JP7259879B2 - Thermally conductive sheet and method for producing thermally conductive sheet - Google Patents
Thermally conductive sheet and method for producing thermally conductive sheet Download PDFInfo
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Description
本発明は、熱伝導シート及び熱伝導シートの製造方法に関する。 TECHNICAL FIELD The present invention relates to a thermally conductive sheet and a method for producing the thermally conductive sheet.
近年、多層配線板、半導体パッケージ等の電子部品装置における配線の密度又は電子部品の搭載密度の増大、半導体素子の高集積化などを背景に、単位面積あたりの発熱量が大きくなる傾向にある。このため、電子部品装置で発生した熱を効率よく放散することが望まれるようになっている。 In recent years, the amount of heat generated per unit area tends to increase against the background of increasing wiring density or mounting density of electronic components in electronic component devices such as multilayer wiring boards and semiconductor packages, as well as higher integration of semiconductor elements. Therefore, it is desired to efficiently dissipate the heat generated in the electronic component device.
電子部品装置で発生した熱を効率よく放散する方法としては、電子部品装置(発熱体)とアルミニウム、銅等の金属部材(放熱体)とを、熱伝導部材を間に挟んで貼り付ける方法が一般的に採用されている。熱伝導部材としては、熱伝導グリース、熱伝導シート等が用いられている。放熱体を発熱体に貼り付ける際の作業性の観点からは熱伝導シートの方が熱伝導グリースよりも優れているが、従来の熱伝導シートの熱伝導性には改善の余地があった。 As a method for efficiently dissipating the heat generated by an electronic component device, there is a method of attaching an electronic component device (heat generating element) and a metal member (heat radiator) such as aluminum or copper with a heat conducting member sandwiched between them. commonly adopted. Thermally conductive grease, thermally conductive sheets, and the like are used as the thermally conductive member. From the viewpoint of workability when attaching a radiator to a heating element, the thermally conductive sheet is superior to the thermally conductive grease, but there is room for improvement in the thermal conductivity of conventional thermally conductive sheets.
熱伝導シートの熱伝導性を向上させる目的で、バインダ樹脂等のマトリックス材料中に、熱伝導性の大きい黒鉛粉末、窒化ホウ素等の粒子を配合した熱伝導性複合材料組成物及びその成形加工品が種々提案されている。 A thermally conductive composite material composition in which particles such as graphite powder and boron nitride having high thermal conductivity are blended in a matrix material such as a binder resin for the purpose of improving the thermal conductivity of the thermally conductive sheet, and molded products thereof. have been proposed.
例えば、特許文献1には、熱伝導性の材料をマトリックス材料中で、シート面に対して垂直方向に配向させ、膜厚方向への熱伝導性を向上させた熱伝導シートが記載されている。特許文献2には、ゲル状物質に分散された炭素繊維が、シート面に対して垂直に配向した構造を有する熱伝導シートが記載されている。特許文献3には、鱗片状、楕球状又は棒状である熱伝導性粒子がシートの膜厚方向に対して斜めに配向した構造を有する熱伝導シートが記載されている。 For example, Patent Document 1 describes a heat conductive sheet in which a heat conductive material is oriented in a matrix material in a direction perpendicular to the sheet surface to improve heat conductivity in the film thickness direction. . Patent Document 2 describes a heat conductive sheet having a structure in which carbon fibers dispersed in a gel substance are oriented perpendicularly to the sheet surface. Patent Literature 3 describes a thermally conductive sheet having a structure in which scaly, elliptical, or rod-shaped thermally conductive particles are oriented obliquely with respect to the film thickness direction of the sheet.
特許文献1及び特許文献2に記載されている熱伝導シートは、熱伝導性粒子が表面に露出するため、シート表面の粘着性(タック性)が低く、発熱体と放熱体との間に挟んで実装する工程において、仮固定しにくく、作業性に改善の余地があった。
特許文献3に記載されている熱伝導シートは、熱伝導性粒子を熱伝導シートの膜厚方向に対して斜めに配向させることで、表面に粘着性(タック性)を発現させ、熱伝導シートを仮固定する際の作業性を向上させている。しかしながら、特許文献3に記載の熱伝導シートも作業性に更なる改善の余地がある。
In the thermally conductive sheets described in Patent Documents 1 and 2, since the thermally conductive particles are exposed on the surface, the adhesiveness (tackiness) of the sheet surface is low. In the mounting process, it was difficult to temporarily fix, and there was room for improvement in workability.
In the heat conductive sheet described in Patent Document 3, by orienting the heat conductive particles obliquely with respect to the film thickness direction of the heat conductive sheet, adhesiveness (tackiness) is expressed on the surface, and the heat conductive sheet It improves the workability when temporarily fixing the However, the heat conductive sheet described in Patent Document 3 also has room for further improvement in workability.
さらに、熱伝導シートは仮固定の作業性に加え、良好な熱伝導性も有している必要がある。従って、表面の粘着性を上げつつも、表面での熱抵抗の上昇が抑制された熱伝導シートが求められている。 Furthermore, the thermally conductive sheet must have good thermal conductivity in addition to workability for temporary fixing. Accordingly, there is a demand for a heat conductive sheet that suppresses an increase in thermal resistance on the surface while increasing the adhesiveness of the surface.
本発明は上記事情に鑑み、仮固定の作業性に優れ、かつ熱抵抗が抑制された熱伝導シート及びその製造方法を提供する。 SUMMARY OF THE INVENTION In view of the above circumstances, the present invention provides a heat conductive sheet excellent in workability of temporary fixing and having suppressed heat resistance, and a method for manufacturing the same.
