TW202332372A - Electromagnetic wave absorbing sheet - Google Patents
Electromagnetic wave absorbing sheet Download PDFInfo
- Publication number
- TW202332372A TW202332372A TW111143732A TW111143732A TW202332372A TW 202332372 A TW202332372 A TW 202332372A TW 111143732 A TW111143732 A TW 111143732A TW 111143732 A TW111143732 A TW 111143732A TW 202332372 A TW202332372 A TW 202332372A
- Authority
- TW
- Taiwan
- Prior art keywords
- heat conduction
- electromagnetic wave
- conduction layer
- wave absorbing
- layer
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/025—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/027—Thermal properties
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Laminated Bodies (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
Description
本發明係關於一種電磁波吸收片。The invention relates to an electromagnetic wave absorbing sheet.
近年來，隨著大容量、高速通訊技術之發展，各種電子機器所具備之電子元件（IC）更微細化，時脈頻率亦提高，隨之發熱量增大，高頻雜訊亦變大。因此，需要一種散熱性優異、且降低電磁波雜訊之材料。In recent years, with the development of large-capacity and high-speed communication technology, the electronic components (IC) of various electronic devices have become more miniaturized, and the clock frequency has also increased. With this, the heat generation has increased, and high-frequency noise has also increased. Therefore, there is a need for a material that is excellent in heat dissipation and reduces electromagnetic wave noise.
於專利文獻1中，揭示了關於熱傳導性電磁波屏蔽片之發明，其於在填充有短纖維狀瀝青系碳纖維之導電性聚矽氧橡膠層之至少單面，積層摻合有熱傳導性填充劑之絕緣性聚矽氧橡膠層而成之熱傳導性電磁波屏蔽片之內部或表面，具有經金屬被覆之樹脂纖維之片狀物。記載了該專利文獻1所記載之熱傳導性電磁波屏蔽片兼具熱傳導性（散熱性）與電磁波屏蔽性兩者。Patent Document 1 discloses an invention related to a thermally conductive electromagnetic wave shielding sheet, which is laminated with a thermally conductive filler on at least one side of a conductive silicone rubber layer filled with short fibrous pitch-based carbon fibers. The interior or surface of the thermally conductive electromagnetic wave shielding sheet made of insulating polysiloxane rubber layer has a sheet of resin fiber coated with metal. It is described that the thermally conductive electromagnetic wave shielding sheet described in this patent document 1 has both thermal conductivity (heat dissipation) and electromagnetic wave shielding properties.
然而，具有電磁波屏蔽性之片材可藉由反射雜訊（電磁波）而抑制雜訊之穿透，但於具備高積體化之電子元件之電子機器中，有所反射之雜訊導致誤動作之虞。因此，需要一種電磁波吸收性優異之材料。However, a sheet with electromagnetic wave shielding can suppress the penetration of noise by reflecting noise (electromagnetic waves), but in electronic devices with highly integrated electronic components, reflected noise may cause malfunctions Yu. Therefore, a material excellent in electromagnetic wave absorption is required.
於專利文獻2中，記載了一種關於導電性不織布之發明，其係至少一面具有金屬層之導電性不織布，片電阻為250～600 Ω/□，且密度為2.0×10 4～8.0×10 5g/m 3，且記載了其具有較高之電波吸收特性。 [先前技術文獻] [專利文獻] In Patent Document 2, an invention related to a conductive nonwoven fabric is described, which is a conductive nonwoven fabric with a metal layer on at least one side, with a sheet resistance of 250-600 Ω/□ and a density of 2.0×10 4 to 8.0×10 5 g/m 3 , and it is recorded that it has high radio wave absorption characteristics. [Prior Art Document] [Patent Document]
專利文獻1：日本特開2001-168573號公報 專利文獻2：日本專利第6846573號公報 Patent Document 1: Japanese Patent Laid-Open No. 2001-168573 Patent Document 2: Japanese Patent No. 6846573
[發明所欲解決之課題][Problem to be Solved by the Invention]
專利文獻2所記載之導電性不織布係藉由濺鍍等在由有機纖維構成之不織布之表面形成金屬層而製造者，所形成之金屬層為極薄之層。因此，存在該導電性不織布之電阻值容易由於壓縮而變化之課題。 通常情況下，熱傳導性片藉由壓縮配置於發熱體與散熱體之間，使自發熱體產生之熱傳遞至散熱體而進行散熱，於為了提高電磁波吸收性而於熱傳導性片之一部分使用導電性不織布之情形時，會由於壓縮而造成電阻值變化，其結果導致電磁波吸收性能降低。 就此種觀點而言，本發明之課題在於：提供具有優異之熱傳導性與電磁波吸收性，且即使進行壓縮電磁波吸收性能亦不易降低之電磁波吸收片。 [解決課題之技術手段] The conductive nonwoven fabric described in Patent Document 2 is produced by forming a metal layer on the surface of a nonwoven fabric made of organic fibers by sputtering or the like, and the formed metal layer is an extremely thin layer. Therefore, there is a problem that the resistance value of the conductive nonwoven fabric is likely to change due to compression. Usually, the thermally conductive sheet is compressed and arranged between the heating body and the heat sink, so that the heat generated from the heating body is transferred to the heat sink to dissipate heat. In order to improve the electromagnetic wave absorption, a conductive sheet is used in part of the heat conductive sheet. In the case of non-woven fabrics, the resistance value changes due to compression, resulting in a decrease in electromagnetic wave absorption performance. From this point of view, the object of the present invention is to provide an electromagnetic wave absorbing sheet that has excellent thermal conductivity and electromagnetic wave absorbing properties, and that does not easily decrease in electromagnetic wave absorbing performance even when compressed. [Technical means to solve the problem]
本發明人為了解決上述課題而進行了努力研究。結果發現藉由下述電磁波吸收片可解決上述課題，從而完成本發明，該電磁波吸收片具有：具備第1熱傳導層、及於具有透孔之電磁波吸收構件含浸有熱傳導性材料之第2熱傳導層之積層結構，無負載狀態下之電阻值R1相對於50%壓縮狀態下之電阻值R2的比（R1/R2）為特定範圍。 即，本發明提供以下之[1]～[6]。 The inventors of the present invention have diligently studied to solve the above-mentioned problems. As a result, it was found that the above-mentioned problems can be solved by an electromagnetic wave absorbing sheet having a first heat conduction layer and a second heat conduction layer impregnated with a heat conductive material in an electromagnetic wave absorbing member having through holes. In the multilayer structure, the ratio (R1/R2) of the resistance value R1 under the no-load state to the resistance value R2 under the 50% compression state is within a specific range. That is, the present invention provides the following [1] to [6].
[1]一種電磁波吸收片，其具有：具備第1熱傳導層、及積層於該第1熱傳導層之第2熱傳導層的積層結構；上述第2熱傳導層為於具有透孔之電磁波吸收構件含浸有熱傳導性材料之層；且無負載狀態下之電阻值R1相對於50%壓縮狀態下之電阻值R2的電阻值比（R1/R2）滿足以下之式（1）： 0.65＜R1/R2＜0.99 式（1）。 [2]如上述[1]之電磁波吸收片，其中，自電磁波吸收片之第1熱傳導層側，藉由 3 mm之柱塞以400 g之負載按壓時之第1熱傳導層的壓縮率C1、第1熱傳導層之厚度T1、及第2熱傳導層之厚度T2滿足以下之式（2）： C1×T1/（T1＋T2）＞0.26 式（2）。 [3]如上述[1]或[2]之電磁波吸收片，其中，上述具有透孔之電磁波吸收構件為於不織布之至少一面具有金屬層之導電性不織布。 [4]如上述[3]之電磁波吸收片，其中，上述導電性不織布之片電阻為10～100 Ω/□。 [5]如上述[1]至[4]中任一項之電磁波吸收片，其中，上述第1熱傳導層包含高分子基質與各向異性填充材料，上述各向異性填充材料於厚度方向配向。 [6]如上述[1]至[5]中任一項之電磁波吸收片，其中，上述第2熱傳導層中之熱傳導性材料包含高分子基質與絕緣性填料。 [發明之效果] [1] An electromagnetic wave absorbing sheet having a laminated structure including a first heat conduction layer and a second heat conduction layer laminated on the first heat conduction layer; the second heat conduction layer is impregnated with an electromagnetic wave absorbing member having through holes. A layer of thermally conductive material; and the resistance value ratio (R1/R2) of the resistance value R1 in the no-load state relative to the resistance value R2 in the 50% compressed state satisfies the following formula (1): 0.65<R1/R2<0.99 Formula 1). [2] The electromagnetic wave absorbing sheet according to the above [1], wherein, from the side of the first heat conduction layer of the electromagnetic wave absorbing sheet, by The compressibility C1 of the first heat conduction layer, the thickness T1 of the first heat conduction layer, and the thickness T2 of the second heat conduction layer when a 3 mm plunger is pressed with a load of 400 g satisfy the following formula (2): C1×T1/ (T1+T2)>0.26 Formula (2). [3] The electromagnetic wave absorbing sheet according to the above [1] or [2], wherein the electromagnetic wave absorbing member having through holes is a conductive nonwoven fabric having a metal layer on at least one surface of the nonwoven fabric. [4] The electromagnetic wave absorbing sheet according to the above [3], wherein the sheet resistance of the conductive nonwoven fabric is 10 to 100 Ω/□. [5] The electromagnetic wave absorbing sheet according to any one of [1] to [4] above, wherein the first heat conduction layer includes a polymer matrix and an anisotropic filler, and the anisotropic filler is aligned in a thickness direction. [6] The electromagnetic wave absorbing sheet according to any one of the above [1] to [5], wherein the heat conductive material in the second heat conduction layer includes a polymer matrix and an insulating filler. [Effect of Invention]
根據本發明，可提供一種具有優異之熱傳導性與電磁波吸收性，且即使進行壓縮電磁波吸收性能亦不易降低之電磁波吸收片。According to the present invention, it is possible to provide an electromagnetic wave absorbing sheet which has excellent thermal conductivity and electromagnetic wave absorbing property, and which does not easily decrease in electromagnetic wave absorbing performance even when compressed.
[電磁波吸收片] 本發明之電磁波吸收片具有：具備第1熱傳導層、及積層於該第1熱傳導層之第2熱傳導層的積層結構，上述第2熱傳導層為於具有透孔之電磁波吸收構件含浸有熱傳導性材料之層，且無負載狀態下之電阻值R1相對於50%壓縮狀態下之電阻值R2的比（R1/R2）滿足以下之式（1）。 0.65＜R1/R2＜0.99 式（1） [Electromagnetic wave absorbing sheet] The electromagnetic wave absorbing sheet of the present invention has a laminated structure including a first heat conduction layer and a second heat conduction layer laminated on the first heat conduction layer, wherein the second heat conduction layer is impregnated with a heat conductive material in an electromagnetic wave absorbing member having through holes. The layer, and the ratio (R1/R2) of the resistance value R1 under the no-load state to the resistance value R2 under the 50% compression state satisfies the following formula (1). 0.65<R1/R2<0.99 Formula (1)
藉由圖1對本發明之電磁波吸收片之一實施方式進行說明。再者，本發明並不受限於圖式之內容。 本發明之電磁波吸收片10具有：具備第1熱傳導層11、及積層於該第1熱傳導層11之第2熱傳導層12的積層結構。第2熱傳導層12為於具有透孔之電磁波吸收構件13含浸有熱傳導性材料之層。 於本發明中，細節如下所述，藉由使電磁波吸收片10之無負載狀態下的電阻值R1相對於50%壓縮狀態下之電阻值R2的比（R1/R2）超過0.65且未達0.99，可抑制壓縮時之電磁波吸收性能降低。 One embodiment of the electromagnetic wave absorbing sheet of the present invention will be described with reference to FIG. 1 . Furthermore, the present invention is not limited by the contents of the drawings. The electromagnetic wave absorbing sheet 10 of the present invention has a laminated structure including a first heat conduction layer 11 and a second heat conduction layer 12 laminated on the first heat conduction layer 11 . The second heat conduction layer 12 is a layer in which the electromagnetic wave absorbing member 13 having through holes is impregnated with a heat conduction material. In the present invention, the details are as follows, by making the ratio (R1/R2) of the resistance value R1 in the no-load state of the electromagnetic wave absorbing sheet 10 to the resistance value R2 in the 50% compressed state exceed 0.65 and not reach 0.99 , It can suppress the reduction of electromagnetic wave absorption performance during compression.
第1熱傳導層11含有高分子基質18與各向異性填充材料19，詳細而言於高分子基質18中分散有各向異性填充材料19。各向異性填充材料19於第1熱傳導層11之厚度方向配向，藉此使電磁波吸收片10之熱傳導性提昇。進而，於第1熱傳導層中，與各向異性填充材料19一同摻合非各向異性填充材料20。藉此，進一步提昇電磁波吸收片10之熱傳導率。 再者，於圖1中表示摻合非各向異性填充材料20之態樣，但第1熱傳導層亦可不摻合非各向異性填充材料20。即，第1熱傳導層11亦可為僅摻合各向異性填充材料19作為填充材料之態樣。 The first heat conduction layer 11 includes a polymer matrix 18 and an anisotropic filler 19 . Specifically, the anisotropic filler 19 is dispersed in the polymer matrix 18 . The anisotropic filling material 19 is oriented in the thickness direction of the first heat conducting layer 11 , thereby improving the heat conductivity of the electromagnetic wave absorbing sheet 10 . Furthermore, an anisotropic filler 20 is blended together with the anisotropic filler 19 in the first heat conduction layer. Thereby, the thermal conductivity of the electromagnetic wave absorbing sheet 10 is further improved. In addition, in FIG. 1, the form which mix|blended the non-anisotropic filler 20 was shown, but the 1st heat conduction layer does not need to mix the anisotropic filler 20. That is, the first heat conduction layer 11 may be an aspect in which only the anisotropic filler 19 is mixed as a filler.
第2熱傳導層12為於具有透孔之電磁波吸收構件13含浸有熱傳導性材料之層。該熱傳導性材料為包含高分子基質16與絕緣性填料17之材料，詳細而言為於高分子基質16中分散有絕緣性填料17之材料。藉由使第2熱傳導層包含絕緣性填料17而對電磁波吸收構件13賦予一定之絕緣性，從而可適用於電子機器等。 由於第2熱傳導層12具有含浸有熱傳導性材料之結構，故可補強電磁波吸收構件13，進而使其與第1熱傳導層之密接性提高，從而防止各層剝離等不良情況。 電磁波吸收構件13於至少一面13a具備金屬層（未圖示），藉此提高電磁波吸收片10之電磁波吸收性能。電磁波吸收構件13較佳為於不織布之至少一面具有金屬層之導電性不織布。 金屬層較佳為設置於電磁波吸收構件的與第1熱傳導層側之面為相反側之面。 The second heat conduction layer 12 is a layer in which the electromagnetic wave absorbing member 13 having through holes is impregnated with a heat conduction material. The thermally conductive material is a material including a polymer matrix 16 and an insulating filler 17 , specifically, a material in which the insulating filler 17 is dispersed in the polymer matrix 16 . By including the insulating filler 17 in the second heat conduction layer, a certain degree of insulation can be imparted to the electromagnetic wave absorbing member 13, so that it can be applied to electronic devices and the like. Since the second heat conduction layer 12 has a structure impregnated with a heat conduction material, the electromagnetic wave absorbing member 13 can be reinforced, thereby improving the adhesion with the first heat conduction layer, thereby preventing problems such as separation of layers. The electromagnetic wave absorbing member 13 has a metal layer (not shown) on at least one surface 13 a, thereby improving the electromagnetic wave absorbing performance of the electromagnetic wave absorbing sheet 10 . The electromagnetic wave absorbing member 13 is preferably a conductive nonwoven fabric having a metal layer on at least one side of the nonwoven fabric. The metal layer is preferably provided on the surface of the electromagnetic wave absorbing member opposite to the surface on the side of the first heat conduction layer.
第2熱傳導層12係自靠近第1熱傳導層之側起，由包含高分子基質16及絕緣性填料17之內部絕緣層14、於透孔內包含高分子基質16及絕緣性填料17之電磁波吸收構件13、包含高分子基質16及絕緣性填料17之表面絕緣層15分別連成層狀而構成。藉由內部絕緣層14，可防止第1熱傳導層11與電磁波吸收構件13之導通。The second heat conduction layer 12 is from the side close to the first heat conduction layer, the electromagnetic wave is absorbed by the inner insulating layer 14 including the polymer matrix 16 and the insulating filler 17, and the polymer matrix 16 and the insulating filler 17 in the through holes. The member 13, the surface insulating layer 15 including the polymer matrix 16 and the insulating filler 17 are respectively connected in layers to form a structure. The internal insulating layer 14 prevents conduction between the first heat conduction layer 11 and the electromagnetic wave absorbing member 13 .
