TWI674305B - Adhesive composition precursor, adhesive composition and manufacturing method thereof, adhesive sheet and manufacturing method thereof, and electronic device with adhesive sheet - Google Patents
Adhesive composition precursor, adhesive composition and manufacturing method thereof, adhesive sheet and manufacturing method thereof, and electronic device with adhesive sheet Download PDFInfo
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Abstract
本發明係提供一種黏著薄片，其係熱傳導性高，具有難燃性，相較於以往係具有更大的黏著力。 The present invention provides an adhesive sheet, which has high thermal conductivity and flame retardancy, and has a larger adhesive force than conventional systems.
本發明之黏著組成物前驅體，其特徵為含有(甲基)丙烯酸共聚物、(甲基)丙烯酸單體與板狀或鱗片狀之含水金屬化合物，前述含水金屬化合物之含量，相對於前述黏著組成物前驅體之全質量為30質量%以上70質量%以下，前述含水金屬化合物之平均粒徑為2μm以上50μm以下，前述含水金屬化合物之長寬比為5以上，前述(甲基)丙烯酸單體之含量，其係相對於前述(甲基)丙烯酸共聚物與前述(甲基)丙烯酸單體之合計質量為75質量%以上99質量%以下。 The adhesive composition precursor of the present invention is characterized by containing a (meth) acrylic copolymer, a (meth) acrylic monomer, and a plate-like or scaly water-containing metal compound. The content of the water-containing metal compound is relative to the adhesion. The total mass of the composition precursor is 30% by mass or more and 70% by mass or less, the average particle diameter of the water-containing metal compound is 2 μm or more and 50 μm or less, the aspect ratio of the water-containing metal compound is 5 or more, and the (meth) acrylic acid monomer It is 75 mass% or more and 99 mass% or less with respect to the total mass of the said (meth) acrylic copolymer and the said (meth) acrylic monomer.
Description
本發明係關於黏著組成物前驅體、黏著組成物及其製造方法、黏著薄片及其製造方法、與含黏著薄片之電子儀器。 The present invention relates to an adhesive composition precursor, an adhesive composition and a method for manufacturing the same, an adhesive sheet and a method for manufacturing the same, and an electronic instrument containing the adhesive sheet.
近年來隨著發光二極體(LED)、電激發光(EL)般的半導體發光元件之實用化，由這些元件所發生的熱之對策就變得越來越重要。此係因為在隨著發光元件之亮度提高而發熱量增加的傾向上，若對於發熱的對策不充分，則會產生元件壽命下降等的問題。另外，在其他的電子儀器亦有隨著零件之高積體化、高性能化，而機器之內部溫度有上昇的傾向，發熱對策就變得越來越重要。 In recent years, with the practical use of semiconductor light-emitting devices such as light-emitting diodes (LEDs) and electro-luminescence (EL), countermeasures against the heat generated by these devices have become increasingly important. This is because there is a tendency that the amount of heat generation increases as the brightness of the light-emitting element increases. If the countermeasure against heat generation is insufficient, problems such as a reduction in the life of the element may occur. In addition, other electronic devices also tend to increase the internal temperature of the machine as parts become more integrated and more efficient, and measures against heat generation become more and more important.
先前，作為電子儀器等之發熱對策，流行將元件、零件等之發熱體，與散熱器、散熱片等之散熱構件之間，經由熱傳導率高的熱傳導性薄片而接合。作為在此熱傳導性薄片所要求的特性，多為接著性、高熱傳導性、另外，就安全性之層面要求難燃性。 Conventionally, as a countermeasure against heat generation in electronic devices, it is popular to join heat generating elements such as elements and parts with heat dissipation members such as heat sinks and heat sinks via a thermally conductive sheet having a high thermal conductivity. As the characteristics required for the thermally conductive sheet, adhesiveness, high thermal conductivity, and flame retardance are required in terms of safety.