上記課題を解決するための手段には、以下の実施態様が含まれる。
<1>熱伝導性粒子及び有機高分子化合物を含む基材シートと、前記基材シートの少なくとも一方の表面上に局在する粘着成分と、を有する熱伝導シート。
<2>前記熱伝導性粒子が鱗片状粒子、楕球状粒子及び棒状粒子からなる群より選択される少なくとも1つである、<1>に記載の熱伝導シート。
<3>前記熱伝導性粒子が黒鉛粒子を含む、<1>又は<2>に記載の熱伝導シート。
<4>前記粘着成分が存在する粘着成分領域の平均厚みが1.5μm以下である、<1>~<3>のいずれか1項に記載の熱伝導シート。
<5>熱伝導性粒子及び有機高分子化合物を含む基材シートの少なくとも一方の表面上に、粘着成分が局在するように前記粘着成分を付与する工程を含む、<1>~<4>のいずれか1項に記載の熱伝導シートの製造方法。
Means for solving the above problems include the following embodiments.
<1> A thermally conductive sheet comprising a substrate sheet containing thermally conductive particles and an organic polymer compound, and an adhesive component localized on at least one surface of the substrate sheet.
<2> The thermally conductive sheet according to <1>, wherein the thermally conductive particles are at least one selected from the group consisting of scaly particles, ellipsoidal particles and rod-like particles.
<3> The thermally conductive sheet according to <1> or <2>, wherein the thermally conductive particles contain graphite particles.
<4> The heat conductive sheet according to any one of <1> to <3>, wherein the adhesive component region in which the adhesive component is present has an average thickness of 1.5 μm or less.
<5><1> to <4>, including a step of applying the adhesive component so that the adhesive component is localized on at least one surface of the base sheet containing the thermally conductive particles and the organic polymer compound. A method for producing a thermally conductive sheet according to any one of the above.
本発明によれば、仮固定の作業性に優れ、かつ熱抵抗が抑制された熱伝導シート及びその製造方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the heat conductive sheet which was excellent in workability|operativity of temporary fixation, and was suppressed in thermal resistance, and its manufacturing method are provided.
以下、本発明を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素(要素ステップ等も含む)は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。 DETAILED DESCRIPTION OF THE INVENTION Embodiments for carrying out the present invention will be described in detail below. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present invention.
本明細書において「工程」との語には、他の工程から独立した工程に加え、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、当該工程も含まれる。
本明細書において「~」を用いて示された数値範囲には、「~」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において組成物中の各成分の含有率は、組成物中に各成分に該当する物質が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率を意味する。
本明細書において組成物中の各成分の粒子径は、組成物中に各成分に該当する粒子が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
本明細書において「層」との語には、当該層が存在する領域を観察したときに、当該領域の全体に形成されている場合に加え、当該領域の一部にのみ形成されている場合も含まれる。
本明細書において「積層」との語は、二以上の層(シート)を積み重ねることを意味し、二以上の層(シート)は結合されていてもよく、着脱可能であってもよい。
As used herein, the term "process" includes a process that is independent of other processes, and even if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes. be
In this specification, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described stepwise in this specification, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps. good. Moreover, in the numerical ranges described in this specification, the upper and lower limits of the numerical ranges may be replaced with the values shown in the examples.
In the present specification, the content of each component in the composition is the total of the multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means the content of
As used herein, the particle size of each component in the composition refers to a mixture of the plurality of types of particles present in the composition when there are multiple types of particles corresponding to each component in the composition, unless otherwise specified. means a value for
In this specification, the term "layer" refers to the case where the layer is formed in the entire region when the region where the layer exists is observed, and the case where the layer is formed only in a part of the region. is also included.
As used herein, the term "laminate" means stacking two or more layers (sheets), and the two or more layers (sheets) may be bonded or detachable.
<熱伝導シート>
本実施形態の熱伝導シートは、熱伝導性粒子及び有機高分子化合物を含む基材シートと、前記基材シートの少なくとも一方の表面上に局在する粘着成分と、を有する。
<Thermal conductive sheet>
The heat conductive sheet of this embodiment has a base sheet containing heat conductive particles and an organic polymer compound, and an adhesive component localized on at least one surface of the base sheet.
上記熱伝導シートは、熱伝導性粒子及び有機高分子化合物を含む基材シートの少なくとも一方の表面上に粘着成分が存在することで、表面の粘着性(タック性)に優れていると考えられる。さらに、粘着成分が局在することで、熱抵抗が低く抑えられていると考えられる。 The heat conductive sheet is considered to have excellent surface adhesiveness (tackiness) due to the presence of an adhesive component on at least one surface of the base sheet containing the heat conductive particles and the organic polymer compound. . Furthermore, it is considered that the heat resistance is kept low due to the localization of the adhesive component.
本明細書において「粘着成分が局在する」とは、基材シートの表面に対向する方向から基材シート表面を観察したときに、基材シートの表面上に粘着成分が存在しかつ粘着成分が存在しない領域で囲まれた領域(以下、粘着成分領域とも称する)が複数存在し、かつ当該複数の粘着成分領域が基材シートの表面上に間隔を空けて配置されている状態を意味する。 As used herein, the term "the adhesive component is localized" means that the adhesive component is present on the surface of the base sheet and the adhesive component is A state in which there are multiple areas surrounded by areas where there is no adhesive component (hereinafter also referred to as adhesive component areas), and the multiple adhesive component areas are arranged on the surface of the base sheet at intervals. .