＜電阻值比（R1/R2）＞ 本發明之電磁波吸收片的無負載狀態下之電阻值R1相對於50%壓縮狀態下之電阻值R2的電阻值比（R1/R2）滿足以下之式（1）。 0.65＜R1/R2＜0.99・・・式（1） 若電磁波吸收片不滿足式（1）之電阻值比（R1/R2），則於壓縮之情形時電磁波吸收性能變得容易降低。電磁波吸收片之電阻值比（R1/R2）較佳為0.75以上，更佳為0.80以上，進而較佳為0.85以上，且較佳為0.95以下。又，電磁波吸收片之電阻值比（R1/R2）之範圍較佳為0.75～0.95，更佳為0.80～0.95，進而較佳為0.85～0.95。 電磁波吸收片之電阻值R1及電阻值R2並無特別限定，例如為10～100 Ω。此處，電阻值R1及電阻值R2分別藉由非接觸電阻測定器而測定。 再者，本說明書中，以「～」所表示之範圍係指「～」前後所記載之規定之數值以上至規定之數值以下之範圍。 <Resistance value ratio (R1/R2)> The resistance value ratio (R1/R2) of the resistance value R1 in the no-load state of the electromagnetic wave absorbing sheet of the present invention to the resistance value R2 in the 50% compressed state satisfies the following formula (1). 0.65<R1/R2<0.99・・・Equation (1) If the electromagnetic wave absorbing sheet does not satisfy the resistance value ratio (R1/R2) of the formula (1), the electromagnetic wave absorbing performance tends to decrease when compressed. The resistance value ratio (R1/R2) of the electromagnetic wave absorbing sheet is preferably at least 0.75, more preferably at least 0.80, further preferably at least 0.85, and more preferably at most 0.95. Also, the range of the resistance value ratio (R1/R2) of the electromagnetic wave absorbing sheet is preferably 0.75-0.95, more preferably 0.80-0.95, and still more preferably 0.85-0.95. The resistance values R1 and R2 of the electromagnetic wave absorbing sheet are not particularly limited, and are, for example, 10-100 Ω. Here, the resistance value R1 and the resistance value R2 are respectively measured by a non-contact resistance measuring device. In addition, in this specification, the range represented by "~" means the range of more than the predetermined numerical value described before and after "~" and below the predetermined numerical value.
圖2係示意性表示電阻值R1及R2之測定方法之圖。 如圖2所示，於本發明之電磁波吸收片10之兩面配置2個按壓板21（材質為聚碳酸酯樹脂，厚度為3 mm），使用間隔件23及螺絲22將2個按壓板21以一定間隔固定。然後，藉由設置於上部之按壓板21上之探針24，利用渦電流法測定電磁波吸收片10之電阻值。電磁波吸收片10以第2熱傳導層側朝向探針24側之方式被配置。 電阻值R1係於電磁波吸收片10處於無負載狀態（承受上表面側之按壓板21之負載，但實質上未壓縮之狀態）下測定電阻值。電阻值R2係對電磁波吸收片10進行50%壓縮（即，以成為原本厚度之50%的方式壓縮）而進行測定。又，各電阻值R1、R2係對於藉3 mm之按壓板而測定之電阻值Rs1、Rs2，設為式（5a）、式（5b）所示之換算值。詳細而言，電阻值Rs1係於電磁波吸收片10處於無負載狀態下藉由圖2所示之方法而測定之電阻值，電阻值Rs2係於電磁波吸收片10處於50%壓縮之狀態下藉由圖2所示之方法而測定之電阻值。此處，壓縮率係利用間隔件23及螺絲22，藉由調節2個按壓板21之間隔而調整至期望之值。又，電阻值之測定於室溫（23℃）進行。 然後根據該等Rs1及Rs2，基於式（5a）及式（5b）而算出電阻值R1及電阻值R2。 R1＝0.18×Rs1 0.93式（5a） R2＝0.18×Rs2 0.93式（5b） Fig. 2 is a diagram schematically showing a method of measuring resistance values R1 and R2. As shown in Figure 2, two pressing plates 21 (material is polycarbonate resin, thickness 3 mm) are arranged on both sides of the electromagnetic wave absorbing sheet 10 of the present invention, and the two pressing plates 21 are fixed by using spacers 23 and screws 22. A certain interval is fixed. Then, the resistance value of the electromagnetic wave absorbing sheet 10 is measured by the eddy current method with the probe 24 arranged on the upper pressing plate 21 . The electromagnetic wave absorbing sheet 10 is arranged so that the second heat conduction layer side faces the probe 24 side. The resistance value R1 is measured when the electromagnetic wave absorbing sheet 10 is in an unloaded state (a state in which the pressing plate 21 on the upper surface side receives a load but is not substantially compressed). The resistance value R2 was measured by compressing the electromagnetic wave absorbing sheet 10 by 50% (that is, compressing so as to become 50% of the original thickness). In addition, the respective resistance values R1 and R2 are converted values shown in formula (5a) and formula (5b) for the resistance values Rs1 and Rs2 measured with a 3 mm pressing plate. Specifically, the resistance value Rs1 is the resistance value measured by the method shown in FIG. 2 when the electromagnetic wave absorbing sheet 10 is in a no-load state, and the resistance value Rs2 is measured when the electromagnetic wave absorbing sheet 10 is in a state of 50% compression. The resistance value measured by the method shown in Figure 2. Here, the compressibility is adjusted to a desired value by adjusting the interval between the two pressing plates 21 using the spacer 23 and the screw 22 . In addition, the measurement of resistance value was performed at room temperature (23 degreeC). Then, based on these Rs1 and Rs2, the resistance value R1 and the resistance value R2 are calculated based on Formula (5a) and Formula (5b). R1＝0.18×Rs1 0.93 formula (5a) R2＝0.18×Rs2 0.93 formula (5b)
電阻值R1及電阻值R2係基於式（5a）及（5b），計算在不使用3 mm之按壓板情況下直接測定之電阻值而算出之值。 即，根據對於預先不同之已知電阻值的3片不織布，於不使用按壓板之情況下直接測定之電阻值與藉3 mm之按壓板以無壓縮狀態下測定之電阻值，繪製橫軸為「藉3 mm之按壓板而測定之電阻值」、縱軸為「直接測定之電阻值」之圖，求出通過3點之近似式的換算式（5a）、（5b）。然後使用換算式根據所獲得之測定值而算出電阻值R1、R2。 再者，作為非接觸電阻測定器，例如可使用Napson公司製造之「EC-80P」。 The resistance value R1 and the resistance value R2 are calculated based on formulas (5a) and (5b) by calculating the resistance value measured directly without using a 3 mm pressing plate. That is, according to the resistance value measured directly without using a pressing plate and the resistance value measured in a non-compressed state with a pressing plate of 3 mm for 3 pieces of non-woven fabrics with different known resistance values in advance, the horizontal axis is plotted as "Resistance value measured by a 3 mm pressing plate", the vertical axis is a graph of "directly measured resistance value", and the conversion formula (5a) and (5b) of the approximate formula passing through 3 points are obtained. Then, the resistance values R1 and R2 are calculated from the obtained measured values using the conversion formula. In addition, as a non-contact resistance measuring device, "EC-80P" by Napson company can be used, for example.
＜壓縮率、厚度之關係＞ 較佳為本發明之電磁波吸收片自電磁波吸收片之第1熱傳導層側，藉由 3 mm之柱塞以400 g之負載按壓時之第1熱傳導層之壓縮率C1、第1熱傳導層之厚度T1、及第2熱傳導層之厚度T2滿足以下之式（2）。 C1×T1/（T1＋T2）＞0.26 式（2） 藉由電磁波吸收片滿足式（2），即C1×T1/（T1＋T2）超過0.26，容易將上述之電阻值比（R1/R2）調整至於式（1）所示之期望之範圍，可抑制於壓縮電磁波吸收片之情形時電磁波吸收性能降低。C1×T1/（T1＋T2）較佳為0.50以上，更佳為0.60以上，而且較佳為1.0以下。又，C1×T1/（T1＋T2）較佳為0.50～1.0，更佳為0.60～1.0。 <Relationship between compressibility and thickness> The electromagnetic wave absorbing sheet of the present invention is preferably from the first heat conduction layer side of the electromagnetic wave absorbing sheet, by The compressibility C1 of the first heat conduction layer, the thickness T1 of the first heat conduction layer, and the thickness T2 of the second heat conduction layer when a 3 mm plunger is pressed with a load of 400 g satisfy the following formula (2). C1×T1/(T1+T2)>0.26 Formula (2) By satisfying the formula (2) of the electromagnetic wave absorbing sheet, that is, C1×T1/(T1+T2) exceeds 0.26, it is easy to adjust the above-mentioned resistance value ratio (R1/R2) to the formula In the desired range shown in (1), it is possible to suppress a decrease in electromagnetic wave absorption performance when the electromagnetic wave absorbing sheet is compressed. C1×T1/(T1+T2) is preferably at least 0.50, more preferably at least 0.60, and more preferably at most 1.0. Moreover, C1*T1/(T1+T2) becomes like this. Preferably it is 0.50-1.0, More preferably, it is 0.60-1.0.
第1熱傳導層越柔軟壓縮率C1越大，第1熱傳導層之厚度相對於熱傳導層總體之厚度的比率越大，T1/（T1＋T2）之值越大。即，第1熱傳導層越柔軟，其厚度越厚，越容易滿足式（2）。換而言之，為了滿足式（2），於第1熱傳導層較硬之情形時，需要使其厚度變厚，另一方面，於第1熱傳導層之厚度較薄之情形時，需要使第1熱傳導層變軟。The softer the first heat conduction layer, the greater the compressibility C1, the greater the ratio of the thickness of the first heat conduction layer to the thickness of the entire heat conduction layer, and the greater the value of T1/(T1+T2). That is, the softer and thicker the first heat conduction layer is, the easier it is to satisfy the formula (2). In other words, in order to satisfy the formula (2), when the first heat conduction layer is hard, it needs to be thicker; on the other hand, when the thickness of the first heat conduction layer is thin, it is necessary to make the first heat conduction layer 1 The heat conduction layer becomes soft.
式（2）中之第1熱傳導層之厚度T1與第2熱傳導層之厚度T2係指將電磁波吸收片以柱塞按壓前狀態之各熱傳導層之厚度。 又，式（2）中之C1係第1熱傳導層之壓縮率，根據以柱塞按壓前之第1熱傳導層之厚度T1、及以柱塞按壓後之按壓部分之第1熱傳導層之厚度T1'，藉由以下之式（3）而求出。 C1＝（T1－T1'）/T1 式（3） 壓縮率C1較佳為0.20～0.95，更佳為0.55～0.90。若壓縮率C1為此種範圍，則容易滿足式（2）。 再者，壓縮率可藉由構成熱傳導層之高分子基質之種類、填充材料（填料）之填充量等而調整。 The thickness T1 of the first heat conduction layer and the thickness T2 of the second heat conduction layer in formula (2) refer to the thickness of each heat conduction layer in the state before the electromagnetic wave absorbing sheet is pressed with a plunger. In addition, C1 in formula (2) is the compressibility of the first heat conduction layer, according to the thickness T1 of the first heat conduction layer before being pressed by the plunger, and the thickness T1 of the first heat conduction layer of the pressed part after being pressed by the plunger ', obtained by the following formula (3). C1＝(T1－T1')/T1 Formula (3) The compression ratio C1 is preferably from 0.20 to 0.95, more preferably from 0.55 to 0.90. When the compression ratio C1 is within such a range, Expression (2) is easily satisfied. Furthermore, the compressibility can be adjusted by the type of the polymer matrix constituting the heat conduction layer, the filling amount of the filling material (filler), and the like.
第1熱傳導層之厚度T1並無特別限定，就抑制壓縮電磁波吸收片時造成電磁波吸收性能降低之觀點、及抑制壓縮時電磁波吸收性能降低之觀點而言，較佳為0.2 mm以上，更佳為1 mm以上，進而較佳為1.2 mm以上。另一方面，第1熱傳導層之厚度T1並無特別限定，就使電磁波吸收片之熱傳導性提昇之觀點而言，較佳為5 mm以下，更佳為3 mm以下，進而較佳為2 mm以下。 又，第1熱傳導層之厚度T1並無特別限定，就使電磁波吸收片之熱傳導性提昇之觀點、及抑制壓縮時電磁波吸收性能降低之觀點而言，較佳為0.2～5 mm，更佳為1～3 mm，進而較佳為1.2～2 mm。 第2熱傳導層之厚度T2並無特別限定，就抑制壓縮電磁波吸收片時造成電磁波吸收性能降低之觀點而言，較佳為0.05 mm以上，更佳為0.08 mm以上，進而較佳為0.1 mm以上。另一方面，第2熱傳導層之厚度T2並無特別限定，就使電磁波吸收片之熱傳導性提昇之觀點而言，較佳為3 mm以下，更佳為2 mm以下，進而較佳為1 mm以下。 又，第2熱傳導層之厚度T2並無特別限定，就使電磁波吸收片之熱傳導性提昇之觀點、及抑制壓縮時電磁波吸收性能降低之觀點而言，較佳為0.05～3 mm，更佳為0.08～2 mm，進而較佳為0.1～1 mm。 就容易滿足式（2）之觀點而言，較佳為第1熱傳導層之厚度T1比第2熱傳導層之厚度T2薄。 The thickness T1 of the first heat conduction layer is not particularly limited, but is preferably 0.2 mm or more, more preferably 1 mm or more, and more preferably 1.2 mm or more. On the other hand, the thickness T1 of the first heat conduction layer is not particularly limited, but is preferably 5 mm or less, more preferably 3 mm or less, and still more preferably 2 mm from the viewpoint of improving the thermal conductivity of the electromagnetic wave absorbing sheet. the following. Also, the thickness T1 of the first heat-conducting layer is not particularly limited, but it is preferably 0.2 to 5 mm, more preferably 1 to 3 mm, more preferably 1.2 to 2 mm. The thickness T2 of the second heat conduction layer is not particularly limited, but is preferably at least 0.05 mm, more preferably at least 0.08 mm, and still more preferably at least 0.1 mm, from the viewpoint of suppressing a decrease in electromagnetic wave absorption performance when the electromagnetic wave absorbing sheet is compressed. . On the other hand, the thickness T2 of the second heat conduction layer is not particularly limited, but is preferably 3 mm or less, more preferably 2 mm or less, and still more preferably 1 mm from the viewpoint of improving the thermal conductivity of the electromagnetic wave absorbing sheet. the following. Also, the thickness T2 of the second heat conduction layer is not particularly limited, but it is preferably 0.05 to 3 mm, more preferably 0.08 to 2 mm, more preferably 0.1 to 1 mm. From the viewpoint of easily satisfying the formula (2), it is preferable that the thickness T1 of the first heat conduction layer is thinner than the thickness T2 of the second heat conduction layer.
自電磁波吸收片之第2熱傳導層側，藉由 3 mm之柱塞以400 g之負載按壓時之第2熱傳導層之壓縮率C2較佳為0.10～0.90，更佳為0.30～0.80。若壓縮率C2為此種範圍，則容易適當地保護電磁波吸收構件。又，就抑制壓縮電磁波吸收片時造成電磁吸收性能降低之觀點而言，壓縮率C2較佳為比上述之壓縮率C1小之值。 C2係第2熱傳導層之壓縮率，根據以柱塞按壓前之第2熱傳導層之厚度T2、及以柱塞按壓後之按壓部分之第2熱傳導層之厚度T2'，藉由以下之式（4）而求出。 C2＝（T2－T2'）/T2 式（4） From the second heat conduction layer side of the electromagnetic wave absorbing sheet, by The compressibility C2 of the second heat conduction layer when a 3 mm plunger is pressed with a load of 400 g is preferably 0.10 to 0.90, more preferably 0.30 to 0.80. When the compressibility C2 is within such a range, it is easy to properly protect the electromagnetic wave absorbing member. In addition, from the viewpoint of suppressing a decrease in electromagnetic absorption performance when the electromagnetic wave absorbing sheet is compressed, the compression ratio C2 is preferably a value smaller than the above-mentioned compression ratio C1. C2 is the compressibility of the second heat conduction layer, according to the thickness T2 of the second heat conduction layer before being pressed by the plunger, and the thickness T2' of the second heat conduction layer of the pressed part after being pressed by the plunger, by the following formula ( 4) and find out. C2＝(T2－T2')/T2 formula (4)
＜第1熱傳導層＞ 本發明之電磁波吸收片具備第1熱傳導層。第1熱傳導層包含配向於該熱傳導層之厚度方向之各向異性填充材料，因此熱傳導性較高，且使電磁波吸收片之散熱性提昇。 第1熱傳導層11含有高分子基質18、及各向異性填充材料19。第1熱傳導層可進而包含非各向異性填充材料20。再者，各向異性填充材料配向之狀態係指各向異性填充材料之長軸方向與規定之方向一致。 ＜1st heat conduction layer＞ The electromagnetic wave absorbing sheet of the present invention includes a first heat conduction layer. The first heat conduction layer includes the anisotropic filling material aligned in the thickness direction of the heat conduction layer, so the thermal conductivity is high, and the heat dissipation of the electromagnetic wave absorbing sheet is improved. The first heat conduction layer 11 includes a polymer matrix 18 and an anisotropic filler 19 . The first heat conduction layer may further include an anisotropic filler 20 . Furthermore, the state of alignment of the anisotropic filler means that the long-axis direction of the anisotropic filler coincides with a predetermined direction.
