paper was made to m 2 , density 0.25 g / cm 3 , and thickness 55 μm, the tensile strength at break was 26.5 N / 20 mm in MD, 23.6 N / 20 mm in TD, and the elastic modulus was 1.7 GPa in MD. 0.6 GPa was obtained by TD. The tensile breaking strength was 12.4 N / 20 mm in MD, 11.2 N / 20 mm in TD, and the elastic modulus was 1.2 GPa and TD 1.2 GPa in MD. Ten sheets of Gurley air permeability was 0.42 seconds. A double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the obtained non-woven fabric was used as a substrate and the thickness was 223 μm.
実施例、比較例として作成した粘着テープについて、以下に示す方法で、波ジワ発生の有無、９０°ピール粘着力、引張破断強度、弾性率、熱伝導性、保持力、粘着剤層損失正接ピーク温度、ゲル分率、を評価した。得られた結果を下表に示した。 About the adhesive tape created as an Example and a comparative example, by the method shown below, presence or absence of wrinkle generation, 90 ° peel adhesive strength, tensile rupture strength, elastic modulus, thermal conductivity, holding power, adhesive layer loss tangent peak Temperature and gel fraction were evaluated. The results obtained are shown in the table below.
［ガーレ式透気度］
上記実施例及び比較例にて使用した中芯基材を、２３℃５０％ＲＨ中にて基材１０枚を重ねてセットし、直径２８．６ｍｍ、重さ５６７ｇの内筒が落下して１００ｍｌの空気が通過する時間を測定した。測定機器として、ＪＩＳ Ｐ８１１７に準拠の東洋精機製作所製のガーレ式透過度を使用した。
[Gurley type air permeability]
The core base material used in the above examples and comparative examples was set by stacking 10 base materials in 23 ° C. and 50% RH, and an inner cylinder with a diameter of 28.6 mm and a weight of 567 g dropped to 100 ml. The time for the air to pass was measured. As a measuring instrument, Gurley type permeability manufactured by Toyo Seiki Seisakusho in accordance with JIS P8117 was used.
［引張弾性率］
上記実施例及び比較例にて得られた基材および粘着テープを、幅２０ｍｍ、長さ１５０ｍｍの試験片を準備する。２３℃５０％ＲＨの環境で、ＪＩＳ Ｋ７１６１に規定の方法にて引っ張り、引張弾性率を測定した。粘着テープの場合、粘着剤層の引張弾性率は無視できるほど小さいため、試料の厚みは基材の厚さとした。（引張速度：１ｍｍ／ｍｉｎ、試験片の形状：ＪＩＳ Ｋ７１２７の試験片タイプ２）。測定機器として、エー・アンド・ディ社製テンシロン万能試験機「ＲＴＡ−１００」を使用し、試験片の標線間距離５０ｍｍ、つかみ間距離１００ｍｍ、つかみ部分長さ５０ｍｍとした。
[Tensile modulus]
A test piece having a width of 20 mm and a length of 150 mm is prepared from the base material and the adhesive tape obtained in the above Examples and Comparative Examples. In an environment of 23 ° C. and 50% RH, the tensile modulus was measured by pulling by the method defined in JIS K7161. In the case of the pressure-sensitive adhesive tape, the tensile elastic modulus of the pressure-sensitive adhesive layer is so small that it can be ignored. Therefore, the thickness of the sample was the thickness of the substrate. (Tensile speed: 1 mm / min, test piece shape: JIS K7127 test piece type 2). A & D Tensilon universal tester "RTA-100" was used as a measuring instrument, and the distance between the marked lines of the test piece was 50 mm, the distance between the grips was 100 mm, and the grip part length was 50 mm.
［引張破断強度］
上記実施例及び比較例にて得られた粘着テープを、幅２０ｍｍ、長さ１５０ｍｍの試験片を準備する。２３℃５０％ＲＨの環境で、ＪＩＳ Ｋ７１６１に規定の方法にて引っ張り、破断時の強度を測定した。（引張速度：３００ｍｍ／ｍｉｎ、試験片の形状：ＪＩＳ Ｋ７１２７の試験片タイプ２）。測定機器として、エー・アンド・ディ社製テンシロン万能試験機「ＲＴＡ−１００」を使用し、試験片の標線間距離５０ｍｍ、つかみ間距離１００ｍｍ、つかみ部分長さ５０ｍｍとした。
[Tensile breaking strength]
A test piece having a width of 20 mm and a length of 150 mm is prepared from the pressure-sensitive adhesive tape obtained in the above Examples and Comparative Examples. In an environment of 23 ° C. and 50% RH, the film was pulled by the method defined in JIS K7161, and the strength at break was measured. (Tensile speed: 300 mm / min, shape of test piece: test piece type 2 of JIS K7127). A & D Tensilon universal tester "RTA-100" was used as a measuring instrument, and the distance between the marked lines of the test piece was 50 mm, the distance between the grips was 100 mm, and the grip part length was 50 mm.