図1に、基材シート1の表面に粘着成分10が局在している様子を模式的に示す。図1に示すように、粘着成分10が存在しかつ粘着成分10が存在しない領域で囲まれた粘着成分領域が、基材シート1の表面上に間隔を空けて複数配置されている。
FIG. 1 schematically shows how the
個々の粘着成分領域の形状は特に制限されない。例えば、基材シートの表面に対向する方向から粘着成分領域を観察したときの形状がドット状、線状、不定形状等であってよい。また、個々の粘着成分領域の大きさ(基材シートとの接触部分の大きさ)は特に制限されない。 The shape of each adhesive component region is not particularly limited. For example, the shape of the adhesive component region when observed from the direction facing the surface of the base sheet may be dot-like, linear, irregular, or the like. Also, the size of each adhesive component region (the size of the contact portion with the base sheet) is not particularly limited.
熱抵抗を低く抑える観点からは、粘着成分領域の平均厚みは1.5μm以下であることが好ましく、0.2μm~1.5μmであることがより好ましく、0.5μm~1.0μmであることが更に好ましく、0.6μm~0.8μmであることが特に好ましい。 From the viewpoint of keeping heat resistance low, the average thickness of the adhesive component region is preferably 1.5 μm or less, more preferably 0.2 μm to 1.5 μm, and more preferably 0.5 μm to 1.0 μm. is more preferable, and 0.6 μm to 0.8 μm is particularly preferable.
粘着成分領域の平均厚みが0.2μm以上であると、表面の粘着性(タック性)が充分に得られる傾向にある。粘着成分領域の平均厚みが1.5μm以下であると、熱抵抗が充分に低く抑えられる傾向にある。 When the average thickness of the adhesive component region is 0.2 μm or more, the adhesiveness (tackiness) of the surface tends to be sufficiently obtained. When the average thickness of the adhesive component region is 1.5 μm or less, the heat resistance tends to be kept sufficiently low.
粘着成分領域の平均厚みは、任意に選択した10個の粘着成分領域の個々の厚みの数平均値とする。粘着成分領域の個々の厚みは、当該粘着成分領域の高さ(基材シートに付与された粘着成分の外周面(外気と接する面)に存在する点から基材シートの表面に引いた垂線の長さの最大値)とする。例えば、基材シートの面方向に対して垂直に切断して得た断面を観察することで測定することができる。 The average thickness of the adhesive component regions is the numerical average value of the individual thicknesses of ten arbitrarily selected adhesive component regions. The thickness of each adhesive component region is the height of the adhesive component region (the vertical line drawn from the point on the outer peripheral surface (the surface in contact with the outside air) of the adhesive component applied to the base sheet to the surface of the base sheet. maximum length). For example, it can be measured by observing a cross section obtained by cutting perpendicularly to the surface direction of the base sheet.
粘着成分領域の厚みは、上述のように実際に粘着成分を付与した基材シートに基づいて測定しても、粘着成分を基材シートに付与する条件と同様の条件で別の基材(シリコン基板等)に粘着成分を付与し、これに基づいて測定してもよい。 Even if the thickness of the adhesive component region is measured based on the base sheet to which the adhesive component is actually applied as described above, it may be measured on another base material (silicon A substrate, etc.) may be applied with an adhesive component and measured based on this.
粘着成分の種類は特に制限されず、熱伝導シートに所望の粘着性を付与できるものから選択できる。
具体的には、アクリル酸ブチル、アクリル酸2-エチルヘキシル等を主要な原料成分とする、ポリ(メタ)アクリル酸エステル系高分子化合物(所謂アクリルゴム)、ポリジメチルシロキサン構造を主構造に有する高分子化合物(所謂シリコーン樹脂)、ポリイソプレン構造を主構造に有する高分子化合物(所謂イソプレンゴム及び天然ゴム)、クロロプレンを主要な原料成分とした高分子化合物(所謂クロロプレンゴム)、ポリブタジエン構造を主構造に有する高分子化合物(所謂ブタジエンゴム)などが挙げられる。これらの高分子化合物は、一般に「ゴム」と総称される柔軟性を有する有機高分子化合物である。粘着成分は1種を単独で用いても、2種以上を併用してもよい。
The type of adhesive component is not particularly limited, and can be selected from those capable of imparting desired adhesiveness to the heat conductive sheet.
Specifically, butyl acrylate, 2-ethylhexyl acrylate, etc. are the main raw material components, poly(meth)acrylic acid ester-based polymer compounds (so-called acrylic rubber), polydimethylsiloxane structure as the main structure Molecular compounds (so-called silicone resins), polymer compounds with polyisoprene structure as the main structure (so-called isoprene rubber and natural rubber), polymer compounds with chloroprene as the main ingredient (so-called chloroprene rubber), polybutadiene structure as the main structure and polymer compounds (so-called butadiene rubber). These polymer compounds are flexible organic polymer compounds generally referred to as "rubber". An adhesive component may be used individually by 1 type, or may use 2 or more types together.
(熱伝導性粒子)
熱伝導性粒子は、熱伝導シートとして所望の性能が達成できる程度の熱伝導性を有するものであれば特に制限されない。具体的には、窒化ホウ素粒子、黒鉛粒子、炭素粒子等が挙げられ、中でも黒鉛粒子が好ましい。熱伝導性粒子は1種を単独で用いても、2種以上を併用してもよい。
(Thermal conductive particles)
The thermally conductive particles are not particularly limited as long as they have thermal conductivity to the extent that the desired performance of the thermally conductive sheet can be achieved. Specific examples include boron nitride particles, graphite particles, carbon particles, etc. Among them, graphite particles are preferred. The thermally conductive particles may be used singly or in combination of two or more.