第1熱傳導層11中所使用之高分子基質18為彈性體或橡膠等高分子化合物，較佳為使用將由主劑與硬化劑等混合系統構成的液狀高分子組成物（硬化性高分子組成物）硬化而形成者。硬化性高分子組成物例如可由未交聯橡膠與交聯劑所構成，亦可包含單體、預聚物等與硬化劑等。又，上述硬化反應可為常溫硬化，亦可為熱硬化。The polymer matrix 18 used in the first heat conduction layer 11 is a polymer compound such as an elastomer or rubber, preferably a liquid polymer composition (curable polymer composition) composed of a mixed system such as a main agent and a hardener. matter) hardened and formed. The curable polymer composition may be composed of uncrosslinked rubber and a crosslinking agent, for example, and may also include monomers, prepolymers, etc., and a curing agent. In addition, the above-mentioned curing reaction may be room temperature curing or thermal curing.
由硬化性高分子組成物所形成之高分子基質較佳為聚矽氧橡膠。於聚矽氧橡膠之情形時，作為高分子基質（硬化性高分子組成物），較佳為使用加成反應硬化型聚矽氧。又，更具體而言，作為硬化性高分子組成物，可使用包含含烯基之有機聚矽氧烷與氫化有機聚矽氧烷者。The polymer matrix formed by the curable polymer composition is preferably silicone rubber. In the case of silicone rubber, it is preferable to use an addition reaction-curable silicone as the polymer matrix (curable polymer composition). Moreover, more specifically, as a curable polymer composition, one containing an alkenyl group-containing organopolysiloxane and a hydrogenated organopolysiloxane can be used.
作為橡膠，可使用除上述以外之各種合成橡膠，作為具體例，例如可列舉：丙烯酸系橡膠、腈橡膠、異戊二烯橡膠、胺酯（urethane）橡膠、乙烯丙烯橡膠、苯乙烯-丁二烯橡膠、丁二烯橡膠、氟橡膠、丁基橡膠等。於使用該等橡膠之情形時，合成橡膠可於第1熱傳導層中交聯，亦可保持未交聯（即未硬化）。未交聯之橡膠主要以流動配向而使用。 又，於交聯（即硬化）之情形時，如上述所說明，高分子基質可為使包含由該等合成橡膠構成之未交聯橡膠、及交聯劑之硬化性高分子組成物硬化而成者。 又，作為彈性體，亦可使用聚酯系熱塑性彈性體、聚胺酯系熱塑性彈性體等熱塑性彈性體、或使由主劑與硬化劑構成之混合系之液狀高分子組成物硬化而形成之熱硬化型彈性體。例如，可例示使包含具有羥基之高分子與異氰酸酯的高分子組成物硬化而形成之聚胺酯系彈性體。 於上述中，例如就硬化後之高分子基質特別柔軟，各向異性填充材料、非各向異性填充材料之填充性良好之方面而言，較佳為使用聚矽氧橡膠，特別是加成反應硬化型聚矽氧。 As the rubber, various synthetic rubbers other than those mentioned above can be used. Specific examples include: acrylic rubber, nitrile rubber, isoprene rubber, urethane rubber, ethylene propylene rubber, styrene-butadiene rubber, etc. Vinyl rubber, butadiene rubber, fluororubber, butyl rubber, etc. In the case of using such rubbers, the synthetic rubber may be cross-linked in the first heat-conducting layer, or may remain uncross-linked (ie, not hardened). Uncrosslinked rubber is mainly used for flow alignment. Also, in the case of crosslinking (that is, hardening), as described above, the polymer matrix can be formed by hardening a curable polymer composition including uncrosslinked rubber composed of these synthetic rubbers and a crosslinking agent. winner. In addition, as the elastomer, thermoplastic elastomers such as polyester-based thermoplastic elastomers and polyurethane-based thermoplastic elastomers, or thermoplastic elastomers formed by hardening a mixed liquid polymer composition composed of a main agent and a curing agent, can also be used. hardened elastomer. For example, a polyurethane-based elastomer obtained by curing a polymer composition containing a polymer having a hydroxyl group and isocyanate can be exemplified. Among the above, for example, the polymer matrix after hardening is particularly soft, and the filling properties of the anisotropic filler and the anisotropic filler are good, it is preferable to use polysiloxane rubber, especially the addition reaction Hardened silicone.
又，用以形成高分子基質之高分子組成物可由高分子化合物單一成分構成，亦可由高分子化合物與塑化劑構成。塑化劑適合於使用合成橡膠之情形時使用，藉由包含塑化劑，可提高未交聯時之高分子基質之柔軟性。 塑化劑使用與高分子化合物具有相容性者，具體而言，較佳為酯系塑化劑或聚矽氧油。作為酯系塑化劑之具體例，例如可列舉：鄰苯二甲酸酯、己二酸酯、1,2,4-苯三甲酸酯、磷酸酯、癸二酸酯、壬二酸酯、順丁烯二酸酯、苯甲酸酯等。作為聚矽氧油，可列舉聚二甲基矽氧烷。 於使用塑化劑之情形時，其含量相對於第1熱傳導層總量較佳為1～30體積%，更佳為5～20體積%。 In addition, the polymer composition used to form the polymer matrix may be composed of a single polymer compound, or may be composed of a polymer compound and a plasticizer. The plasticizer is suitable for use when synthetic rubber is used, and the flexibility of the uncrosslinked polymer matrix can be improved by including the plasticizer. The plasticizer used is compatible with polymer compounds, specifically, ester-based plasticizers or polysiloxane oils are preferred. Specific examples of ester-based plasticizers include phthalates, adipates, 1,2,4-benzenetricarboxylates, phosphoric acid esters, sebacates, azelates, Maleate, benzoate, etc. Examples of the silicone oil include polydimethylsiloxane. When a plasticizer is used, its content is preferably 1 to 30% by volume, more preferably 5 to 20% by volume, relative to the total amount of the first heat conduction layer.
作為高分子基質之含量，相對於第1熱傳導層總量，較佳為15～50體積%，更佳為20～45體積%。The content of the polymer matrix is preferably from 15 to 50% by volume, more preferably from 20 to 45% by volume, relative to the total amount of the first heat conduction layer.
（各向異性填充材料） 高分子基質18中所摻合之各向異性填充材料19為於形狀上具有各向異性之填充材料，為可配向之填充材料。各向異性填充材料19為熱傳導填充材料。作為各向異性填充材料19，可列舉：纖維材料、鱗片狀材料等。各向異性填充材料19係縱橫比較高者，具體而言縱橫比超過2，較佳為縱橫比為5以上。藉由縱橫比大於2，容易使各向異性填充材料19於厚度方向配向，容易提高第1熱傳導層之熱傳導性。 又，縱橫比之上限並無特別限定，但實用上為100。 因此，上述縱橫比較佳為超過2且100以下，更佳為5～100。 再者，縱橫比係指各向異性填充材料19之長軸方向之長度相對於短軸方向之長度之比，於纖維材料中，係指纖維長度/纖維直徑，於鱗片狀材料中係指鱗片狀材料之長軸方向之長度/厚度。 作為各向異性填充材料19，就提高熱傳導性之觀點而言，較佳為纖維材料。 (anisotropic filling material) The anisotropic filling material 19 mixed in the polymer matrix 18 is an anisotropic filling material in shape, and is an alignable filling material. The anisotropic filling material 19 is a thermally conductive filling material. As the anisotropic filler 19, a fibrous material, a scaly material, etc. are mentioned. The anisotropic filler 19 has a high aspect ratio, specifically, the aspect ratio exceeds 2, and preferably the aspect ratio is 5 or more. When the aspect ratio is greater than 2, it is easy to align the anisotropic filling material 19 in the thickness direction, and it is easy to improve the thermal conductivity of the first thermal conductive layer. Moreover, although the upper limit of an aspect ratio is not specifically limited, It is 100 practically. Therefore, the above-mentioned aspect ratio is preferably more than 2 and 100 or less, more preferably 5-100. Furthermore, the aspect ratio refers to the ratio of the length of the long axis direction of the anisotropic filler material 19 to the length of the short axis direction. In fibrous materials, it refers to fiber length/fiber diameter. In scaly materials, it refers to scales. The length/thickness of the long axis direction of the shape material. The anisotropic filler 19 is preferably a fiber material from the viewpoint of improving thermal conductivity.
作為第1熱傳導層11中各向異性填充材料19之含量，相對於第1熱傳導層總量，較佳為5～35體積%，更佳為8～30體積%。 藉由將各向異性填充材料19之含量設為5體積%以上，容易提高熱傳導性，藉由設為35體積%以下，容易使下述之第1熱傳導層用組成物之黏度變得適度，各向異性填充材料19之配向性變得良好。 The content of the anisotropic filler 19 in the first heat conduction layer 11 is preferably 5 to 35% by volume, more preferably 8 to 30% by volume, based on the total amount of the first heat conduction layer. By setting the content of the anisotropic filler 19 to 5% by volume or more, it is easy to improve thermal conductivity, and by setting the content of the anisotropic filler 19 to 35% by volume or less, it is easy to moderate the viscosity of the composition for the first heat conduction layer described below, The orientation of the anisotropic filler 19 becomes good.
於各向異性填充材料19為纖維材料之情形時，其平均纖維長度較佳為50～500 μm，更佳為70～350 μm。若將平均纖維長度設為50 μm以上，則於第1熱傳導層11內部，各向異性填充材料彼此適度接觸，確保熱之傳遞路徑。 另一方面，若將平均纖維長度設為500 μm以下，則各向異性填充材料之體積變低，可高度填充於高分子基質中。 再者，上述之平均纖維長度可藉由顯微鏡觀察各向異性填充材料而算出。更具體而言，例如可使用電子顯微鏡或光學顯微鏡，測定任意50個各向異性填充材料之纖維長度，將其平均值（算術平均值）作為平均纖維長度。 When the anisotropic filling material 19 is a fiber material, the average fiber length is preferably 50-500 μm, more preferably 70-350 μm. If the average fiber length is set to be 50 μm or more, the anisotropic fillers will be in moderate contact with each other inside the first heat conduction layer 11, thereby securing a heat transfer path. On the other hand, if the average fiber length is set to 500 μm or less, the volume of the anisotropic filler becomes low, and it can be highly filled in the polymer matrix. In addition, the above-mentioned average fiber length can be calculated by observing the anisotropic filler under a microscope. More specifically, for example, the fiber lengths of 50 arbitrary anisotropic fillers can be measured using an electron microscope or an optical microscope, and the average value (arithmetic mean) thereof can be regarded as the average fiber length.
又，纖維材料之平均纖維長度較佳為短於第1熱傳導層11之厚度。藉由短於厚度，可防止纖維材料自第1熱傳導層11之自表面突出需要程度以上。 又，於各向異性填充材料19為鱗片狀材料之情形時，其平均粒徑較佳為5～300 μm，更佳為10～100 μm。又，特佳為10～50 μm。藉由將平均粒徑設為5 μm以上，於第1熱傳導層中容易使各向異性填充材料19彼此接觸，確保熱之傳遞路徑。另一方面，若將平均粒徑設為300 μm以下，則第1熱傳導層之體積變低，可於高分子基質18中高度填充各向異性填充材料19。 再者，鱗片狀材料之平均粒徑可藉由顯微鏡觀察各向異性填充材料，算出長徑作為直徑。更具體而言，例如可使用電子顯微鏡或光學顯微鏡，測定任意50個各向異性填充材料之長徑，將其平均值（算術平均值）作為平均纖維長度。 Also, the average fiber length of the fiber material is preferably shorter than the thickness of the first heat conduction layer 11 . By being shorter than the thickness, it is possible to prevent the fiber material from protruding from the surface of the first heat conduction layer 11 more than necessary. Also, when the anisotropic filler 19 is a scaly material, its average particle size is preferably 5-300 μm, more preferably 10-100 μm. Also, particularly preferably, it is 10 to 50 μm. By setting the average particle size to 5 μm or more, the anisotropic fillers 19 are easily brought into contact with each other in the first heat conduction layer, thereby securing a heat transfer path. On the other hand, if the average particle diameter is set to be 300 μm or less, the volume of the first heat conduction layer becomes low, and the anisotropic filler 19 can be highly filled in the polymer matrix 18 . Furthermore, the average particle size of the flaky material can be obtained by observing the anisotropic filling material with a microscope, and calculating the long axis as the diameter. More specifically, for example, the long diameters of arbitrary 50 anisotropic fillers can be measured using an electron microscope or an optical microscope, and the average (arithmetic mean) thereof can be defined as the average fiber length.
各向異性填充材料19可使用具有熱傳導性之公知材料，較佳為以可如下所述地進行磁場配向之方式具備抗磁性。 作為各向異性填充材料19之具體例，可列舉：以碳纖維、或鱗片狀碳粉末為代表之碳系材料；以金屬纖維為代表之金屬材料或金屬氧化物、氮化硼或金屬氮化物、金屬碳化物、金屬氫氧化物等。於該等中，碳系材料由於比重較小，且向高分子基質12中之分散性良好，故而較佳，其中，更佳為熱傳導率較高之石墨化碳材料。石墨化碳材料由於石墨面與規定方向一致而具備抗磁性。又，氮化硼等亦由於結晶面與規定方向一致而具備抗磁性。又，各向異性填充材料19特佳為碳纖維。 As the anisotropic filler 19, a known material having thermal conductivity can be used, and it is preferable to have diamagnetism so that magnetic field alignment can be performed as described below. Specific examples of the anisotropic filler 19 include: carbon-based materials represented by carbon fibers or scaly carbon powders; metal materials represented by metal fibers or metal oxides, boron nitride or metal nitrides , metal carbides, metal hydroxides, etc. Among them, carbon-based materials are preferable because of their small specific gravity and good dispersion in the polymer matrix 12 , and among them, graphitized carbon materials with high thermal conductivity are more preferable. Graphitized carbon materials are diamagnetic because the graphite surfaces are aligned with the prescribed direction. In addition, boron nitride and the like also have diamagnetism because the crystal plane is aligned with a predetermined direction. Also, the anisotropic filler 19 is particularly preferably carbon fiber.
又，各向異性填充材料19並無特別限定，沿具有各向異性之方向（即長軸方向）之熱傳導率通常為60 W/m･K以上，較佳為400 W/m･K。各向異性填充材料19之熱傳導率之上限並無特別限定，例如為2000 W/m･K以下。熱傳導率之測定方法為雷射閃光法。 Also, the anisotropic filling material 19 is not particularly limited, and the thermal conductivity along the anisotropic direction (ie, the long-axis direction) is usually 60 W/m·K or more, preferably 400 W/m·K. The upper limit of the thermal conductivity of the anisotropic filler 19 is not particularly limited, and is, for example, 2000 W/m·K or less. The measurement method of thermal conductivity is the laser flash method.
各向異性填充材料19可單獨使用1種，亦可併用2種以上。例如，作為各向異性填充材料19，可使用具有至少2種互不相同之平均粒徑或平均纖維長度的各向異性填充材料19。認為若使用大小不同之各向異性填充材料，則較小之各向異性填充材料進入相對大之各向異性填充材料之間，從而可於高分子基質中高密度地填充各向異性填充材料，並且提高熱之傳導效率。 The anisotropic filler 19 may be used alone or in combination of two or more. For example, as the anisotropic filler 19, the anisotropic filler 19 which has at least 2 types of average particle diameters or average fiber length which differ from each other can be used. It is considered that if anisotropic fillers with different sizes are used, the smaller anisotropic fillers will enter between the relatively larger anisotropic fillers, so that the anisotropic fillers can be densely filled in the polymer matrix, and Improve heat conduction efficiency.
用作各向異性填充材料19之碳纖維較佳為石墨化碳纖維。又，作為鱗片狀碳粉末，較佳為鱗片狀石墨粉末。作為各向異性填充材料19，該等中更佳為石墨化碳纖維。 石墨化碳纖維的石墨之結晶面於纖維軸方向相連，而於該纖維軸方向具備較高之熱傳導率。因此，藉由使該纖維軸方向與規定之方向一致，可提高特定方向之熱傳導率。又，鱗片狀石墨粉末的石墨之結晶面於鱗片面之面內方向相連，而於該面內方向具備較高之熱傳導率。因此，藉由使該鱗片面與規定之方向一致，可提高特定方向之熱傳導率。石墨化碳纖維及鱗片石墨粉末較佳為具有高石墨化度者。 Carbon fibers used as the anisotropic filler material 19 are preferably graphitized carbon fibers. Also, as the flaky carbon powder, flaky graphite powder is preferable. As the anisotropic filler 19, among these, graphitized carbon fibers are more preferable. The graphite crystal planes of the graphitized carbon fiber are connected in the direction of the fiber axis, and have high thermal conductivity in the direction of the fiber axis. Therefore, by aligning the fiber axis direction with a predetermined direction, the thermal conductivity in a specific direction can be improved. In addition, the graphite crystal planes of the flake graphite powder are connected in the in-plane direction of the scale plane, and have high thermal conductivity in the in-plane direction. Therefore, by aligning the surface of the scales with a predetermined direction, the thermal conductivity in a specific direction can be increased. The graphitized carbon fiber and flake graphite powder preferably have a high degree of graphitization.