［粘着剤層損失正接ピーク温度］
上記実施例及び比較例にて得られた粘着テープを５ｍｍ厚にまで重ね合わせて試験片とし、レオメトリックス社製粘弾性試験機アレス２ｋＳＴＤに直径７．９ｍｍのパラレルプレートを装着し、試験片を挟み込み周波数１Ｈｚ、温度分散法で測定した。
[Adhesive layer loss tangent peak temperature]
The adhesive tapes obtained in the above Examples and Comparative Examples were superposed to a thickness of 5 mm to obtain a test piece. A parallel plate having a diameter of 7.9 mm was attached to a rheometrics viscoelasticity tester Ares 2 kSTD. Measurement was performed by a temperature dispersion method with a sandwiching frequency of 1 Hz.
［ゲル分率］
上記実施例および比較例にて得られた粘着テープを４０ｍｍ×５０ｍｍに切断し、天秤で重量を測定後、トルエンに浸漬し常温下で２４時間静置した。浸漬後に粘着テープを取り出し、乾燥機で１０５℃で１時間乾燥させ、室温で冷却した後に粘着テープの重量を測定した。トルエン浸漬前のフィラーを差し引いた粘着剤組成物重量に対するトルエン不溶分の粘着剤重量の割合を百分率で求めた。
[Gel fraction]
The adhesive tapes obtained in the above examples and comparative examples were cut into 40 mm × 50 mm, weighed with a balance, immersed in toluene, and allowed to stand at room temperature for 24 hours. After the immersion, the adhesive tape was taken out, dried at 105 ° C. for 1 hour with a dryer, cooled at room temperature, and then the weight of the adhesive tape was measured. The ratio of the weight of the pressure-sensitive adhesive insoluble in the pressure-sensitive adhesive composition after subtracting the filler before immersion in toluene was determined as a percentage.
［熱伝導率］
上記実施例及び比較例にて得られた粘着テープを空気を巻き込まないように５００μｍになるまで貼り重ねせた。最外面は厚さ６μｍのＰＥＴフィルムを貼合した。得られた試料を５ｃｍ×１５ｃｍに切断して測定用試料を作製した。得られた測定用試料を京都電子工業性熱伝導率測定機ＱＴＭ−５００と、薄膜法測定用ソフトＱＴＭ−５Ｗを使用し測定を行った。
[Thermal conductivity]
The pressure-sensitive adhesive tapes obtained in the above examples and comparative examples were laminated to 500 μm so as not to entrain air. The outermost surface was bonded with a PET film having a thickness of 6 μm. The obtained sample was cut into 5 cm × 15 cm to prepare a measurement sample. The obtained measurement sample was measured using a Kyoto Electronics Industrial thermal conductivity measuring device QTM-500 and a thin film method measurement software QTM-5W.
［９０°ピール粘着力］
上記実施例及び比較例にて得られた粘着テープの片面に厚さ５０μｍのアルミ箔を貼合し２０ｍｍ幅に切断した。２３℃５０％ＲＨ雰囲気下でもう一方の粘着面をアルミ板に２ｋｇローラー１往復の加圧条件で貼付し、１時間静置後に９０°方向へ３００ｍｍ／分の引張速度で引き剥がした際の粘着力を測定した。
[90 ° peel adhesive strength]
An aluminum foil having a thickness of 50 μm was bonded to one side of the pressure-sensitive adhesive tape obtained in the above examples and comparative examples, and cut into a width of 20 mm. When the other adhesive surface was affixed to an aluminum plate under a reciprocating pressure of 2 kg roller in an atmosphere of 23 ° C. and 50% RH, and left for 1 hour, it was peeled off at a tensile rate of 300 mm / min in the 90 ° direction. The adhesive strength was measured.
［リワーク性］
上記実施例及び比較例にて得られた粘着テープの５ｍｍ幅×１００ｍｍ長さとした試料を、片面の剥離ライナーを残した状態で２３℃５０％ＲＨ中で厚さ５００μｍのアルミ板へ貼付し、２ｋｇローラー１往復１往復の加圧条件で貼付し、すぐに９０°方向へ３００ｍｍ／分の引張速度で引き剥がした。引き剥がした際に粘着テープが伸びたり、アルミ板上へ粘着剤が残留した場合を×とし、粘着テープが伸びなかったり、アルミ板上へ粘着剤が残留しなかった場合を○とした。
[Reworkability]
A sample of 5 mm width × 100 mm length of the pressure-sensitive adhesive tape obtained in the above Examples and Comparative Examples was attached to an aluminum plate having a thickness of 500 μm in 23 ° C. and 50% RH with a single-sided release liner remaining. A 2 kg roller was applied under one reciprocating and one reciprocating pressure conditions, and immediately peeled off at a pulling speed of 300 mm / min in the 90 ° direction. The case where the adhesive tape was stretched when peeled or the pressure-sensitive adhesive remained on the aluminum plate was rated as x, and the case where the pressure-sensitive adhesive tape was not stretched or the pressure-sensitive adhesive did not remain on the aluminum plate was marked as ◯.