熱伝導性粒子は、鱗片状粒子、楕球状粒子及び棒状粒子からなる群より選択される少なくとも1つであることが好ましい。 The thermally conductive particles are preferably at least one selected from the group consisting of scaly particles, ellipsoidal particles and rod-like particles.
熱伝導シートの熱伝導率は、基材シートの一方の面から他方の面まで貫通する熱伝導性粒子が多く含まれているほど高くなる傾向にある。従って、熱伝導性粒子の長軸(粒子の長さがもっとも長くなる部分)の長さが、基材シートの厚みよりも長い形状及び大きさの熱伝導性粒子を原料として選択することが好ましい。 The thermal conductivity of the thermally conductive sheet tends to increase as the base sheet contains more thermally conductive particles penetrating from one surface to the other surface of the base sheet. Therefore, it is preferable to select as a raw material thermally conductive particles having a shape and size in which the length of the long axis (the longest part of the particle) is longer than the thickness of the base sheet. .
原料としての熱伝導性粒子の大きさは特に制限されず、基材シートの厚み等によって選択できる。例えば、長軸の長さの平均値が250μm以上である熱伝導性粒子、長軸の長さの平均値が500μm~1000μmである熱伝導性粒子、及び長軸の長さの平均値が1500μm~2000μmである熱伝導性粒子からなる群より選択される少なくとも1つを選択し、原料として用いることができる。 The size of the thermally conductive particles used as the raw material is not particularly limited, and can be selected according to the thickness of the base sheet and the like. For example, thermally conductive particles having an average major axis length of 250 μm or more, thermally conductive particles having an average major axis length of 500 μm to 1000 μm, and an average major axis length of 1500 μm At least one selected from the group consisting of thermally conductive particles having a diameter of up to 2000 μm can be selected and used as a raw material.
基材シート中の熱伝導性粒子の含有率は、特に制限されない。例えば、基材シートの全体積の10体積%~50体積%であることが好ましく、30体積%~45体積%であることがより好ましい。 The content of thermally conductive particles in the base sheet is not particularly limited. For example, it is preferably 10% to 50% by volume, more preferably 30% to 45% by volume, of the total volume of the base sheet.
(有機高分子化合物)
有機高分子化合物の種類は、特に制限されない。熱伝導性シートに良好な柔軟性と、発熱体及び放熱体に対する良好な密着性と、を付与する観点からは、Tg(ガラス転移温度)が50℃以下である有機高分子化合物が好ましく、Tgが-70℃~20℃である有機高分子化合物がより好ましく、Tgが-60℃~0℃である有機高分子化合物が更に好ましい。
(Organic polymer compound)
The type of organic polymer compound is not particularly limited. From the viewpoint of imparting good flexibility to the thermally conductive sheet and good adhesion to the heating element and the heat dissipating element, an organic polymer compound having a Tg (glass transition temperature) of 50° C. or less is preferable. is more preferably from -70°C to 20°C, and more preferably from -60°C to 0°C.
有機高分子化合物として具体的には、アクリル酸ブチル、アクリル酸2-エチルヘキシル等を主要な原料成分とした、ポリ(メタ)アクリル酸エステル系高分子化合物(所謂アクリルゴム)、ポリジメチルシロキサン構造を主構造に有する高分子化合物(所謂シリコーン樹脂)、ポリイソプレン構造を主構造に有する高分子化合物(所謂イソプレンゴム、及び天然ゴム)、クロロプレンを主要な原料成分とした高分子化合物(所謂クロロプレンゴム)、ポリブタジエン構造を主構造に有する高分子化合物(所謂ブタジエンゴム)などが挙げられる。これらの高分子化合物は、一般に「ゴム」と総称される柔軟性を有する有機高分子化合物である。有機高分子化合物は1種を単独で用いても、2種以上を併用してもよい。 Specific examples of organic polymer compounds include poly(meth)acrylic acid ester-based polymer compounds (so-called acrylic rubber) and polydimethylsiloxane structures containing butyl acrylate, 2-ethylhexyl acrylate, etc. as main ingredients. Polymer compounds having a main structure (so-called silicone resin), polymer compounds having a polyisoprene structure as a main structure (so-called isoprene rubber and natural rubber), polymer compounds containing chloroprene as a main ingredient (so-called chloroprene rubber) , polymer compounds having a polybutadiene structure as the main structure (so-called butadiene rubber), and the like. These polymer compounds are flexible organic polymer compounds generally referred to as "rubber". An organic polymer compound may be used individually by 1 type, or may use 2 or more types together.
熱伝導シートの柔軟性、化学的安定性、加工性、粘着性の制御しやすさ、原料価格等の観点からは、上記の有機高分子化合物の中でもポリ(メタ)アクリル酸エステル系高分子化合物が好ましく、アクリル酸ブチル及びアクリル酸2-エチルヘキシルのうちいずれか一方又は両方を共重合成分として含み、かつこれらの共重合成分中の比率が、共重合成分全体の50質量%以上であるポリ(メタ)アクリル酸エステル系高分子化合物がより好ましい。 Among the above organic polymer compounds, poly(meth)acrylic acid ester-based polymer compounds are preferred from the viewpoint of heat conductive sheet flexibility, chemical stability, workability, ease of adhesiveness control, raw material costs, etc. Poly ( A meth)acrylic acid ester-based polymer compound is more preferable.