作為上述石墨化碳纖維、鱗片狀石墨粉末等石墨化碳材料，可使用將以下原料石墨化而成者。例如可列舉：萘等縮合多環烴化合物、PAN（聚丙烯腈）、瀝青等縮合雜環化合物等，尤佳為使用石墨化度較高之石墨化中間相瀝青或聚醯亞胺、聚苯并唑（poly benzazole）。例如藉由使用中間相瀝青，而於下述之紡絲步驟中，瀝青由於其各向異性而配向於纖維軸方向，從而可獲得於其纖維軸方向具有優異之熱傳導性之石墨化碳纖維。 作為石墨化碳纖維中之中間相瀝青之使用態樣，只要可紡絲就沒有特別限定，可單獨使用中間相瀝青，亦可組合使用其他原料。其中，就高熱傳導化、紡絲性及品質之穩定性之方面而言，最佳為單獨使用中間相瀝青，即，中間相瀝青含量為100%之石墨化碳纖維。 As graphitized carbon materials such as the above-mentioned graphitized carbon fiber and flaky graphite powder, those obtained by graphitizing the following raw materials can be used. Examples include: condensed polycyclic hydrocarbon compounds such as naphthalene, condensed heterocyclic compounds such as PAN (polyacrylonitrile), pitch, etc., and it is especially preferable to use graphitized mesophase pitch with a high degree of graphitization or polyimide, polyphenylene, etc. Polybenzole. For example, by using mesophase pitch, the pitch is aligned in the fiber axis direction due to its anisotropy in the spinning step described below, so that graphitized carbon fibers having excellent thermal conductivity in the fiber axis direction can be obtained. The use of the mesophase pitch in the graphitized carbon fiber is not particularly limited as long as it can be spun, and the mesophase pitch may be used alone or in combination with other materials. Among them, in terms of high heat conductivity, spinnability, and quality stability, it is most preferable to use mesophase pitch alone, that is, graphitized carbon fibers with a mesophase pitch content of 100%.
石墨化碳纖維使用依序進行紡絲、不熔化及碳化各處理，於粉碎或切斷為規定粒徑後進行石墨化而成者，或於碳化後進行粉碎或切斷後進行石墨化而成者。於石墨化前進行粉碎或切斷之情形時，由於在因粉碎而新露出於表面之表面中，在石墨化處理時容易進行縮聚反應、環化反應，故可獲得石墨化度提高、熱傳導性進一步提昇之石墨化碳纖維。另一方面，於將紡絲之碳纖維石墨化後進行粉碎之情形時，由於石墨化後之碳纖維是剛性的而容易粉碎，藉由短時間之粉碎可獲得纖維長度分佈較窄之碳纖維粉末。 The graphitized carbon fibers are those obtained by performing spinning, infusibility, and carbonization in sequence, and then graphitized after crushing or cutting to a predetermined particle size, or graphitized after carbonization and crushing or cutting. In the case of pulverization or cutting before graphitization, since the surface newly exposed by the pulverization is easy to undergo polycondensation reaction and cyclization reaction during graphitization treatment, it is possible to obtain improved graphitization degree and thermal conductivity. Further improved graphitized carbon fiber. On the other hand, when the spun carbon fiber is graphitized and then pulverized, since the graphitized carbon fiber is rigid and easy to pulverize, a carbon fiber powder with a narrow fiber length distribution can be obtained by pulverizing for a short time.
各向異性填充材料19如上所述地配向於厚度方向，長軸方向不必嚴格平行於厚度方向，即使長軸方向多少會相對於厚度方向傾斜，亦可作為配向於厚度方向者。具體而言，長軸方向傾斜未達20°之程度者亦設為配向於厚度方向之各向異性填充材料19，若此種各向異性填充材料19於第1熱傳導層中占大部分（例如，相對於各向異性填充材料之總數超過60%，較佳為超過80%），則將其作為配向於厚度方向者。 The anisotropic filling material 19 is aligned in the thickness direction as described above, and the long axis direction does not have to be strictly parallel to the thickness direction. Even if the long axis direction is somewhat inclined relative to the thickness direction, it can also be aligned in the thickness direction. Specifically, those whose long-axis direction is inclined less than 20° are also regarded as anisotropic filling materials 19 aligned in the thickness direction. , relative to the total amount of anisotropic filling materials exceeding 60%, preferably exceeding 80%), it is regarded as those aligned in the thickness direction.
＜非各向異性填充材料＞ 非各向異性填充材料20係與各向異性填充材料19分開含有於第1熱傳導層中之熱傳導性填充材料，與各向異性填充材料19一同對第1熱傳導層賦予熱傳導性之材料。又，於各向異性填充材料19之間，例如若纖維長度變大，則填充材料彼此之接觸面積難以增大，但藉由非各向異性填充材料20充填其間之空間，可形成傳熱路徑，從而獲得熱傳導率較高之第1熱傳導層。 非各向異性填充材料20係於形狀方面實質上不具有各向異性之填充材料，其係即使於下述之磁力線之產生或剪力之作用等之情形下，使各向異性填充材料19配向於規定方向之環境下，亦不配向於該規定方向之填充材料。 ＜Anisotropic Filling Material＞ The non-anisotropic filler 20 is a thermally conductive filler contained in the first thermally conductive layer separately from the anisotropic filler 19 , and is a material that imparts thermal conductivity to the first thermally conductive layer together with the anisotropic filler 19 . Also, between the anisotropic fillers 19, for example, if the fiber length becomes longer, the contact area between the fillers is difficult to increase, but by filling the space between them with the anisotropic filler 20, a heat transfer path can be formed. , so as to obtain the first heat conduction layer with high thermal conductivity. The non-anisotropic filler 20 is a filler that does not substantially have anisotropy in shape, and it aligns the anisotropic filler 19 even under the generation of magnetic lines of force or the action of shear force as described below. In the environment of the specified direction, the filling material is not aligned in the specified direction.
作為非各向異性填充材料20，其縱橫比為2以下，較佳為1.5以下。於本實施方式中，藉由含有縱橫比如此低之非各向異性填充材料20，使具有熱傳導性之填充材料適當地介存於各向異性填充材料19之間隙，從而獲得熱傳導率較高之第1熱傳導層。又，藉由將縱橫比設為2以下，可防止下述之第1熱傳導層用組成物之黏度上升，實現高度填充。 The non-anisotropic filler 20 has an aspect ratio of 2 or less, preferably 1.5 or less. In the present embodiment, by including the anisotropic filler 20 with such a low aspect ratio, the thermally conductive filler is properly interposed in the gap between the anisotropic filler 19, thereby obtaining a high thermal conductivity. 1st heat transfer layer. In addition, by setting the aspect ratio to 2 or less, it is possible to prevent the viscosity of the composition for the first heat conduction layer described below from increasing, and to achieve a high degree of filling.
作為非各向異性填充材料20之具體例，例如可列舉：金屬、金屬氧化物、金屬氮化物、金屬氫氧化物、碳材料、金屬以外之氧化物、氮化物、碳化物等。又，非各向異性填充材料20之形狀可列舉球狀、不定形之粉末等。 於非各向異性填充材料20中，作為金屬，可例示：鋁、銅、鎳等；作為金屬氧化物，可例示：以礬土為代表之氧化鋁、氧化鎂、氧化鋅等；作為金屬氮化物可例示氮化鋁等。作為金屬氫氧化物，可列舉氫氧化鋁。進而，作為碳材料可列舉球狀石墨等。作為金屬以外之氧化物、氮化物、碳化物，可列舉：石英、氮化硼、碳化矽等。 作為非各向異性填充材料20，上述中較佳為選自由礬土、鋁、氫氧化鋁、氧化鋅、氮化硼、及氮化鋁所組成之群中之1種以上，更佳為選自由礬土、鋁、及氫氧化鋁所組成之群中之1種以上。 非各向異性填充材料20可單獨使用上述材料之1種，亦可併用2種以上。 Specific examples of the anisotropic filler 20 include metals, metal oxides, metal nitrides, metal hydroxides, carbon materials, oxides other than metals, nitrides, and carbides. Also, examples of the shape of the non-anisotropic filler 20 include spherical shape, amorphous powder, and the like. In the anisotropic filler 20, examples of metals include aluminum, copper, nickel, etc.; examples of metal oxides include alumina, magnesium oxide, zinc oxide, etc. represented by alumina; examples of metal nitrogen As the compound, aluminum nitride and the like can be exemplified. Aluminum hydroxide is mentioned as a metal hydroxide. Furthermore, spherical graphite etc. are mentioned as a carbon material. Examples of oxides, nitrides, and carbides other than metals include quartz, boron nitride, and silicon carbide. As the non-anisotropic filling material 20, among the above, one or more selected from the group consisting of alumina, aluminum, aluminum hydroxide, zinc oxide, boron nitride, and aluminum nitride is preferred, and more preferably One or more species selected from the group consisting of alumina, aluminum, and aluminum hydroxide. As the non-anisotropic filler 20, one of the above-mentioned materials may be used alone, or two or more of them may be used in combination.
非各向異性填充材料20之平均粒徑較佳為0.1～50 μm，更佳為0.5～35 μm。又，特佳為1～20 μm。藉由將平均粒徑設為50 μm以下，難以產生各向異性填充材料19之配向紊亂等不良情況。又，藉由將平均粒徑設為0.1 μm以上，非各向異性填充材料20之比表面積不會超過需要，即使大量摻合，第1熱傳導層用組成物之黏度亦難以上升，容易高度填充非各向異性填充材料20。 至於非各向異性填充材料20，例如可使用具有至少2種互不相同之平均粒徑之非各向異性填充材料20作為非各向異性填充材料20。 再者，非各向異性填充材料20之平均粒徑可藉由電子顯微鏡等進行觀察而測定。更具體而言，例如可使用電子顯微鏡或光學顯微鏡，測定任意50個非各向異性填充材料之粒徑，將其平均值（算術平均值）作為平均粒徑。 The average particle size of the non-anisotropic filler 20 is preferably 0.1-50 μm, more preferably 0.5-35 μm. Also, particularly preferably, it is 1 to 20 μm. By setting the average particle size to 50 μm or less, troubles such as disordered alignment of the anisotropic filler 19 are less likely to occur. In addition, by setting the average particle size to 0.1 μm or more, the specific surface area of the anisotropic filler 20 does not exceed the requirement, and even if a large amount is blended, the viscosity of the first heat-conducting layer composition is difficult to increase, and a high degree of filling is easy Non-anisotropic filling material 20 . As the non-anisotropic filler 20 , for example, non-anisotropic fillers 20 having at least two different average particle diameters can be used as the non-anisotropic filler 20 . In addition, the average particle size of the non-anisotropic filler 20 can be measured by observing with an electron microscope or the like. More specifically, for example, the particle diameters of arbitrary 50 non-anisotropic fillers can be measured using an electron microscope or an optical microscope, and the average value (arithmetic mean) thereof can be regarded as the average particle diameter.
作為非各向異性填充材料20之含量，相對於第1熱傳導層總量，較佳為30～60體積%，更佳為35～55體積%。藉由將非各向異性填充材料20之含量設為30體積%以上，介存於各向異性填充材料19彼此之間隙的非各向異性填充材料20之量變得充足，熱傳導性變得良好。又，藉由將非各向異性填充材料20之含量設為60體積%以下，亦不會由於非各向異性填充材料20而抑制各向異性填充材料19之熱傳導。 The content of the non-anisotropic filler 20 is preferably 30 to 60% by volume, more preferably 35 to 55% by volume, relative to the total amount of the first heat conduction layer. By setting the content of the non-anisotropic filler 20 to 30 volume % or more, the amount of the non-anisotropic filler 20 interposed in the gap between the anisotropic fillers 19 becomes sufficient, and thermal conductivity becomes favorable. Moreover, by making content of the non-anisotropic filler 20 into 60 volume% or less, the heat conduction of the anisotropic filler 19 is not suppressed by the anisotropic filler 20, either.
（添加劑） 於第1熱傳導層11中，亦可進而於不損及作為第1熱傳導層之功能的範圍內，於高分子基質18中摻合各種添加劑。作為添加劑，例如可列舉選自分散劑、偶合劑、黏著劑、難燃劑、抗氧化劑、著色劑、沈澱防止劑等中之至少1種以上。又，於如上所述地使硬化性高分子組成物交聯、硬化等情形時，作為添加劑，可摻合促進交聯、硬化之交聯促進劑、硬化促進劑等。 (additive) In the first heat conduction layer 11, various additives may further be blended into the polymer matrix 18 within the range not to impair the function as the first heat conduction layer. As an additive, for example, at least one or more selected from the group consisting of dispersants, coupling agents, adhesives, flame retardants, antioxidants, colorants, and anti-sedimentation agents may be mentioned. Also, when the curable polymer composition is crosslinked and hardened as described above, a crosslinking accelerator, a hardening accelerator, etc. for accelerating crosslinking and hardening may be blended as additives.
（E硬度） 第1熱傳導層11之由JIS K6253規定之E型硬度較佳為15以上，更佳為17以上，進而較佳為18以上。進而，第1熱傳導層11之E型硬度較佳為70以下，更佳為65以下，進而較佳為60以下。 又，第1熱傳導層11之E型硬度較佳為15～70，更佳為17～65，進而較佳為18～60。若第1熱傳導層之E型硬度為該等上限值以下，則第1熱傳導層之柔軟性提昇，容易抑制於壓縮電磁波吸收片之情形時電磁波吸收性能之降低。若第1熱傳導層之E型硬度為該等下限值以上，則第1熱傳導層之製造變容易。 (E hardness) The E-type hardness defined by JIS K6253 of the first heat conduction layer 11 is preferably 15 or higher, more preferably 17 or higher, and still more preferably 18 or higher. Furthermore, the E-type hardness of the first heat conduction layer 11 is preferably 70 or less, more preferably 65 or less, and still more preferably 60 or less. Moreover, the E-type hardness of the 1st heat conduction layer 11 becomes like this. Preferably it is 15-70, More preferably, it is 17-65, More preferably, it is 18-60. When the E-type hardness of the first heat conduction layer is below these upper limits, the flexibility of the first heat conduction layer is improved, and it is easy to suppress a decrease in electromagnetic wave absorption performance when the electromagnetic wave absorbing sheet is compressed. The manufacture of a 1st heat conduction layer becomes easy that the E-type hardness of a 1st heat conduction layer is more than these lower limits.
＜第1熱傳導層之製造方法＞ 第1熱傳導層並無特別限定，例如可藉由具備以下步驟（A）、及（B）之方法而製造。 步驟（A）：於第1熱傳導層中，將各向異性填充材料沿成為厚度方向之一方向配向而獲得配向成形體之步驟 步驟（B）：將配向成形體切割而製成片狀，從而獲得第1熱傳導層之步驟 以下，對於各步驟進行更詳細之說明。 <Manufacturing method of the first heat conduction layer> The first heat conduction layer is not particularly limited, and can be produced, for example, by a method including the following steps (A) and (B). Step (A): In the first heat conduction layer, the step of aligning the anisotropic filling material in one of the thickness directions to obtain an aligned molded body Step (B): The step of cutting the aligned molded body into a sheet to obtain the first heat conduction layer Hereinafter, each step will be described in more detail.
[步驟（A）] 於步驟（A）中，由包含各向異性填充材料、與成為高分子基質之原料之高分子組成物的第1熱傳導層用組成物而成形配向成形體。該第1熱傳導層用組成物可進而包含非各向異性填充材料。第1熱傳導層用組成物較佳為硬化而成為配向成形體。配向成形體更具體而言可藉由磁場配向製法、流動配向製法而獲得，該等中較佳為磁場配向製法。 [Step (A)] In the step (A), an aligned molded body is formed from the composition for the first heat-conducting layer including the anisotropic filler and the polymer composition that becomes the raw material of the polymer matrix. The composition for the first heat conduction layer may further include an anisotropic filler. The composition for the first heat conduction layer is preferably cured to form an aligned molded body. More specifically, the aligned molded body can be obtained by a magnetic field alignment method and a flow alignment method, and among these, a magnetic field alignment method is preferable.
（磁場配向製法） 於磁場配向製法中，將包含於硬化後成為高分子基質之液狀高分子組成物、與各向異性填充材料及視需要之非各向異性填充材料之第1熱傳導層用組成物注入至模具等之內部後放置於磁場，使各向異性填充材料沿磁場配向後，使高分子組成物硬化，藉此獲得配向成形體。作為配向成形體，較佳為塊狀者。 又，於模具內部中，亦可於與第1熱傳導層用組成物接觸之部分配置剝離膜。剝離膜例如可使用剝離性良好之樹脂膜、或藉由剝離劑等對單面進行了剝離處理之樹脂膜。藉由使用剝離膜，配向成形體可容易地自模具脫模。 (Magnetic field alignment method) In the magnetic field alignment method, inject the composition for the first heat conduction layer including the liquid polymer composition that becomes the polymer matrix after hardening, the anisotropic filler, and the optional non-anisotropic filler into the mold After placing them in a magnetic field, the anisotropic filling material is aligned along the magnetic field, and the polymer composition is hardened, thereby obtaining an aligned molded body. As an alignment molded body, a block-like one is preferable. Moreover, in the inside of a mold, you may arrange|position a peeling film in the part which contacts with the composition for 1st heat conduction layers. As the release film, for example, a resin film having good releasability, or a resin film that has been subjected to a release treatment on one side with a release agent or the like can be used. By using a release film, the alignment molded body can be easily released from the mold.