［波ジワ発生の有無］
上記実施例及び比較例にて得られた粘着テープを、直径１８０ｍｍの円筒に沿わせて湾曲させた１．２ｍｍ厚さ×７ｍｍ幅×１５０ｍｍ長さのアルミ板の凸面側へ貼付した。２３℃５０％ＲＨ中に１日放置後、１秒間でアルミ板を平坦な直線状へ曲げ戻し、波ジワ発生の有無を目視確認した。
◎：波ジワ発生無し
○：若干の波ジワが発生するが突起にならない
×：波ジワ発生し、波ジワ部が突起となる
[Presence of wrinkles]
The adhesive tapes obtained in the above examples and comparative examples were affixed to the convex side of a 1.2 mm thick × 7 mm wide × 150 mm long aluminum plate curved along a cylinder having a diameter of 180 mm. After leaving in 23 ° C. and 50% RH for 1 day, the aluminum plate was bent back into a flat straight line in 1 second, and the presence or absence of wrinkles was visually confirmed.
◎: No wrinkle generation ○: Some wrinkles are generated but no protrusions ×: Wave wrinkles are generated and the wrinkle part is a protrusion
上記表から明らかなように、実施例１〜１２の本願発明の熱伝導性粘着テープは、好適な接着性とリワーク性とを有するものであった。また、実施例１〜１２の熱伝導性粘着テープは、湾曲した被着体へ貼付した後、直線状に戻されても波ジワの発生がなく、あるいは若干の波ジワが発生しても波ジワ部が突起とならないことから、被着体との密着が良好であり、好適な熱伝導性を実現できるものであった。一方、比較例１の熱伝導性粘着テープは、リワーク性に乏しいものであった。また、比較例２〜４の熱伝導性粘着テープは、被着体が平らな直線状に曲げ戻された際に突起状に波ジワが発生し、被着体と接着した際に熱伝導のロスが生じるものであった。 As is clear from the above table, the heat conductive pressure-sensitive adhesive tapes of the present invention of Examples 1 to 12 had suitable adhesiveness and reworkability. In addition, the heat conductive adhesive tapes of Examples 1 to 12 were not wrinkled even when they were returned to a linear shape after being applied to a curved adherend, or even if some wrinkles were generated. Since the wrinkle portion does not become a protrusion, the adhesion with the adherend is good, and a suitable thermal conductivity can be realized. On the other hand, the heat conductive adhesive tape of Comparative Example 1 was poor in reworkability. In addition, the heat conductive adhesive tapes of Comparative Examples 2 to 4 generate wrinkles in a protruding shape when the adherend is bent back into a flat linear shape, and the heat conductive adhesive tape adheres to the adherend. Loss occurred.
Claims (6)
前記基材が、１０枚積層してＪＩＳＰ８１１７に準拠して測定されるガーレ式透気度が０．３５ｓｅｃ／１００ｍｌ以下であり、引張弾性率が３ＧＰａ以下であり、厚さが１０〜５０μｍであることを特徴とする熱伝導性粘着テープ。 A heat conductive adhesive tape having a heat conductive adhesive layer on at least one surface of a substrate,
The Gurley type air permeability measured in accordance with JISP8117 after laminating 10 base materials is 0.35 sec / 100 ml or less, the tensile elastic modulus is 3 GPa or less, and the thickness is 10 to 50 μm. The heat conductive adhesive tape characterized by this.
前記粘着剤組成物中の無機フィラーの含有量が、アクリル共重合体１００質量部に対して２００質量部以上である請求項１又は２に記載の熱伝導性粘着テープ。 The thermally conductive pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition containing an acrylic copolymer containing (meth) acrylate as a main monomer component and an inorganic filler,
The heat conductive adhesive tape according to claim 1 or 2, wherein the content of the inorganic filler in the adhesive composition is 200 parts by mass or more with respect to 100 parts by mass of the acrylic copolymer.
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| WO2017002634A1 (en) * | 2015-06-29 | 2017-01-05 | Dic株式会社 | Pressure-sensitive adhesive tape, harness-bundling sheet, and article |
| JP2018203829A (en) * | 2017-05-31 | 2018-12-27 | 王子ホールディングス株式会社 | Adhesive sheet |
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