熱伝導シートに長期間の密着保持性と強度を付与する観点からは、柔軟性を損なわない範囲で、有機高分子化合物に架橋構造を含ませてもよい。有機高分子化合物に架橋構造を含ませる方法は、特に制限されない。例えば、水酸基を有するポリマーに、複数のイソシアネート基を持つ化合物を反応させる方法が挙げられる。 From the viewpoint of imparting long-term adhesion retention and strength to the heat conductive sheet, the organic polymer compound may contain a crosslinked structure within a range that does not impair flexibility. A method for incorporating a crosslinked structure into the organic polymer compound is not particularly limited. For example, there is a method of reacting a compound having a plurality of isocyanate groups with a polymer having hydroxyl groups.
有機高分子化合物の含有率は、特に制限されない。例えば、基材シートの全体積の10体積%~70体積%であることが好ましく、20体積%~50体積%であることがより好ましい。 The content of the organic polymer compound is not particularly limited. For example, it is preferably 10% to 70% by volume, more preferably 20% to 50% by volume, of the total volume of the base sheet.
(難燃剤)
基材シートは、難燃剤を含有してもよい。難燃剤の種類は特に限定されず、赤リン系難燃剤、リン酸エステル系難燃剤等が挙げられる。難燃剤は1種を単独で用いても、2種以上を併用してもよい。
(Flame retardants)
The base sheet may contain a flame retardant. The type of flame retardant is not particularly limited, and examples thereof include red phosphorus flame retardants, phosphate ester flame retardants, and the like. A flame retardant may be used individually by 1 type, or may use 2 or more types together.
赤リン系難燃剤としては、純粋な赤リン粉末の他に、安全性と安定性を高める目的で種々のコーティングを施したもの、マスターバッチになっているもの等が挙げられる。具体的には、燐化学工業株式会社製の商品名:ノーバレッド、ノーバエクセル、ノーバクエル、ノーバペレット等が挙げられる。 Examples of red phosphorus flame retardants include, in addition to pure red phosphorus powder, those coated with various coatings for the purpose of enhancing safety and stability, and masterbatches. Specifically, product names of Rin Kagaku Kogyo Co., Ltd.: Novaled, Nova Excel, Novaquel, Nova Pellet, etc. may be mentioned.
リン酸エステル系難燃剤としては、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート等の脂肪族リン酸エステル;トリフェニルホスフェート、トリクレジルホスフェート、クレジルジフェニルホスフェート、トリキシレニルホスフェート、クレジル-2,6-キシレニルホスフェート、トリス(t-ブチル化フェニル)ホスフェート、トリス(イソプロピル化フェニル)ホスフェート、リン酸トリアリールイソプロピル化物等の芳香族リン酸エステル;レゾルシノールビスジフェニルホスフェート、ビスフェノールAビス(ジフェニルホスフェート)、レゾルシノールビスジキシレニルホスフェート等の芳香族縮合リン酸エステル;などが挙げられる。 Phosphate flame retardants include aliphatic phosphates such as trimethyl phosphate, triethyl phosphate and tributyl phosphate; aromatic phosphates such as xylenyl phosphate, tris(t-butylated phenyl) phosphate, tris(isopropylated phenyl) phosphate, triaryl isopropyl phosphate; resorcinol bisdiphenyl phosphate, bisphenol A bis(diphenyl phosphate), aromatic condensed phosphates such as resorcinol bisdixylenyl phosphate;
柔軟性及びタック性と、難燃性との両立しやすさの観点からは、難燃剤はリン酸エステル系難燃剤であることが好ましく、凝固点が15℃以下であり、沸点が120℃以上である液状物としてのリン酸エステル系化合物であることがより好ましい。
凝固点が15℃以下であり、沸点が120℃以上である液状物としてのリン酸エステル系難燃剤としては、トリメチルホスフェート、トリエチルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、クレジル-2,6-キシレニルホスフェート、レゾルシノールビスジフェニルホスフェート、ビスフェノールAビス(ジフェニルホスフェート)等が挙げられる。
From the viewpoint of compatibility between flexibility and tackiness and flame retardancy, the flame retardant is preferably a phosphate ester flame retardant, and has a freezing point of 15° C. or lower and a boiling point of 120° C. or higher. It is more preferable to use a phosphoric acid ester compound as a liquid substance.
Phosphate ester-based flame retardants as liquid substances having a freezing point of 15° C. or lower and a boiling point of 120° C. or higher include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl -2,6-xylenyl phosphate, resorcinol bisdiphenyl phosphate, bisphenol A bis(diphenyl phosphate) and the like.
基材シートが難燃剤を含む場合、その含有率は特に制限されない。例えば、基材シートの全体積の5体積%~50体積%であることが好ましく、10体積%~40体積%であることがより好ましい。難燃剤の含有率が5体積%以上であると充分な難燃性が発現される傾向にあり、40体積%以下であると充分なシート強度が得られる傾向にある。 When the base sheet contains a flame retardant, its content is not particularly limited. For example, it is preferably 5% to 50% by volume, more preferably 10% to 40% by volume, of the total volume of the base sheet. When the content of the flame retardant is 5% by volume or more, sufficient flame retardancy tends to be exhibited, and when it is 40% by volume or less, sufficient sheet strength tends to be obtained.