作為於磁場配向製法中所使用之第1熱傳導層用組成物之黏度，為了進行磁場配向，較佳為10～300 Pa･s。藉由設為10 Pa･s以上，各向異性填充材料或非各向異性填充材料難以沈澱。又，藉由設為300 Pa･s以下，流動性變得良好，藉由磁場使各向異性填充材料適當地配向，亦不會產生配向需要時間過多之不良情況。再者，所謂黏度，係使用旋轉黏度計（布氏黏度計DV-E，轉軸SC4-14）於25℃，以10 rpm之旋轉速度測定之黏度。 其中，於使用難以沈澱之各向異性填充材料或非各向異性填充材料，或組合沈澱防止劑等添加劑之情形時，第1熱傳導層用組成物之黏度可未達10 Pa･s。 The viscosity of the composition for the first heat conduction layer used in the magnetic field alignment method is preferably 10 to 300 Pa·s for magnetic field alignment. By setting it to 10 Pa･s or more, it becomes difficult for an anisotropic filling material or an anisotropic filling material to settle. Moreover, by setting it to 300 Pa·s or less, the fluidity becomes good, and the anisotropic filling material is properly aligned by a magnetic field, and there is no problem that too much time is required for alignment. Furthermore, the so-called viscosity is the viscosity measured at 25°C with a rotational speed of 10 rpm using a rotational viscometer (Brookfield viscometer DV-E, spindle SC4-14). Among them, when using an anisotropic or non-anisotropic filler that is difficult to precipitate, or in combination with additives such as an anti-sedimentation agent, the viscosity of the composition for the first heat conduction layer may be less than 10 Pa･s.
於磁場配向製法中，作為用以施加磁力線之磁力線產生源，可列舉：超導磁鐵、永久磁鐵、電磁鐵等，就可產生磁通密度較高之磁場的方面而言，較佳為超導磁鐵。自該等磁力線產生源所產生之磁場之磁通密度較佳為1～30特士拉。若將磁通密度設為1特士拉以上，則由碳材料等構成之上述之各向異性填充材料可容易地配向。又，藉由為30特士拉以下，可實用化地製造。 高分子組成物之硬化可藉由加熱而進行，例如，可以50～150℃左右之溫度進行。又，加熱時間例如為10分鐘～3小時左右。 In the magnetic field alignment method, as the source of magnetic force lines for applying magnetic force lines, there are superconducting magnets, permanent magnets, electromagnets, etc., and superconducting magnets are preferred in terms of generating a magnetic field with a high magnetic flux density. magnet. The magnetic flux density of the magnetic field generated from these magnetic flux generation sources is preferably 1-30 Tesla. If the magnetic flux density is set to 1 Tesla or more, the above-mentioned anisotropic filler made of a carbon material or the like can be easily aligned. In addition, it can be manufactured practically by being 30 Tesla or less. The hardening of the polymer composition can be performed by heating, for example, at a temperature of about 50-150°C. Moreover, heating time is about 10 minutes - 3 hours, for example.
（流動配向製法） 於流動配向製法中，可對第1熱傳導層用組成物施加剪力，製造各向異性填充材料配向於表面方向之預備片，將其複數之積層而製造積層塊，將該積層塊作為配向成形體。 更具體而言，於流動配向製法中，首先，製備第1熱傳導層用組成物，其係於高分子組成物混入各向異性填充材料、及視需要混入非各向異性填充材料、各種添加劑並進行攪拌，使所混入之固形物均勻分散而成者。此處，高分子組成物所使用之高分子化合物可包含於常溫（23℃）為液狀之高分子化合物，亦可包含於常溫下為固體狀之高分子化合物。又，高分子組成物可含有塑化劑。 第1熱傳導層用組成物具有較高之黏度以便於伸長為片狀時施加剪力，第1熱傳導層用組成物之黏度具體而言較佳為3～50 Pa･s。第1熱傳導層用組成物為了獲得上述黏度，較佳為摻合溶劑。 (flow alignment method) In the flow alignment manufacturing method, a shear force can be applied to the composition for the first heat conduction layer to manufacture a preparatory sheet in which the anisotropic filler material is aligned in the surface direction, and a plurality of these can be laminated to manufacture a laminated block, and the laminated block can be used as an alignment molding body. More specifically, in the flow alignment method, first, a composition for the first heat conduction layer is prepared, which is mixed with an anisotropic filler, an anisotropic filler, various additives and Stirring to disperse the mixed solids evenly. Here, the polymer compound used for the polymer composition may include a polymer compound that is liquid at normal temperature (23° C.), or a polymer compound that is solid at normal temperature. Also, the polymer composition may contain a plasticizer. The composition for the first heat conduction layer has a high viscosity so that shear force can be applied when stretched into a sheet shape, and the viscosity of the composition for the first heat conduction layer is specifically preferably 3 to 50 Pa･s. In order to obtain the above-mentioned viscosity, the composition for the first heat conduction layer is preferably blended with a solvent.
其次，一面對第1熱傳導層用組成物賦予剪力一面使其扁平地伸長而成形為片狀（預備片）。藉由施加剪力，可使各向異性填充材料配向於剪切方向。作為片材之成形手段，例如可藉由棒式塗佈機或刮刀等塗佈用敷料器、或擠出成形或自噴嘴噴出等，於基材膜上塗佈第1熱傳導層用組成物，其後視需要進行乾燥，或使第1熱傳導層用組成物半硬化。預備片之厚度較佳為50～250 μm左右。於預備片中，各向異性填充材於沿片材之表面方向之一個方向配向。 繼而，可將複數之預備片以配向方向相同之方式重疊而積層後，視需要藉由加熱、紫外線照射等使第1熱傳導層用組成物硬化，且藉由熱壓等使預備片彼此接著，由此形成積層塊，將該積層塊作為配向成形體。 Next, while applying shear force to the composition for the first heat conduction layer, it is stretched flat and formed into a sheet (preparation sheet). By applying a shear force, the anisotropic filling material can be aligned in the shear direction. As means for forming the sheet, for example, the composition for the first heat-conducting layer can be coated on the base film by a coating applicator such as a bar coater or a doctor blade, extrusion molding, or spraying from a nozzle. Thereafter, drying is performed as necessary, or the composition for the first heat conduction layer is semi-hardened. The thickness of the preparation sheet is preferably about 50-250 μm. In the prepared sheet, the anisotropic filler is aligned in one direction along the surface direction of the sheet. Next, a plurality of preliminary sheets can be stacked so that the alignment direction is the same, and if necessary, the composition for the first heat-conducting layer is cured by heating, ultraviolet radiation, etc., and the preliminary sheets are bonded to each other by hot pressing, etc. Thereby, a build-up block was formed, and this build-up block was used as an alignment molding.
[步驟（B）] 於步驟（B）中，將藉由步驟（A）所獲得之配向成形體垂直於各向異性填充材料配向之方向進行切片等而切斷，獲得第1熱傳導層。切片例如可藉由剪切刀片等進行。 對於所獲得之第1熱傳導層之表面，可視需要進行研磨。表面之研磨例如可使用研磨紙而進行。作為研磨紙，可列舉研磨粒之平均粒徑（D50）為3～60 μm者。 [Step (B)] In the step (B), the aligned molded body obtained in the step (A) is sliced perpendicular to the direction in which the anisotropic filler is aligned, and then cut to obtain the first heat conduction layer. Slicing can be performed, for example, with a shear blade or the like. The surface of the obtained first heat conduction layer may be polished as necessary. Polishing of the surface can be performed using abrasive paper, for example. As abrasive paper, the thing whose average particle diameter (D50) of abrasive grain is 3-60 micrometers is mentioned.
＜第2熱傳導層＞ 第2熱傳導層12係於具有透孔之電磁波吸收構件13含浸有熱傳導性材料之層。 ＜Second heat transfer layer＞ The second heat conduction layer 12 is a layer in which the electromagnetic wave absorbing member 13 having through holes is impregnated with a heat conduction material.
（具有透孔之電磁波吸收構件） 本發明之具有透孔之電磁波吸收構件13係具有電磁波吸收性能之片狀構件，只要是形成有可使熱傳導性材料含浸於構件內部之透孔的構件，就沒有特別限制。其中，作為具有透孔之電磁波吸收構件13，較佳為至少於具有透孔之基材之一個表面具有金屬層之電磁波吸收構件。 作為上述基材，較佳為織布、不織布、針織物（knit）等布料。作為上述電磁波吸收構件，可例示：於織布之至少一面具有金屬層之導電性織布、於不織布之至少一面具有金屬層之導電性不織布、於針織物之至少一面具有金屬層之導電性針織物。該等中更佳為於不織布之至少一面具有金屬層之導電性不織布、及於針織物之至少一面具有金屬層之導電性針織物。 (Electromagnetic wave absorbing member with through holes) The electromagnetic wave absorbing member 13 with through holes of the present invention is a sheet member having electromagnetic wave absorbing performance, and is not particularly limited as long as it has through holes for impregnating the inside of the member with thermally conductive material. Among them, as the electromagnetic wave absorbing member 13 having through holes, an electromagnetic wave absorbing member having a metal layer on at least one surface of the substrate having through holes is preferable. As said base material, cloth, such as a woven fabric, a nonwoven fabric, and a knitted fabric (knit), are preferable. Examples of the electromagnetic wave absorbing member include: a conductive woven fabric having a metal layer on at least one side of a woven fabric, a conductive nonwoven fabric having a metal layer on at least one side of a nonwoven fabric, and a conductive knitted fabric having a metal layer on at least one side of a knitted fabric. things. Among these, conductive nonwoven fabric having a metal layer on at least one side of the nonwoven fabric, and conductive knitted fabric having a metal layer on at least one side of the knitted fabric are more preferable.
（導電性不織布） 本發明之導電性不織布的至少一面之片電阻較佳為10 Ω/□，更佳為15 Ω/□以上，進而較佳為20 Ω/□以上。另一方面，導電性不織布之至少一面之片電阻較佳為100 Ω/□以下，更佳為50 Ω/□以下，進而較佳為30 Ω/□以下。 又，本發明之導電性不織布的至少一面之片電阻較佳為10～100 Ω/□，更佳為15～50 Ω/□，進而較佳為20～30 Ω/□。若導電性不織布之片電阻為此種範圍，則電磁波之低反射性提昇，電磁波吸收性能提高。 該片電阻係導電性不織布之金屬層側之表面上的表面電阻值，可使用表面電阻計（例如，MITSUBISHI CHEMICAL ANALYTECH公司製造（商品名：Loresta-EP），或其同等品）藉由四端子法進行測定。於測定時使用ESP探針（MCP-TP08P或其同等品），使探針所有之針均勻地壓抵於試樣上而進行測定。 (conductive non-woven fabric) The sheet resistance of at least one side of the conductive nonwoven fabric of the present invention is preferably 10 Ω/□, more preferably 15 Ω/□ or more, still more preferably 20 Ω/□ or more. On the other hand, the sheet resistance of at least one side of the conductive nonwoven fabric is preferably at most 100 Ω/□, more preferably at most 50 Ω/□, still more preferably at most 30 Ω/□. In addition, the sheet resistance of at least one side of the conductive nonwoven fabric of the present invention is preferably 10 to 100 Ω/□, more preferably 15 to 50 Ω/□, and still more preferably 20 to 30 Ω/□. When the sheet resistance of the conductive nonwoven fabric is in such a range, the low reflectivity of electromagnetic waves is improved, and the electromagnetic wave absorption performance is improved. The sheet resistance is the surface resistance value on the surface of the metal layer side of the conductive nonwoven fabric, and can be measured by a surface resistance meter (for example, manufactured by MITSUBISHI CHEMICAL ANALYTECH Co., Ltd. (trade name: Loresta-EP), or its equivalent) with four terminals. method to measure. Use the ESP probe (MCP-TP08P or its equivalent) during the measurement, so that all the needles of the probe are evenly pressed against the sample for measurement.
構成導電性不織布之不織布只要是由纖維構成者，就沒有特別限制。只要不顯著地損及本發明之效果，不織布亦可包含纖維以外之成分、物質等。於該情形時，不織布中之纖維之合計量例如為80質量%以上，較佳為90質量%以上，更佳為95質量%以上，進而較佳為99質量%以上，通常未達100質量%。The nonwoven fabric constituting the conductive nonwoven fabric is not particularly limited as long as it is composed of fibers. As long as the effect of the present invention is not significantly impaired, the nonwoven fabric may contain components, substances, etc. other than fibers. In this case, the total amount of fibers in the nonwoven fabric is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 99% by mass or more, and usually less than 100% by mass .
不織布之層構成並無特別限制。不織布可由單獨1種不織布構成，亦可由2種以上之不織布多種組合而成。The layer composition of the nonwoven fabric is not particularly limited. The non-woven fabric can be composed of a single type of non-woven fabric, or can be composed of two or more types of non-woven fabrics.
構成纖維之素材只要是纖維狀或可成形為纖維狀之素材，就沒有特別限制。作為纖維之素材，例如可列舉：聚對苯二甲酸乙二酯（PET）、聚對苯二甲酸丁二酯（PBT）、聚萘二甲酸乙二酯、改質聚酯等聚酯系樹脂；聚乙烯（PE）樹脂、聚丙烯（PP）樹脂、聚苯乙烯樹脂、環狀烯烴系樹脂等聚烯烴類樹脂；聚氯乙烯、聚偏二氯乙烯等乙烯系樹脂；聚乙烯醇縮丁醛（PVB）等聚乙烯醇縮醛樹脂；聚醚醚酮（PEEK）樹脂、聚碸（PSF）樹脂、聚醚碸（PES）樹脂、聚碳酸酯（PC）樹脂、聚醯胺樹脂、聚醯亞胺樹脂、丙烯酸樹脂、三乙醯纖維素（TAC）樹脂、聚芳酯（PAR）樹脂、液晶聚合物（LCP）等合成樹脂、天然樹脂、纖維素、玻璃等。於該等中，作為纖維之素材，較佳為聚對苯二甲酸乙二酯（PET）、聚芳酯（PAR）樹脂、液晶聚合物（LCP）。 纖維可由單獨1種纖維素材構成，亦可由2種以上之纖維素材多種組合而成。 The material constituting the fiber is not particularly limited as long as it is fibrous or fibrous. Examples of fiber materials include polyester-based resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate, and modified polyester. ;Polyolefin resins such as polyethylene (PE) resin, polypropylene (PP) resin, polystyrene resin, and cyclic olefin resin; vinyl resin such as polyvinyl chloride and polyvinylidene chloride; polyvinyl butyrate Aldehyde (PVB) and other polyvinyl acetal resin; polyetheretherketone (PEEK) resin, polyether (PSF) resin, polyether ketone (PES) resin, polycarbonate (PC) resin, polyamide resin, poly Synthetic resins such as imide resin, acrylic resin, triacetyl cellulose (TAC) resin, polyarylate (PAR) resin, liquid crystal polymer (LCP), natural resin, cellulose, glass, etc. Among them, polyethylene terephthalate (PET), polyarylate (PAR) resin, and liquid crystal polymer (LCP) are preferable as the material of the fiber. The fiber may be composed of a single fiber material, or may be composed of multiple combinations of two or more fiber materials.
不織布之單位面積重量（基重）例如為0.5～200 g/m 2，較佳為0.5～50 g/m 2，更佳為1～10 g/m 2。 不織布之厚度例如為1～500 μm，較佳為5～100 μm，更佳為10～30 μm。 若不織布之單位面積重量及厚度為此種範圍，則容易調整至下述之密度範圍。 The weight per unit area (basis weight) of the nonwoven fabric is, for example, 0.5-200 g/m 2 , preferably 0.5-50 g/m 2 , more preferably 1-10 g/m 2 . The thickness of the nonwoven fabric is, for example, 1-500 μm, preferably 5-100 μm, more preferably 10-30 μm. If the weight per unit area and thickness of the nonwoven fabric are in this range, it is easy to adjust to the following density range.
不織布之密度較佳為2.0×10 4～8.0×10 5g/m 3，更佳為5.0×10 4～6.0×10 5g/m 3，進而較佳為1.0×10 5～5.0×10 5g/m 3。若不織布之密度為此種範圍，則容易吸收電磁波，電磁波吸收性能提高。 若不織布之密度為如上所述之範圍，則電磁波吸收性能提高之理由未明，但認為藉由使用密度為特定範圍之不織布，金屬不僅附著於不織布表面，還滲入至不織布內部，因此電波吸收特性（特別是吸收性）提昇。 The density of the nonwoven fabric is preferably 2.0×10 4 to 8.0×10 5 g/m 3 , more preferably 5.0×10 4 to 6.0×10 5 g/m 3 , and still more preferably 1.0×10 5 to 5.0×10 5 g/m 3 . When the density of the nonwoven fabric is in such a range, electromagnetic waves are easily absorbed, and the electromagnetic wave absorption performance is improved. If the density of the non-woven fabric is in the above range, the reason why the electromagnetic wave absorption performance is improved is not clear, but it is considered that by using a non-woven fabric with a density in a specific range, the metal not only adheres to the surface of the non-woven fabric, but also penetrates into the interior of the non-woven fabric. Therefore, the electromagnetic wave absorption performance ( Especially absorbency) improved.
導電性金屬層為於不織布之至少一面具有金屬層之導電性不織布。 金屬層只要是包含金屬作為素材之層，就沒有特別限制。只要不顯著地損及本發明之效果，金屬層亦可包含除金屬以外之成分。於該情形時，金屬層中之金屬量例如為80質量%以上，較佳為90質量%以上，更佳為95質量%以上，進而較佳為99質量%以上，通常未達100質量%。 The conductive metal layer is a conductive non-woven fabric having a metal layer on at least one side of the non-woven fabric. The metal layer is not particularly limited as long as it contains metal as a material. As long as the effect of the present invention is not significantly impaired, the metal layer may also contain components other than metal. In this case, the amount of metal in the metal layer is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 99% by mass or more, and usually less than 100% by mass.
於本發明中，作為構成金屬層之金屬，只要可發揮電波吸收特性，就沒有特別限制。作為金屬，例如可列舉：鎳、鉬、鉻、鈦、鋁、金、銀、銅、鋅、錫、鉑、鐵、銦、包含該等金屬之合金、及包含該等金屬或該等金屬之合金的金屬化合物等。作為金屬層，就抑制導電性不織布之電波吸收特性之經時變化（耐久性）之觀點而言，較佳為含有選自由鎳、鉬、鉻、鈦、及鋁所組成之群中之至少1種金屬元素。In the present invention, the metal constituting the metal layer is not particularly limited as long as it can exhibit radio wave absorption characteristics. Examples of metals include nickel, molybdenum, chromium, titanium, aluminum, gold, silver, copper, zinc, tin, platinum, iron, indium, alloys containing these metals, and alloys containing these metals or these metals. Alloy metal compounds, etc. As the metal layer, it is preferable to contain at least 1 element selected from the group consisting of nickel, molybdenum, chromium, titanium, and aluminum from the viewpoint of suppressing the change over time (durability) of the radio wave absorption characteristics of the conductive nonwoven fabric. metal elements.
於上述含有選自由鎳、鉬、鉻、鈦、及鋁所組成之群中之至少1種金屬元素的情形時，其含量（合計含量）例如為10質量%以上，較佳為20質量%以上，更佳為40質量%以上，進而較佳為60質量%以上，通常未達100質量%。When at least one metal element selected from the group consisting of nickel, molybdenum, chromium, titanium, and aluminum is contained, the content (total content) thereof is, for example, 10% by mass or more, preferably 20% by mass or more , more preferably at least 40% by mass, further preferably at least 60% by mass, and usually less than 100% by mass.
作為金屬層，就耐久性、容易調整片電阻之觀點而言，較佳為使用含有鉬之金屬層。作為金屬層中之鉬之含量，就進一步提高耐久性之觀點而言，較佳為5質量%以上，更佳為7質量%以上，進而較佳為9質量%以上，進而較佳為11質量%以上，進而較佳為13質量%以上，進而較佳為15質量%以上，進而較佳為16質量%以上。又，作為上述鉬之含量，就容易調整表面電阻值之觀點而言，較佳為70質量%以下，更佳為30質量%以下，進而較佳為25質量%以下，進而較佳為20質量%以下。As the metal layer, it is preferable to use a metal layer containing molybdenum from the viewpoint of durability and easy adjustment of sheet resistance. The content of molybdenum in the metal layer is preferably at least 5% by mass, more preferably at least 7% by mass, further preferably at least 9% by mass, and still more preferably at least 11% by mass, from the viewpoint of further improving durability. % or more, more preferably 13 mass % or more, further preferably 15 mass % or more, further preferably 16 mass % or more. In addition, the molybdenum content is preferably at most 70% by mass, more preferably at most 30% by mass, further preferably at most 25% by mass, and still more preferably at most 20% by mass, from the viewpoint of easy adjustment of the surface resistance value. %the following.
於金屬層含有鉬之情形時，更佳為進而含有鎳及鉻。藉由於金屬層中除鉬以外亦含有鎳及鉻，可製成耐久性更優異之導電性不織布。作為含有鎳、鉻及鉬之合金，例如可列舉：赫史特合金B-2、B-3、C-4、C-2000、C-22、C-276、G-30、N、W、X等各種等級。When the metal layer contains molybdenum, it is more preferable to further contain nickel and chromium. By containing nickel and chromium in addition to molybdenum in the metal layer, a conductive nonwoven fabric with better durability can be produced. Examples of alloys containing nickel, chromium, and molybdenum include: Hoechst alloys B-2, B-3, C-4, C-2000, C-22, C-276, G-30, N, W, X and other grades.
於金屬層含有鉬、鎳及鉻之情形時，作為該等之含量，就獲得耐久性優異之導電性不織布之觀點而言，較佳為如下所示地調整。 較佳為鉬之含量為5質量%以上，鎳之含量為40質量%以上，鉻之含量為1質量%以上。藉由使鉬、鎳及鉻之含量為上述範圍，可製成耐久性更優異之導電性不織布。作為上述鉬、鎳及鉻之含量，更佳為鉬含量為7質量%以上，鎳含量為45質量%以上，鉻含量為3質量%以上。作為上述鉬、鎳及鉻之含量，進而較佳為鉬含量為9質量%以上，鎳含量為47質量%以上，鉻含量為5質量%以上。作為上述鉬、鎳及鉻之含量，進而更佳為鉬含量為11質量%以上，鎳含量為50質量%以上，鉻含量為10質量%以上。作為上述鉬、鎳及鉻之含量，特佳為鉬含量為13質量%以上，鎳含量為53質量%以上，鉻含量為12質量%以上。作為上述鉬、鎳及鉻之含量，尤較佳為鉬含量為15質量%以上，鎳含量為55質量%以上，鉻含量為15質量%以上。作為上述鉬、鎳及鉻之含量，最佳為鉬含量為16質量%以上，鎳含量為57質量%以上，鉻含量為16質量%以上。又，作為上述鎳之含量，較佳為80質量%以下，更佳為70質量%以下，進而較佳為65質量%以下。作為上述鉻含量，較佳為50質量%以下，更佳為40質量%以下，進而較佳為35質量%以下。 When the metal layer contains molybdenum, nickel, and chromium, these contents are preferably adjusted as follows from the viewpoint of obtaining a conductive nonwoven fabric excellent in durability. Preferably, the content of molybdenum is 5% by mass or more, the content of nickel is 40% by mass or more, and the content of chromium is 1% by mass or more. By making the content of molybdenum, nickel, and chromium into the above-mentioned range, a conductive nonwoven fabric more excellent in durability can be obtained. As the content of molybdenum, nickel, and chromium, it is more preferable that the molybdenum content is 7% by mass or more, the nickel content is 45% by mass or more, and the chromium content is 3% by mass or more. The molybdenum, nickel, and chromium contents are more preferably at least 9% by mass, at least 47% by mass of nickel, and at least 5% by mass of chromium. The molybdenum, nickel, and chromium contents are more preferably at least 11% by mass, at least 50% by mass of nickel, and at least 10% by mass of chromium. The molybdenum, nickel, and chromium contents are particularly preferably at least 13% by mass, at least 53% by mass of nickel, and at least 12% by mass of chromium. As the content of molybdenum, nickel and chromium, it is particularly preferable that the molybdenum content is 15% by mass or more, the nickel content is 55% by mass or more, and the chromium content is 15% by mass or more. As the content of molybdenum, nickel, and chromium, it is preferable that the molybdenum content is 16% by mass or more, the nickel content is 57% by mass or more, and the chromium content is 16% by mass or more. Moreover, as content of the said nickel, Preferably it is 80 mass % or less, More preferably, it is 70 mass % or less, More preferably, it is 65 mass % or less. The chromium content is preferably at most 50% by mass, more preferably at most 40% by mass, and still more preferably at most 35% by mass.
金屬層亦可含有除上述鉬、鎳及鉻以外之金屬。作為此種金屬，例如可列舉：鐵、鈷、鎢、錳、鈦等。於金屬層含有鉬、鎳及鉻之情形時，作為上述除鉬、鎳及鉻以外之金屬之合計含量，就金屬層之耐久性之觀點而言，較佳為45質量%以下，更佳為40質量%以下，進而較佳為35質量%以下，進而更佳為30質量%以下，特佳為25質量%以下，尤佳為23質量%以下。上述除鉬、鎳及鉻以外之金屬之合計含量例如為1質量%以上。The metal layer may also contain metals other than the aforementioned molybdenum, nickel, and chromium. As such a metal, iron, cobalt, tungsten, manganese, titanium etc. are mentioned, for example. When the metal layer contains molybdenum, nickel, and chromium, the total content of the metals other than molybdenum, nickel, and chromium is preferably at most 45% by mass, more preferably at most, from the viewpoint of durability of the metal layer. 40 mass % or less, more preferably 35 mass % or less, still more preferably 30 mass % or less, particularly preferably 25 mass % or less, especially preferably 23 mass % or less. The total content of the above-mentioned metals other than molybdenum, nickel, and chromium is, for example, 1% by mass or more.
於金屬層含有鐵之情形時，就金屬層之耐久性之觀點而言，鐵之含量較佳為25質量%以下，更佳為20質量%以下，進而較佳為15質量%以下，較佳為1質量%以上。於金屬層含有鈷及/或錳之情形時，就金屬層之耐久性之觀點而言，分別獨立，含量較佳為5質量%以下，更佳為4質量%以下，進而較佳為3質量%以下，較佳為0.1質量%以上。於上述金屬層含有鎢之情形時，就金屬層之耐久性之觀點而言，含量較佳為8質量%以下，更佳為6質量%以下，進而較佳為4質量%以下，較佳為1質量%以上。When the metal layer contains iron, the iron content is preferably at most 25% by mass, more preferably at most 20% by mass, still more preferably at most 15% by mass, and more preferably not more than 15% by mass from the viewpoint of durability of the metal layer. 1% by mass or more. When the metal layer contains cobalt and/or manganese, from the viewpoint of the durability of the metal layer, the content is independently preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass % or less, preferably 0.1% by mass or more. When the above-mentioned metal layer contains tungsten, from the viewpoint of the durability of the metal layer, the content is preferably at most 8% by mass, more preferably at most 6% by mass, still more preferably at most 4% by mass, more preferably 1% by mass or more.
金屬層亦可含有矽等半金屬元素或碳。金屬層中之矽等半金屬元素及碳之含量分別獨立，較佳為1質量%以下，更佳為0.5質量%以下。於金屬層含有矽等半金屬元素及碳中之一者或兩者之情形時，該等含量較佳為合計0.01質量%以上。The metal layer may also contain semi-metal elements such as silicon or carbon. The contents of semi-metal elements such as silicon and carbon in the metal layer are independent, preferably 1% by mass or less, more preferably 0.5% by mass or less. When the metal layer contains one or both of semi-metallic elements such as silicon and carbon, these contents are preferably at least 0.01% by mass in total.
作為構成金屬層之元素之附著量，就將片電阻設為期望之範圍之觀點而言，例如為5～200 μg/cm 2，較佳為50～150 μg/cm 2，更佳為80～120 μg/cm 2。構成金屬層之元素之附著量係指金屬元素與半金屬元素之合計之附著量。 元素之附著量可藉由螢光X射線分析而求出。具體而言，使用掃描式螢光X射線分析裝置（例如，Rigaku公司製造之掃描式螢光X射線分析裝置 ZSX PrimusIII+或同等品）將加速電壓設為50 kV，加速電流設為50 mA，積分時間設為60秒而進行分析。測定出待測定對象之成分之Kα射線的X射線強度，除峰值位置以外亦測定出背景位置之強度，從而可算出淨強度。根據預先製作之校準曲線，可將所測出之強度值換算為附著量。對同一樣品進行5次分析，將其平均值作為附著量。 The adhesion amount of the elements constituting the metal layer is, for example, 5 to 200 μg/cm 2 , preferably 50 to 150 μg/cm 2 , more preferably 80 to 120 μg/cm 2 . The adhesion amount of elements constituting the metal layer refers to the total adhesion amount of metal elements and semi-metal elements. The amount of attached elements can be determined by fluorescent X-ray analysis. Specifically, using a scanning fluorescent X-ray analyzer (for example, scanning fluorescent X-ray analyzer ZSX PrimusIII+ manufactured by Rigaku Corporation or equivalent), set the accelerating voltage to 50 kV, the accelerating current to 50 mA, and integrate The time was set to 60 seconds and analyzed. The X-ray intensity of the Kα ray of the component to be measured is measured, and the intensity of the background position is also measured in addition to the peak position, so that the net intensity can be calculated. According to the pre-made calibration curve, the measured strength value can be converted into the adhesion amount. The same sample was analyzed 5 times, and the average value was used as the adhesion amount.
金屬層之層構成並無特別限制。金屬層可由單獨1種金屬層構成，亦可由2種以上之金屬層複數種組合而成。The layer composition of the metal layer is not particularly limited. The metal layer may consist of a single metal layer, or may consist of a combination of two or more metal layers.
導電性不織布可藉由包含使金屬附著於不織布之表面之步驟的方法而獲得。於除金屬層以外亦具有其他層（例如障壁層等）之情形時，可進而藉由包含使其他層之構成元素附著於不織布之表面、金屬層之表面等之步驟的方法而獲得。 上述附著例如可藉由濺鍍法、真空蒸鍍法、離子鍍覆法、化學蒸鍍法、脈衝雷射沈積法等進行。於該等中，就膜厚控制性、電波吸收特性等觀點而言，較佳為濺鍍法。作為濺鍍法，並無特別限定，例如可列舉：直流磁控濺鍍、高頻磁控濺鍍及離子束濺鍍等。又，濺鍍裝置可為分批方式，亦可為輥對輥方式。 藉由實行使金屬附著於不織布之一個表面的步驟，而可獲得於一面具有金屬層之導電性不織布。又，藉由實行使金屬附著於不織布之兩面之步驟，而可獲得於正反兩面具有金屬層之導電性不織布。 The conductive nonwoven fabric can be obtained by a method including the step of attaching metal to the surface of the nonwoven fabric. In the case of having other layers (such as a barrier layer, etc.) in addition to the metal layer, it can be obtained by a method including a step of attaching constituent elements of other layers to the surface of the nonwoven fabric or the surface of the metal layer. The above-mentioned attachment can be performed, for example, by sputtering, vacuum evaporation, ion plating, chemical evaporation, pulsed laser deposition, and the like. Among them, the sputtering method is preferable from the viewpoints of film thickness controllability and radio wave absorption characteristics. Although it does not specifically limit as a sputtering method, For example, DC magnetron sputtering, high frequency magnetron sputtering, ion beam sputtering, etc. are mentioned. In addition, the sputtering apparatus may be a batch system or a roll-to-roll system. A conductive nonwoven fabric having a metal layer on one side can be obtained by carrying out the step of attaching metal to one surface of the nonwoven fabric. Also, by carrying out the step of attaching metal to both sides of the nonwoven fabric, a conductive nonwoven fabric having a metal layer on both front and back sides can be obtained.
金屬層於其至少一面上具有障壁層，較佳為於兩個面上具有障壁層。 障壁層只要是可保護金屬層，抑制其劣化之層，就沒有特別限制，較佳為其組成與金屬層不同。作為障壁層之素材，例如可列舉：金屬、半金屬、合金、金屬化合物、半金屬化合物等。只要不顯著地損及本發明之效果，障壁層亦可包含除上述素材以外之成分。於該情形時，障壁層中之上述素材量例如為80質量%以上，較佳為90質量%以上，更佳為95質量%以上，進而較佳為99質量%以上，通常未達100質量%。 The metal layer has a barrier layer on at least one side thereof, preferably has a barrier layer on both sides. The barrier layer is not particularly limited as long as it can protect the metal layer and suppress its deterioration, and preferably has a composition different from that of the metal layer. Examples of materials for the barrier layer include metals, semimetals, alloys, metal compounds, and semimetal compounds. As long as the effect of the present invention is not significantly impaired, the barrier layer may also contain components other than the above-mentioned materials. In this case, the amount of the above-mentioned material in the barrier layer is, for example, 80 mass % or more, preferably 90 mass % or more, more preferably 95 mass % or more, further preferably 99 mass % or more, usually less than 100 mass % .
作為適合用於障壁層之金屬，例如可列舉：鎳、鈦、鋁、鈮、鈷等。作為適合用於障壁層之半金屬，例如可列舉：矽、鍺、銻、鉍等。As a metal suitably used for a barrier layer, nickel, titanium, aluminum, niobium, cobalt, etc. are mentioned, for example. Examples of semimetals suitable for use in the barrier layer include silicon, germanium, antimony, and bismuth.