(他の成分)
基材シートは、必要に応じてウレタンアクリレート等の靭性改良剤;酸化カルシウム、酸化マグネシウム等の吸湿剤;シランカップリング剤、チタンカップリング剤、酸無水物等の接着力向上剤;ノニオン系界面活性剤、フッ素系界面活性剤等の濡れ向上剤;シリコーン油等の消泡剤;無機イオン交換体等のイオントラップ剤;などを含んでもよい。
(other ingredients)
The base sheet may contain a toughness improver such as urethane acrylate as required; a moisture absorber such as calcium oxide and magnesium oxide; an adhesive force improver such as a silane coupling agent, titanium coupling agent and acid anhydride; Wetting agents such as activators and fluorosurfactants; antifoaming agents such as silicone oils; ion trapping agents such as inorganic ion exchangers;
<熱伝導シートの製造方法>
本実施形態の熱伝導シートの製造方法は、熱伝導性粒子と、有機高分子化合物と、を含む基材シートの少なくとも一方の表面上に、粘着成分が局在するように前記粘着成分を付与する工程(粘着成分付与工程)を含む。
<Method for manufacturing heat conductive sheet>
In the method for producing a thermally conductive sheet of the present embodiment, the adhesive component is applied to at least one surface of a base sheet containing thermally conductive particles and an organic polymer compound so that the adhesive component is localized. and a step of applying the adhesive component (adhesive component applying step).
基材シートの少なくとも片面上に粘着成分を付与する方法は特に制限されず、スプレー法、印刷法、インクジェット法等の公知の方法から選択できる。簡便かつ効率的に所望の粘着成分領域を形成する観点からは、スプレー法が好ましい。 The method of applying the adhesive component to at least one side of the base sheet is not particularly limited, and can be selected from known methods such as spraying, printing, and ink-jetting. A spray method is preferable from the viewpoint of forming a desired adhesive component region simply and efficiently.
基材シートに粘着成分を付与するにあたり、粘着成分を有機溶媒等で希釈してもよい。粘着成分を希釈する場合の倍率は特に制限されず、粘着成分の種類等に応じて選択できる。 In applying the adhesive component to the base sheet, the adhesive component may be diluted with an organic solvent or the like. The ratio for diluting the adhesive component is not particularly limited, and can be selected according to the type of the adhesive component.
熱伝導シートの製造方法はさらに、基材シートを製造する工程を含んでもよい。以下、基材シートの製造工程の一実施態様について説明する。 The method for producing a heat conductive sheet may further include the step of producing a base sheet. An embodiment of the manufacturing process of the base sheet will be described below.
ある実施態様では、基材シートの製造は、熱伝導性粒子と有機高分子化合物、及び必要に応じてその他の成分を混合して混錬物を得る工程(混錬工程)と、得られた混錬物をシート状に成形して1次シートを作製する工程(1次シート作製工程)と、1次シートを複数枚重ねて積層体を得る工程(積層工程)と、積層体をスライスして基材シートを得る工程(スライス工程)とをこの順に行う。必要に応じて、基材シートを圧縮する工程(ロールプレス工程)を行ってもよい。 In one embodiment, the production of the base sheet includes a step of mixing the thermally conductive particles, the organic polymer compound, and optionally other components to obtain a kneaded product (kneading step); A step of forming the kneaded material into a sheet to prepare a primary sheet (primary sheet preparation step), a step of stacking a plurality of primary sheets to obtain a laminate (laminating step), and slicing the laminate. and a step of obtaining a base sheet (slicing step) are performed in this order. If necessary, a step of compressing the base sheet (roll press step) may be performed.
混錬工程では、熱伝導性粒子と有機高分子化合物、及び必要に応じてその他の成分を混合して混錬物を得る。混錬物に含まれる熱伝導性粒子の大きさは、スライス工程で得られる基材シートの厚みを考慮して選択することが好ましい。混錬の方法は特に制限されず、一般的な装置を用いて行うことができる。例えば、2本ロール又はニーダーを用いて行うことができる。 In the kneading step, the thermally conductive particles, the organic polymer compound, and optionally other components are mixed to obtain a kneaded material. The size of the thermally conductive particles contained in the kneaded material is preferably selected in consideration of the thickness of the base sheet obtained in the slicing step. The kneading method is not particularly limited, and can be performed using a general apparatus. For example, it can be carried out using two rolls or a kneader.
1次シート作製工程では、混練物をシート状に成形する。成形は、例えば、混練物を押しつぶすことで行うことができる。混練物を押しつぶす方法は特に制限されず、一般的な装置を用いて行うことができる。例えば、平板プレス又はメタルロールを用いて行うことができる。成形の際の温度条件は、有機高分子化合物の脆性化を抑制する観点からは150℃以下とすることが好ましく、有機高分子化合物の軟化を促進する観点からは25℃以上とすることが好ましい。1次シートの厚みは特に制限されず、薄いほど好ましい。例えば、0.2mm~1.0mmの範囲内とすることが好ましい。 In the primary sheet production step, the kneaded material is formed into a sheet. Molding can be performed, for example, by crushing the kneaded material. The method of crushing the kneaded material is not particularly limited, and it can be performed using a general apparatus. For example, it can be carried out using a flat plate press or metal rolls. The temperature conditions during molding are preferably 150° C. or lower from the viewpoint of suppressing embrittlement of the organic polymer compound, and preferably 25° C. or higher from the viewpoint of promoting softening of the organic polymer compound. . The thickness of the primary sheet is not particularly limited, and the thinner the better. For example, it is preferably within the range of 0.2 mm to 1.0 mm.