作為用於障壁層之金屬化合物及半金屬化合物之具體例，可列舉：SiO 2、SiOx（X表示氧化數，0＜X＜2）、Al 2O 3、MgAl 2O 4、CuO、CuN、TiO 2、TiN、AZO（摻鋁氧化鋅）等。 Specific examples of metal compounds and semimetal compounds used in the barrier layer include: SiO 2 , SiOx (X represents the oxidation number, 0<X<2), Al 2 O 3 , MgAl 2 O 4 , CuO, CuN, TiO 2 , TiN, AZO (aluminum-doped zinc oxide), etc.
障壁層較佳為含有選自由鎳、矽、鈦、及鋁所組成之群中之至少1種元素。於該等中，較佳為可列舉矽。The barrier layer preferably contains at least one element selected from the group consisting of nickel, silicon, titanium, and aluminum. Among these, silicon is preferably mentioned.
作為構成障壁層之元素之附著量，只要可滿足上述之片電阻，就沒有特別限制。構成障壁層之元素之附著量例如為0.5～15 μg/cm 2，較佳為1～10 μg/cm 2，更佳為2～5 μg/cm 2。所謂構成障壁層之元素之附著量，係指金屬元素與半金屬元素之合計之附著量。 再者，在於金屬層之兩面形成障壁層之情形時，各個障壁層之元素之附著量應處於上述之範圍內。 障壁層之層構成並無特別限制。障壁層可由單獨1種障壁層構成，亦可由2種以上之障壁層多種組合而成。 The amount of the elements constituting the barrier layer is not particularly limited as long as the above-mentioned sheet resistance can be satisfied. The adhesion amount of elements constituting the barrier layer is, for example, 0.5-15 μg/cm 2 , preferably 1-10 μg/cm 2 , more preferably 2-5 μg/cm 2 . The so-called adhesion amount of elements constituting the barrier layer refers to the total adhesion amount of metal elements and semi-metal elements. Furthermore, in the case of forming barrier layers on both sides of the metal layer, the adhesion amount of elements in each barrier layer should be within the above-mentioned range. The composition of the barrier layer is not particularly limited. The barrier layer may be composed of a single type of barrier layer, or may be composed of multiple combinations of two or more types of barrier layers.
又，藉由將上述不織布替換為織布或針織物，可獲得導電性織布及導電性針織物。Moreover, by replacing the above-mentioned nonwoven fabric with a woven fabric or a knitted fabric, a conductive woven fabric and a conductive knitted fabric can be obtained.
導電性織布抑制形成織布之纖維方向之延伸的效果較高，因此於電磁波吸收構件之表面方向之形狀難以變形之方面而言較佳。 又，導電性針織物容易向表面方向變形，因此於獲得例如向立體形狀之追隨性優異之電磁波吸收構件之方面而言較佳。特別是就即便使電磁波吸收構件變形亦難以破損之方面而言，適用於覆蓋極面狀之被附著體、或複數個發熱體之凹凸的用途等。 The conductive woven fabric has a high effect of suppressing the elongation of the fibers forming the woven fabric in the direction of the fabric, so it is preferable in that the shape of the electromagnetic wave absorbing member in the surface direction is hardly deformed. Also, since the conductive knitted fabric is easily deformed in the surface direction, it is preferable in terms of obtaining an electromagnetic wave absorbing member excellent in followability to a three-dimensional shape, for example. In particular, the electromagnetic wave absorbing member is not easily damaged even if it is deformed, and it is suitable for applications such as covering a polar surface-shaped adherend or unevenness of a plurality of heating elements.
（熱傳導性材料） 第2熱傳導層12由電磁波吸收構件13、及含浸於該電磁波吸收構件13中之熱傳導性材料構成。熱傳導性材料包含高分子基質16與絕緣性填料17。 (thermally conductive material) The second heat conduction layer 12 is composed of an electromagnetic wave absorbing member 13 and a heat conductive material impregnated in the electromagnetic wave absorbing member 13 . The thermally conductive material includes a polymer matrix 16 and an insulating filler 17 .
（高分子基質） 作為高分子基質16，可無特別限制地使用在上述第1熱傳導層11中所述之高分子基質18中所說明者。又，較佳之高分子基質之種類亦相同，用以形成高分子基質之高分子組成物、硬化性高分子組成物亦相同。 即，作為高分子基質16，較佳為聚矽氧橡膠，作為形成高分子基質16之高分子組成物（硬化性高分子組成物），較佳為使用包含含烯基之有機聚矽氧烷與氫化有機聚矽氧烷者。 於用以形成高分子基質16之高分子組成物中，亦可包含上述之塑化劑或聚矽氧油。 作為高分子基質之含量，相對於熱傳導性材料總量，較佳為10～50體積%，更佳為25～45體積%。 (polymer matrix) As the polymer matrix 16, those described in the polymer matrix 18 described above for the first heat conduction layer 11 can be used without particular limitation. Also, the type of preferable polymer matrix is the same, and the polymer composition and curable polymer composition used to form the polymer matrix are also the same. That is, as the polymer matrix 16, polysiloxane rubber is preferable, and as the polymer composition (curable polymer composition) forming the polymer matrix 16, it is preferable to use an organopolysiloxane containing an alkenyl group. With hydrogenated organopolysiloxane. The polymer composition used to form the polymer matrix 16 may also contain the aforementioned plasticizer or silicone oil. The content of the polymer matrix is preferably from 10 to 50% by volume, more preferably from 25 to 45% by volume, relative to the total amount of the thermally conductive material.
於高分子基質16中，進而可於不損及作為第2熱傳導層之功能之範圍內摻合各種添加劑。作為添加劑，例如可列舉選自分散劑、偶合劑、黏著劑、難燃劑、抗氧化劑、著色劑、沈澱防止劑等中之至少1種以上。於使硬化性高分子組成物交聯、硬化等情形時，作為添加劑，可摻合促進交聯、硬化之交聯促進劑、硬化促進劑等。Further, various additives can be blended in the polymer matrix 16 within the range that does not impair the function as the second heat conduction layer. As an additive, for example, at least one or more selected from the group consisting of dispersants, coupling agents, adhesives, flame retardants, antioxidants, colorants, and anti-sedimentation agents may be mentioned. When crosslinking and hardening the curable polymer composition, a crosslinking accelerator, a hardening accelerator, etc. for accelerating crosslinking and hardening may be blended as additives.
（絕緣性填料） 作為絕緣性填料17，可適當使用體積電阻率為10 6Ω･cm以上之無機填料。作為絕緣性填料17，例如可列舉：礬土、氧化鎂、氧化鋅、碳化矽、氮化硼、氮化鋁等，其中較佳為礬土。該等絕緣性填料之絕緣性優異，並且熱傳導性亦優異。因此，第2熱傳導層之絕緣性及熱傳導性優異。 絕緣性填料17之縱橫比為2以下，較佳為1.5以下。又，絕緣性填料17之形狀可列舉：球狀、不定形之粉末等。 (Insulating filler) As the insulating filler 17 , an inorganic filler having a volume resistivity of 10 6 Ω·cm or more can be appropriately used. Examples of the insulating filler 17 include alumina, magnesium oxide, zinc oxide, silicon carbide, boron nitride, and aluminum nitride, among which alumina is preferred. These insulating fillers are excellent in insulation and also excellent in thermal conductivity. Therefore, the insulation and thermal conductivity of the second heat conduction layer are excellent. The aspect ratio of the insulating filler 17 is 2 or less, preferably 1.5 or less. In addition, the shape of the insulating filler 17 includes spherical shape, amorphous powder, and the like.
絕緣性填料17之平均粒徑較佳為0.1～200 μm，更佳為0.3～100 μm，進而較佳為0.5～70 μm。 絕緣性填料17較佳為併用平均粒徑為0.1 μm以上5 μm以下之小粒徑絕緣性填料、及平均粒徑為超過5 μm且200 μm以下之大粒徑絕緣性填料。藉由使用平均粒徑不同之絕緣性填料，可提高填充率。 再者，絕緣性填料之平均粒徑可藉由電子顯微鏡等進行觀察而測定。更具體而言，例如可使用電子顯微鏡或光學顯微鏡，測定任意50個絕緣性填料之粒徑，將其平均值（算術平均值）作為平均粒徑。 The average particle diameter of the insulating filler 17 is preferably 0.1-200 μm, more preferably 0.3-100 μm, and still more preferably 0.5-70 μm. The insulating filler 17 is preferably a small particle size insulating filler with an average particle size of 0.1 μm to 5 μm and a large particle size insulating filler with an average particle size of more than 5 μm to 200 μm. The filling rate can be increased by using insulating fillers with different average particle diameters. In addition, the average particle diameter of an insulating filler can be measured by observation with an electron microscope etc. More specifically, for example, the particle diameters of arbitrary 50 insulating fillers can be measured using an electron microscope or an optical microscope, and the average (arithmetic mean) thereof can be defined as the average particle diameter.
作為熱傳導性材料中之絕緣性填料17之含量，就提昇第2熱傳導層之絕緣性及熱傳導性之觀點而言，相對於熱傳導性材料總量，較佳為50～90體積%，更佳為55～75體積%。The content of the insulating filler 17 in the thermally conductive material is preferably 50 to 90% by volume relative to the total amount of the thermally conductive material, more preferably 55-75% by volume.
第2熱傳導層12係如上所述地自靠近第1熱傳導層之側起，由包含高分子基質16及絕緣性填料17之內部絕緣層14、於透孔內包含高分子基質16及絕緣性填料17之電磁波吸收構件13、包含高分子基質16及絕緣性填料17之表面絕緣層15分別連成層狀而構成。 換而言之，第2熱傳導層係將由熱傳導性材料構成之內部絕緣層14、於透孔內包含熱傳導性材料之電磁波吸收構件13、由熱傳導性材料構成之表面絕緣層15依序重疊而成之結構。 藉由內部絕緣層14，可防止第1熱傳導層11與電磁波吸收構件13之導通。內部絕緣層14之厚度例如為1～200 μm，較佳為5～50 μm。 於透孔內包含熱傳導性材料之電磁波吸收構件13之厚度例如為1～500 μm，較佳為5～100 μm，更佳為10～30 μm。 表面絕緣層15之厚度例如為20～2000 μm，較佳為50～1500 μm，更佳為100～1000 μm。 The second heat conduction layer 12 is as described above from the side close to the first heat conduction layer, consisting of the inner insulating layer 14 comprising the polymer matrix 16 and the insulating filler 17, and the polymer matrix 16 and the insulating filler comprising the polymer matrix 16 and the insulating filler in the through holes. The electromagnetic wave absorbing member 13 of 17 and the surface insulating layer 15 including the polymer matrix 16 and the insulating filler 17 are respectively connected in layers to form a structure. In other words, the second heat-conducting layer is formed by sequentially stacking the inner insulating layer 14 made of heat-conductive material, the electromagnetic wave absorbing member 13 containing heat-conductive material in the through hole, and the surface insulating layer 15 made of heat-conductive material. The structure. The internal insulating layer 14 prevents conduction between the first heat conduction layer 11 and the electromagnetic wave absorbing member 13 . The thickness of the inner insulating layer 14 is, for example, 1-200 μm, preferably 5-50 μm. The thickness of the electromagnetic wave absorbing member 13 containing a thermally conductive material in the through hole is, for example, 1-500 μm, preferably 5-100 μm, more preferably 10-30 μm. The thickness of the surface insulating layer 15 is, for example, 20-2000 μm, preferably 50-1500 μm, more preferably 100-1000 μm.
（E硬度） 第2熱傳導層12之由JIS K6253規定之E型硬度較佳為20～100，更佳為30～90，進而較佳為40～80。若第2熱傳導層之E型硬度為此種範圍，則可適當地保護電磁波吸收構件，且容易抑制於壓縮電磁波吸收片之情形時電磁波吸收性能降低。 (E hardness) The E-type hardness defined by JIS K6253 of the second heat conduction layer 12 is preferably 20-100, more preferably 30-90, and still more preferably 40-80. When the E-type hardness of the second heat conduction layer is within such a range, the electromagnetic wave absorbing member can be properly protected, and it is easy to suppress a decrease in electromagnetic wave absorbing performance when the electromagnetic wave absorbing sheet is compressed.
＜電磁波吸收片之製造方法＞ 本發明之電磁波吸收片之製造方法並無特別限定，較佳為具備下述之步驟1～步驟3。 （步驟1）製造第1熱傳導層之步驟 （步驟2）於該第1熱傳導層之一面配置電磁波吸收構件之步驟 （步驟3）將用以形成第2熱傳導層之第2熱傳導層用組成物塗佈於電磁波吸收構件之表面之步驟 ＜Manufacturing method of electromagnetic wave absorbing sheet＞ The manufacturing method of the electromagnetic wave absorbing sheet of the present invention is not particularly limited, but preferably includes the following steps 1 to 3. (Step 1) The step of manufacturing the first heat conduction layer (Step 2) The step of arranging an electromagnetic wave absorbing member on one side of the first heat conduction layer (Step 3) The step of applying the composition for the second heat conduction layer to form the second heat conduction layer on the surface of the electromagnetic wave absorbing member
由於步驟1之製造第1熱傳導層之步驟如上所述，故省略此處之說明。 步驟2係於步驟1中所獲得之第1熱傳導層之一面配置電磁波吸收構件之步驟。於電磁波吸收構件為上述之導電性不織布之情形時，較佳為以金屬層成為與第1熱傳導層相反之側之方式配置導電性不織布。 Since the steps of manufacturing the first heat conduction layer in step 1 are as described above, the description here is omitted. Step 2 is a step of arranging an electromagnetic wave absorbing member on one side of the first heat conduction layer obtained in step 1. When the electromagnetic wave absorbing member is the above-mentioned conductive nonwoven fabric, it is preferable to arrange the conductive nonwoven fabric so that the metal layer is on the side opposite to the first heat conduction layer.
步驟3係於步驟2之後，於電磁波吸收構件之表面塗佈用以形成第2熱傳導層之第2熱傳導層用組成物之步驟。 第2熱傳導層用組成物為包含絕緣性填料17、及成為高分子基質之原料之高分子組成物的組成物。如上所述，作為高分子組成物，較佳為包含含烯基之有機聚矽氧烷與氫化有機聚矽氧烷之硬化性高分子組成物。 第2熱傳導層用組成物之黏度並無特別限定，例如為10～500 Pa･s左右。再者，所謂黏度，係使用旋轉黏度計（布氏黏度計DV-E，轉軸SC4-14）於25℃，以10 rpm之旋轉速度測定之黏度。 Step 3 is a step of coating the composition for the second heat conduction layer for forming the second heat conduction layer on the surface of the electromagnetic wave absorbing member after the step 2. The composition for the second heat conduction layer is a composition including the insulating filler 17 and a polymer composition which becomes a raw material of the polymer matrix. As described above, the polymer composition is preferably a curable polymer composition containing an alkenyl group-containing organopolysiloxane and a hydrogenated organopolysiloxane. The viscosity of the composition for the second heat conduction layer is not particularly limited, and is, for example, about 10 to 500 Pa·s. Furthermore, the so-called viscosity is the viscosity measured at 25°C with a rotational speed of 10 rpm using a rotational viscometer (Brookfield viscometer DV-E, spindle SC4-14).
若於電磁波吸收構件之表面塗佈第2熱傳導層用組成物，則組成物浸透至電磁波吸收構件所具備之透孔，經過一定時間後，組成物自塗佈了組成物之電磁波吸收構件之表面的相反面滲出一部分，到達第1熱傳導層之表面。其後，於第2熱傳導層用組成物包含硬化性高分子組成物之情形時，進行加熱而使其硬化，藉此可於第1熱傳導層上形成第2熱傳導層，從而獲得電磁波吸收片。If the composition for the second heat conduction layer is coated on the surface of the electromagnetic wave absorbing member, the composition penetrates into the through holes of the electromagnetic wave absorbing member, and after a certain period of time, the composition is released from the surface of the electromagnetic wave absorbing member coated with the composition. Part of the opposite side seeps out and reaches the surface of the first heat conduction layer. Thereafter, when the composition for the second heat conduction layer contains a curable polymer composition, it is heated and cured, whereby the second heat conduction layer can be formed on the first heat conduction layer, thereby obtaining an electromagnetic wave absorbing sheet.
以此種方式所獲得之電磁波吸收片之第1熱傳導層與第2熱傳導層密接性良好地固定。 又，本發明之電磁波吸收片具備第1熱傳導層、及具有電磁波吸收構件之第2熱傳導層，具有優異之熱傳導性及電磁波吸收特性。進而，如上所述，本發明之電磁波吸收片係即使進行壓縮電磁波吸收性能亦不易降低者。因此，於例如各種電子機器等中，將其壓縮而配置於發熱體與散熱體之間的用途中，可發揮優異之熱傳導性及電磁波吸收特性。 [實施例] In the electromagnetic wave absorbing sheet thus obtained, the first heat conduction layer and the second heat conduction layer were fixed with good adhesion. Furthermore, the electromagnetic wave absorbing sheet of the present invention includes a first heat conduction layer and a second heat conduction layer having an electromagnetic wave absorbing member, and has excellent heat conductivity and electromagnetic wave absorption characteristics. Furthermore, as described above, the electromagnetic wave absorbing sheet of the present invention is one in which the electromagnetic wave absorbing performance is not easily lowered even if it is compressed. Therefore, for example, in various electronic devices, it can exhibit excellent thermal conductivity and electromagnetic wave absorption characteristics when it is compressed and arranged between a heat generating body and a heat sink. [Example]
以下，藉由實施例對本發明進行更詳細之說明，但本發明並不受該等例任何限定。Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited by these examples.
[E硬度] 自電磁波吸收片之兩面，測定由JIS K6253規定之E型硬度。 將自第1熱傳導層側（表面）測定之E型硬度作為第1熱傳導層之E型硬度，將自第2熱傳導層側（表面）測定之E型硬度作為第2熱傳導層之E型硬度。 [E hardness] The E-type hardness specified in JIS K6253 is measured from both sides of the electromagnetic wave absorbing sheet. The E-type hardness measured from the first heat conduction layer side (surface) is taken as the E-type hardness of the first heat conduction layer, and the E-type hardness measured from the second heat conduction layer side (surface) is taken as the E-type hardness of the second heat conduction layer.
[電阻值比（R1/R2）] 無負載狀態下之電阻值R1相對於50%壓縮狀態下之電阻值R2的電阻值比（R1/R2）係使用非接觸電阻測定器（Napson公司製造之「EC-80P」），藉由說明書中記載之方法而測定。 [Resistance value ratio (R1/R2)] The resistance value ratio (R1/R2) of the resistance value R1 in the no-load state to the resistance value R2 in the 50% compressed state is obtained by using a non-contact resistance tester ("EC-80P" manufactured by Napson Co., Ltd.) Measured by the method described in.
[壓縮率C1、壓縮率C2] 測定自電磁波吸收片之第1熱傳導層側，藉由 3 mm之柱塞以400 g之負載按壓時之第1熱傳導層之壓縮率C1，及自電磁波吸收片之第2熱傳導層側，藉由 3 mm之柱塞以400 g之負載按壓時第2熱傳導層之壓縮率C2。 3 mm之柱塞之前端為 3 mm（直徑為3 mm）之圓柱形狀。 測定藉由數位式測力計（IMADA公司製造之「ZTS-5S」）及電動測定台（IMADA公司製造之「MX-500N-E」）而進行。 [Compression ratio C1, compression ratio C2] Measured from the first heat conduction layer side of the electromagnetic wave absorbing sheet, by Compression ratio C1 of the first heat conduction layer when a 3 mm plunger is pressed with a load of 400 g, and from the side of the second heat conduction layer of the electromagnetic wave absorbing sheet, by The compressibility C2 of the second heat conduction layer when a 3 mm plunger is pressed with a load of 400 g. The front end of the 3 mm plunger is 3 mm (3 mm in diameter) cylindrical shape. The measurement was performed with a digital force gauge ("ZTS-5S" manufactured by IMADA Corporation) and an electric measuring table ("MX-500N-E" manufactured by IMADA Corporation).
[電磁波吸收率] 按照依據IEC62333標準之微帶線法，測定電磁波吸收片50%壓縮狀態下之電磁波吸收率（損耗率）。 具體而言，將如圖2所示之電阻值測定之方法變更如下而進行測定。即，於電阻值測定中，將電磁波吸收片配置於2個按壓板（材質為聚碳酸酯樹脂，厚度為3 mm）之間，將其中一個按壓板替換為形成有阻抗為50 Ω之微帶線之基板，於按壓板與基板之間配置電磁波吸收片。此時，將按壓板與基板之間隔調整為電磁波吸收片之初始厚度之50%。又，電磁波吸收片配置為第2熱傳導層側朝向基板側。 其次，自網路分析儀（惠普製作之E8361A）向微帶線入射0.1 GHz～10.0 GHz之高頻訊號，測定S參數。然後，使用所測定之自試樣之堆載位置的反射量：S11及穿透量：S21，根據以下之式（6）而算出損耗率。 損耗率（Ploss/Pin）＝1－（S11 2＋S21 2）/1 式（6） 根據所獲得之電磁波吸收率（%），藉由以下標準進行評價。 （電磁波吸收性能之評價） A 電磁波吸收率（損耗率）為70%以上 B 電磁波吸收率（損耗率）為60%以上且未達70% C 電磁波吸收率（損耗率）未達60% [Electromagnetic wave absorption rate] According to the microstrip line method based on the IEC62333 standard, the electromagnetic wave absorption rate (loss rate) of the electromagnetic wave absorbing sheet under 50% compression is measured. Specifically, the method of measuring the resistance value shown in FIG. 2 was changed and measured as follows. That is, in the resistance value measurement, the electromagnetic wave absorbing sheet is arranged between two pressing plates (made of polycarbonate resin, thickness 3 mm), and one of the pressing plates is replaced with a microstrip with an impedance of 50 Ω For the substrate of the wire, an electromagnetic wave absorbing sheet is arranged between the pressing plate and the substrate. At this time, the distance between the pressing plate and the substrate was adjusted to 50% of the initial thickness of the electromagnetic wave absorbing sheet. In addition, the electromagnetic wave absorbing sheet is disposed so that the second heat conduction layer side faces the substrate side. Next, a high-frequency signal from 0.1 GHz to 10.0 GHz is incident on the microstrip line from a network analyzer (E8361A manufactured by Hewlett-Packard) to measure S parameters. Then, the loss rate was calculated according to the following formula (6) using the measured reflection amount from the loading position of the sample: S11 and the penetration amount: S21. Loss rate (Ploss/Pin)=1-(S11 2 +S21 2 )/1 Formula (6) Based on the obtained electromagnetic wave absorption rate (%), evaluation was performed according to the following criteria. (Evaluation of electromagnetic wave absorption performance) A The electromagnetic wave absorption rate (loss rate) is 70% or more B The electromagnetic wave absorption rate (loss rate) is 60% or more but less than 70% C The electromagnetic wave absorption rate (loss rate) is less than 60%
各實施例及比較例中所使用之原料如下所述。 （第1熱傳導層、第2熱傳導層之原料） ・聚矽氧A材料：包含含烯基之有機聚矽氧烷及微量之加成反應觸媒（鉑觸媒） ・聚矽氧B材料：包含含烯基之有機聚矽氧烷及氫化有機聚矽氧烷 ・聚矽氧油：於25℃之黏度為1000 cs ・鋁：形狀：球狀，平均粒徑3 μm ・礬土1：形狀：多面體，平均粒徑：0.5 μm ・礬土2：形狀：多面體，平均粒徑：3 μm ・礬土3：形狀：球形，平均粒徑：20 μm ・礬土4：形狀：球形，平均粒徑：45 μm ・氫氧化鋁1：形狀：破碎狀，平均粒徑：1.3 μm ・氫氧化鋁2：形狀：破碎狀，平均粒徑：8.3 μm ・碳纖維1：形狀：纖維狀，平均纖維長度：300 μm ・碳纖維2：形狀：纖維狀，平均纖維長度：200 μm ・碳纖維3：形狀：纖維狀，平均纖維長度：100 μm ・鱗片石墨：形狀：鱗片狀，平均粒徑：15 μm The raw materials used in each Example and Comparative Example are as follows. (Materials for the first heat conduction layer and the second heat conduction layer) ・Polysiloxane A material: Contains alkenyl-containing organopolysiloxane and a small amount of addition reaction catalyst (platinum catalyst) ・Polysiloxane B material: Contains alkenyl-containing organopolysiloxane and hydrogenated organopolysiloxane ・Polysilicone oil: viscosity at 25°C is 1000 cs ・Aluminum: Shape: spherical, average particle size 3 μm ・Alumina 1: Shape: polyhedron, average particle size: 0.5 μm ・Alumina 2: Shape: polyhedron, average particle size: 3 μm ・Alumina 3: Shape: spherical, average particle size: 20 μm ・Alumina 4: Shape: spherical, average particle size: 45 μm ・Aluminum hydroxide 1: shape: crushed, average particle size: 1.3 μm ・Aluminum hydroxide 2: shape: crushed, average particle size: 8.3 μm ・Carbon fiber 1: shape: fibrous, average fiber length: 300 μm ・Carbon fiber 2: shape: fibrous, average fiber length: 200 μm ・Carbon fiber 3: shape: fibrous, average fiber length: 100 μm ・Flake graphite: shape: scaly, average particle size: 15 μm
鋁、礬土1～4及氫氧化鋁1～2為非各向異性填充材料。碳纖維1～3為各向異性填充材料。礬土1～4相當於絕緣性填料。Aluminum, alumina 1-4 and aluminum hydroxide 1-2 are non-anisotropic filling materials. Carbon fibers 1-3 are anisotropic filling materials. Alumina 1 to 4 correspond to insulating fillers.
（導電性不織布） 各實施例及比較例中所使用之導電性不織布藉由以下方法而準備。 準備厚度為18 μm、單位面積重量為6 g/m 2、密度為3.3×10 5g/m 3之聚芳酯樹脂（PAR）製造之不織布。其次，將該不織布設置於真空裝置內，進行真空排氣直至成為5.0×10 -4Pa以下。繼而，導入氬氣而使氣壓成為0.5 Pa，藉由DC磁控濺鍍法，於不織布之單面依序積層由矽構成之障壁層1（厚度15 nm）、由赫史特合金構成之金屬層（108 nm）、及由矽構成之障壁層2（15 nm），從而獲得於一面具有金屬層之導電性不織布。作為各層之元素附著量，障壁層1為3.6 μg/cm 2，金屬層為96 μg/cm 2，障壁層2為3.6 μg/cm 2。赫史特合金係組成為鉬16.4質量%、鎳55.2質量%、鉻18.9質量%、鐵5.5質量%、鎢3.5質量%、氧化矽0.5質量%之合金。 又，導電性不織布之片電阻為26～28 Ω/□。 (Conductive nonwoven fabric) The conductive nonwoven fabric used in each Example and the comparative example was prepared by the following method. A nonwoven fabric made of polyarylate resin (PAR) with a thickness of 18 μm, a weight per unit area of 6 g/m 2 , and a density of 3.3×10 5 g/m 3 was prepared. Next, this nonwoven fabric was placed in a vacuum device, and the vacuum was exhausted until it became 5.0×10 -4 Pa or less. Next, argon gas was introduced to make the pressure 0.5 Pa, and a barrier layer 1 made of silicon (thickness 15 nm) and a metal made of Hoechst alloy were sequentially laminated on one side of the nonwoven fabric by DC magnetron sputtering method. layer (108 nm), and the barrier layer 2 (15 nm) made of silicon, so as to obtain a conductive nonwoven fabric with a metal layer on one side. The amount of element deposition in each layer was 3.6 μg/cm 2 for the barrier layer 1 , 96 μg/cm 2 for the metal layer, and 3.6 μg/cm 2 for the barrier layer 2 . The composition of Hoechst alloy is 16.4% by mass of molybdenum, 55.2% by mass of nickel, 18.9% by mass of chromium, 5.5% by mass of iron, 3.5% by mass of tungsten, and 0.5% by mass of silicon oxide. Also, the sheet resistance of the conductive nonwoven fabric was 26 to 28 Ω/□.
[實施例1] 將表1所示之組成1之各成分加以混合而獲得第1熱傳導層用組成物。繼而，將上述第1熱傳導層用組成物注入至設定為厚度比對於形成之第1熱傳導層而言足夠大之模具中，在厚度方向上施加8 T之磁場而使碳纖維於厚度方向配向後，以80℃加熱60分鐘而使基質硬化，從而獲得塊狀之配向成形體。 其次，藉由使用剪切刀片，將塊狀之配向成形體切片為片狀，從而製成片狀而獲得第1熱傳導層。 於所獲得之第1熱傳導層之一面配置導電性不織布。此時，以導電性不織布之金屬層成為與第1熱傳導層側相反之側之方式進行配置。 其次，將表1所示之組成4之各成分加以混合而製作第2熱傳導層用組成物。將該第2熱傳導層用組成物塗佈於第1熱傳導層上之導電性不織布之表面，使其浸透於透孔內後，以80℃加熱60分鐘，使第2熱傳導層用組成物之基質硬化，形成第2熱傳導層，從而獲得電磁波吸收片。將結果示於表2。 [Example 1] The components of composition 1 shown in Table 1 were mixed to obtain a composition for a first heat conduction layer. Next, inject the above-mentioned composition for the first heat conduction layer into a mold whose thickness ratio is sufficiently large for the formed first heat conduction layer, apply a magnetic field of 8 T in the thickness direction to align the carbon fibers in the thickness direction, The matrix was hardened by heating at 80° C. for 60 minutes to obtain a block-shaped alignment molding. Next, by using a shear blade, the block-shaped alignment molded body was sliced into sheets to form a sheet to obtain a first heat-conducting layer. A conductive nonwoven fabric was disposed on one side of the obtained first heat conduction layer. At this time, it arrange|positions so that the metal layer of an electroconductive nonwoven fabric may become the side opposite to the 1st heat conduction layer side. Next, each component of the composition 4 shown in Table 1 was mixed, and the composition for the 2nd heat conduction layer was produced. Apply the composition for the second heat conduction layer on the surface of the conductive nonwoven fabric on the first heat conduction layer, soak it into the through holes, and heat at 80°C for 60 minutes to make the matrix of the composition for the second heat conduction layer It is cured to form a second heat conduction layer to obtain an electromagnetic wave absorbing sheet. The results are shown in Table 2.
[實施例2～19、比較例1～2] 如表2及3所示地變更第1熱傳導層用組成物、及第2熱傳導層用組成物之組成之種類、以及第1熱傳導層之厚度T1及第2熱傳導層之厚度T2，除此以外，設為與實施例1相同而獲得電磁波吸收片。將結果示於表2及3。再者，實施例1～19、比較例1～2之內部絕緣層之厚度全部同等級為20～30 μm。 [Examples 2-19, Comparative Examples 1-2] As shown in Tables 2 and 3, the types of the composition for the first heat conduction layer and the composition of the second heat conduction layer, and the thickness T1 of the first heat conduction layer and the thickness T2 of the second heat conduction layer were changed. , and obtained an electromagnetic wave absorbing sheet in the same manner as in Example 1. The results are shown in Tables 2 and 3. Furthermore, the thicknesses of the inner insulating layers of Examples 1-19 and Comparative Examples 1-2 are all in the same range of 20-30 μm.
[表1]
[表2]
[表3]
各實施例中所示之本發明之電磁波吸收片的電阻值比（R1/R2）為式（1）之範圍內，即使於壓縮之情形時亦顯示出良好之電磁波吸收性能。特別是，由第1熱傳導層側之壓縮率與第1熱傳導層之厚度之比率的乘積所定之「C1×T1/（T1＋T2）」之值為0.5以上之實施例顯示出優異之電磁波吸收性能。又，各實施例之電磁波吸收片中之第1熱傳導層所含有之碳纖維配向於熱傳導層之厚度方向，故電磁波吸收片顯示出優異之熱傳導性。 相對於此，電阻值比（R1/R2）在式（1）之範圍之外的各比較例之電磁波吸收片，表現出在壓縮之情形時電磁波吸收性能差於實施例之結果。 The resistance value ratio (R1/R2) of the electromagnetic wave absorbing sheet of the present invention shown in each example is within the range of formula (1), and exhibits good electromagnetic wave absorbing performance even when compressed. In particular, examples in which the value of "C1 x T1 / (T1 + T2)" determined by the ratio of the ratio of the compressibility of the first heat conduction layer side to the thickness of the first heat conduction layer was 0.5 or more showed excellent electromagnetic wave absorption performance. In addition, the carbon fibers contained in the first heat conduction layer in the electromagnetic wave absorbing sheet of each example were oriented in the thickness direction of the heat conduction layer, so the electromagnetic wave absorbing sheet exhibited excellent heat conductivity. On the other hand, the electromagnetic wave absorbing sheets of the comparative examples in which the resistance value ratio (R1/R2) was out of the range of the formula (1) showed a result that the electromagnetic wave absorbing performance was inferior to that of the examples when compressed.
10:電磁波吸收片 11:第1熱傳導層 12:第2熱傳導層 13:電磁波吸收構件 14:內部絕緣層 15:表面絕緣層 16:高分子基質 17:絕緣性填料 18:高分子基質 19:各向異性填充材料 20:非各向異性填充材料 21:按壓板 22:螺絲 23:間隔件 24:探針 10: Electromagnetic wave absorbing sheet 11: The first heat conduction layer 12: The second heat conduction layer 13: Electromagnetic wave absorbing member 14: Inner insulating layer 15: Surface insulation layer 16: Polymer matrix 17: insulating filler 18: Polymer matrix 19:Anisotropic filling material 20: Non-anisotropic filling material 21: Press plate 22: screw 23: spacer 24: Probe
[圖1]係示意性表示本發明之電磁波吸收片之一實施方式的剖視圖。 [圖2]係示意性表示電阻值R1及R2之測定方法之圖。 [ Fig. 1] Fig. 1 is a cross-sectional view schematically showing an embodiment of an electromagnetic wave absorbing sheet of the present invention. [ Fig. 2 ] is a diagram schematically showing a method of measuring resistance values R1 and R2.
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