積層工程では、所定の大きさに切断した1次シートを複数枚重ねて積層体を得る。積層する方法は特に制限されない。積層体を得た後は、1次シート同士を密着させるために圧縮してもよい。圧縮する方法は特に制限されず、一般的な装置を用いて行うことができる。例えば、平板プレス又はメタルロールを用いて行うことができる。積層体を圧縮する場合の圧縮量は特に制限されない。例えば、圧縮前の積層体の厚みの3%~20%であることが好ましい。 In the lamination step, a laminate is obtained by laminating a plurality of primary sheets cut into a predetermined size. The lamination method is not particularly limited. After obtaining the laminate, the primary sheets may be compressed to adhere to each other. The compression method is not particularly limited, and can be performed using a common device. For example, it can be carried out using a flat plate press or metal rolls. The amount of compression when compressing the laminate is not particularly limited. For example, it is preferably 3% to 20% of the thickness of the laminate before compression.
スライス工程では、積層体をスライスして基材シートを得る。スライスする方法は特に制限されず、一般的な方法で行うことができる。具体的には、マルチブレード法、レーザー加工法、ウォータージェット法、ナイフ加工法等が挙げられる。基材シートの厚みを一定に保ちやすく、切りくずの発生が少ない点では、ナイフ加工法が好ましい。 In the slicing step, the laminate is sliced to obtain a base sheet. A slicing method is not particularly limited, and a general method can be used. Specific examples include a multi-blade method, a laser processing method, a water jet method, a knife processing method, and the like. The knife processing method is preferable in that the thickness of the base sheet can be easily kept constant and the generation of chips is small.
スライスする際の切断具は特に制限されない。例えば、スリットを有する平滑な盤面と、このスリット部より突出した刃部と、を有するカンナの部位を有するスライス部材であって、基材シートの所望の厚みに応じて、スリット部からの前記刃部の突出長さが調節可能である切断具は、得られる基材シートの表面近傍の熱伝導性粒子の配向を乱し難く、基材シートの厚みが薄くてもスライスを行いやすいために好適である。 A cutting tool for slicing is not particularly limited. For example, a slicing member having a plane portion having a smooth board surface with a slit and a blade portion protruding from the slit portion, and depending on the desired thickness of the base sheet, the blade from the slit portion A cutting tool with an adjustable protruding length is suitable because it is difficult to disturb the orientation of the thermally conductive particles in the vicinity of the surface of the obtained base sheet, and it is easy to slice even if the thickness of the base sheet is thin. is.
積層体のスライスは、積層体の主面の法線の方向に沿って行うことで、基材シートがその厚み方向に沿って垂直に又は斜めに配向した熱伝導性粒子を含むようにすることができる。 The laminate is sliced along the direction normal to the main surface of the laminate so that the base sheet contains thermally conductive particles oriented vertically or obliquely along the thickness direction. can be done.
以下、本実施形態を実施例により具体的に説明するが、本実施形態はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the present embodiment will be specifically described with reference to Examples, but the present embodiment is not limited to these Examples.
<熱伝導シートの作製>
(1)混錬工程
下記の材料を含む組成物を加圧ニーダーを用いて混錬し、混錬物を得た。混錬条件は、組成物の質量が3.5kgであり、温度100℃で40分間とした。
熱伝導性粒子として、鱗片状の黒鉛粒子(長軸の長さが500μm~1000μm)を使用した。黒鉛粒子の含有率は、組成物の全体積の45体積%とした。
有機高分子化合物として、アクリル酸ブチルが、その共重合成分中の76質量%であるポリ(メタ)アクリル酸エステル系高分子化合物を使用した。有機高分子化合物の含有率は、組成物の全体積の30体積%とした。
難燃剤として、リン酸エステル系難燃剤であるビスフェノールAビス(ジフェニルホスフェート)を使用した。難燃剤の含有率は、組成物の全体積の25体積%とした。
<Preparation of heat conductive sheet>
(1) Kneading step A composition containing the following materials was kneaded using a pressure kneader to obtain a kneaded product. The kneading conditions were that the mass of the composition was 3.5 kg, and the temperature was 100° C. for 40 minutes.
As the thermally conductive particles, scale-like graphite particles (long axis length of 500 μm to 1000 μm) were used. The content of graphite particles was 45% by volume of the total volume of the composition.
As the organic polymer compound, a poly(meth)acrylic acid ester polymer compound containing 76% by mass of butyl acrylate in the copolymer component was used. The content of the organic polymer compound was 30% by volume of the total volume of the composition.
As a flame retardant, bisphenol A bis(diphenyl phosphate), which is a phosphate flame retardant, was used. The content of the flame retardant was 25% by volume of the total volume of the composition.
(2)1次シート作製工程
得られた混練物を、油圧プレスにより圧縮し、更に、80℃のメタルロールを数回通して、1.0mm厚の1次シートを作製した。
(2) Primary sheet production process The obtained kneaded material was compressed by a hydraulic press and passed through a metal roll at 80°C several times to produce a primary sheet with a thickness of 1.0 mm.
(3)積層工程
得られた1次シートを、50mm×200mmの大きさに切断したものを複数用意した。これらを、高さが50mmになるまで積層した。更に油圧プレスを用いて、0.1MPa以下の圧力で加圧して圧縮して積層体を得た。
(3) Lamination Step The obtained primary sheet was cut into a size of 50 mm×200 mm, and a plurality of pieces were prepared. These were stacked up to a height of 50 mm. Further, a hydraulic press was used to pressurize and compress at a pressure of 0.1 MPa or less to obtain a laminate.
(4)スライス工程
得られた積層体を、その主面の法線の方向に沿った方向に、カンナと同様の機構を持った装置を用いてスライスした。スライスは、得られる基材シートの厚みが0.25mmになるように刃の突出量を調整し、積層体の温度を10℃、加工速度を54mm/分、刃自体の先端角度を32°とした条件で行った。
(4) Slicing step The laminate thus obtained was sliced along the direction of the normal to its main surface using an apparatus having a mechanism similar to that of a plane. For slicing, the protrusion amount of the blade is adjusted so that the thickness of the base sheet obtained is 0.25 mm, the temperature of the laminate is 10° C., the processing speed is 54 mm/min, and the tip angle of the blade itself is 32°. It was performed under the following conditions.
(5)粘着成分付与工程
スライスして得られた基材シートの片面に、粘着成分としてアクリルゴムの10質量%溶液をスプレー法により付与し、粘着成分領域を形成した。ここで、スプレー法により付与する粘着成分の量を変更することで、実施例1~3の熱伝導シートを作製した。得られた熱伝導シートの粘着成分領域の平均厚み(μm)を測定した結果を表1に示す。比較例の熱伝導シートには、粘着成分を付与しなかった。
(5) Adhesive Component
<粘着性の評価>
熱伝導シートの粘着性の評価は、タック力(g)を測定することにより行った。具体的には、プローブ試験装置を使用し、測定条件は、温度:23℃、プローブ直径:5mm、プローブ接触面積:19.6mm2、プローブ荷重:50g、押付け時間:1秒で行った。
<Adhesive evaluation>
Adhesiveness of the heat conductive sheet was evaluated by measuring the tack force (g). Specifically, a probe test apparatus was used, and the measurement conditions were temperature: 23° C., probe diameter: 5 mm, probe contact area: 19.6 mm 2 , probe load: 50 g, pressing time: 1 second.
<熱抵抗の評価>
熱伝導シートの熱抵抗の評価は、トランジスタを熱源とする方法で測定した値により行った。具体的には、熱伝導シートを1cm×1.5cmの大きさにカットして試験シートを作製し、これを発熱体としてのトランジスタ(2SC2233)と、放熱体としてのアルミニウム放熱ブロックとの間に挟み、0.5MPaの圧力でトランジスタを加圧して電流を通じた。トランジスタの温度:T1(℃)と、放熱ブロックの温度:T2(℃)を測定し、測定値と印加電力:W1(W)から、次式(1)によって熱抵抗:X(℃/W)を算出した。熱抵抗改善率は比較例との比率で、マイナスの数値は熱抵抗が比較例より劣ることを意味する。
X=(T1-T2)/W1 ・・・ 式(1)
<Evaluation of thermal resistance>
The thermal resistance of the thermally conductive sheet was evaluated based on the value measured by a method using a transistor as a heat source. Specifically, a test sheet was prepared by cutting a thermal conductive sheet into a size of 1 cm x 1.5 cm, and this was placed between a transistor (2SC2233) as a heating element and an aluminum heat dissipation block as a radiator. Then, a pressure of 0.5 MPa was applied to the transistor to pass a current. The temperature of the transistor: T1 (°C) and the temperature of the heat dissipation block: T2 (°C) are measured, and from the measured value and the applied power: W1 (W), the thermal resistance: X (°C/W) is obtained by the following formula (1). was calculated. The thermal resistance improvement rate is the ratio to the comparative example, and a negative number means that the thermal resistance is inferior to the comparative example.
X=(T1-T2)/W1... Formula (1)
表1の結果に示されるように、粘着成分領域の平均厚みが0.6μmである実施例1の熱伝導シートは、粘着成分領域を形成していない比較例の熱伝導シートに比べ、タック力が上昇していた。さらに、比較例の熱伝導シートに比べて熱抵抗も改善していた。 As shown in Table 1, the thermally conductive sheet of Example 1, in which the adhesive component region has an average thickness of 0.6 μm, has a higher tack force than the thermally conductive sheet of Comparative Example, which does not form an adhesive component region. was rising. Furthermore, the heat resistance was improved as compared with the heat conductive sheet of the comparative example.
粘着成分領域の平均厚みが1.5μmである実施例2の熱伝導シートは、粘着成分領域を形成していない比較例の熱伝導シートに比べ、タック力が上昇していた。さらに、比較例の熱伝導シートと同程度の熱抵抗であった。 The thermally conductive sheet of Example 2, in which the adhesive component region had an average thickness of 1.5 μm, had a higher tack force than the thermally conductive sheet of Comparative Example, in which no adhesive component region was formed. Furthermore, the heat resistance was about the same as that of the heat conductive sheet of the comparative example.
粘着成分領域の平均厚みが3μmである実施例3の熱伝導シートは、粘着成分領域を形成していない比較例の熱伝導シートに比べ、タック力が上昇していた。なお、実施例3の熱伝導シートは比較例の熱伝導シートに比べて熱抵抗が悪化しているが、実用上は支障のない範囲と判断できる。 The thermally conductive sheet of Example 3, in which the adhesive component region had an average thickness of 3 μm, had a higher tack force than the thermally conductive sheet of Comparative Example, in which no adhesive component region was formed. Although the thermally conductive sheet of Example 3 has a worse thermal resistance than the thermally conductive sheet of Comparative Example, it can be judged that the thermal resistance is within a practically acceptable range.
1…基材シート、10…粘着成分 DESCRIPTION OF SYMBOLS 1... Base material sheet, 10... Adhesive component
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