因此，為了滿足上述特性，進行了各式各樣的研討，作為該一例，提案有含無機填料與丙烯酸系共聚物的黏著膠帶(專利文獻1)。在此提案，於熱傳導性及難燃性為必要的用途中，理想係使用具有熱傳導性及難燃性的熱傳導難燃性填料，作為該例設為使用金屬氫氧化物。另外，關於黏著力之提高，作為丙烯酸系共聚物之單體成分，設為使用經由碳數為2以上之飽和烴基而在分子鏈末端具有羧基的(甲基)丙烯酸酯。在專利文獻1中，藉由使用於丙烯酸系共聚物之單體成分經由碳數為2以上之飽和烴基而在分子鏈末端具有羧基的(甲基)丙烯酸酯，即使為了熱傳導性、難燃性提高而大量調配無機填料亦使黏著劑層之凝集性與流動性併立，顯現出優異的黏著物性。如此，先前在具有熱傳導機能的黏著膠帶中，關於熱傳導性及難燃性係以無機填料之種類而調整，關於黏著性之提高係以黏著劑組成而調整之方式進行。 Therefore, in order to satisfy the above-mentioned characteristics, various studies have been conducted. As an example, an adhesive tape containing an inorganic filler and an acrylic copolymer has been proposed (Patent Document 1). In this proposal, in applications where thermal conductivity and flame retardancy are necessary, it is desirable to use a thermally conductive flame-retardant filler having thermal conductivity and flame retardance, and it is assumed that a metal hydroxide is used as this example. In addition, regarding the improvement of the adhesive force, as a monomer component of the acrylic copolymer, a (meth) acrylic acid ester having a carboxyl group at a molecular chain terminal via a saturated hydrocarbon group having 2 or more carbon atoms is used. In Patent Document 1, a (meth) acrylic acid ester having a carboxyl group at the terminal of a molecular chain through a saturated hydrocarbon group having a carbon number of 2 or more via a monomer component used in an acrylic copolymer, even for thermal conductivity and flame retardancy It is improved and a large amount of inorganic filler is blended to make the cohesiveness and fluidity of the adhesive layer stand side by side, showing excellent adhesive properties. As described above, in the adhesive tape having a heat conduction function, the thermal conductivity and flame retardancy were previously adjusted by the type of the inorganic filler, and the improvement of the adhesion was adjusted by the composition of the adhesive.
另一方面，提案有在含有熱傳導性之無機材料與有機高分子化合物的熱傳導薄片中，將無機粒子之形狀設為鱗片狀、橢球狀、板狀或棒狀，使無機粒子配向於熱傳導薄片之厚度方向(專利文獻2)。在此提案中，實現於膜厚方向為高熱傳導的熱傳導薄片。 On the other hand, it has been proposed that the shape of the inorganic particles be scaly, ellipsoidal, plate-shaped, or rod-shaped in a thermally conductive sheet containing a thermally conductive inorganic material and an organic polymer compound, and the inorganic particles are aligned with the thermally conductive sheet. Thickness direction (Patent Document 2). In this proposal, a thermally conductive sheet having high thermal conductivity in the film thickness direction is realized.
[專利文獻1]日本特開2013-87214號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2013-87214
[專利文獻2]日本特開2010-114421號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2010-114421
然而，最近，期待有黏著薄片係在電子儀器領域由零件之假固定等之附屬的構件，朝向為了使用在無併用小螺絲固定的單獨接合之正式的固定構件之擴展。為了將如此的黏著薄片設為正式的固定構件，所以更要求黏著力提高。 Recently, however, there has been an expectation that the adhesive sheet is an accessory member that is attached by false fixing of parts in the field of electronic equipment, and is intended to be used as a formal fixing member that is individually joined without using a small screw. In order to make such an adhesive sheet into a formal fixing member, it is further required to improve the adhesive force.
本發明係鑑於上述狀況而為者，提供熱傳導性高，具有難燃性，具有比先前更大的黏著力的黏著薄片。 The present invention has been made in view of the above circumstances, and provides an adhesive sheet having high thermal conductivity, flame resistance, and greater adhesive force than before.
本發明之黏著組成物前驅體，其係含有(甲基)丙烯酸共聚物、與(甲基)丙烯酸單體、與板狀或鱗片狀之含水金屬化合物之黏著組成物前驅體，其特徵為前述含水金屬化合物之含量相對於前述黏著組成物前驅體之全質量為30質量%以上70質量%以下，前述含水金屬化合物之平均粒徑為2μm以上50μm以下，前述含水金屬化合物之長寬比為5以上，前述(甲基)丙烯酸單體之含量相對於前述(甲基)丙烯酸共聚物與前述(甲基)丙烯酸單體之合計質量為75質量%以上99質量%以下。 The adhesive composition precursor of the present invention is an adhesive composition precursor containing a (meth) acrylic copolymer, a (meth) acrylic monomer, and a plate-like or scaly water-containing metal compound, which is characterized in that The content of the water-containing metal compound is 30% by mass or more and 70% by mass or less with respect to the total mass of the aforementioned adhesive composition precursor, the average particle diameter of the water-containing metal compound is 2 μm or more and 50 μm or less, and the aspect ratio of the water-containing metal compound is 5 As described above, the content of the (meth) acrylic monomer is 75% by mass or more and 99% by mass or less with respect to the total mass of the (meth) acrylic copolymer and the (meth) acrylic monomer.
另外，本發明之黏著組成物，其特徵為將含 有上述本發明之黏著組成物前驅體的(甲基)丙烯酸單體進行聚合而形成。 In addition, the adhesive composition of the present invention is characterized in that The (meth) acrylic monomer having the adhesive composition precursor of the present invention is polymerized and formed.
另外，本發明之黏著薄片，其特徵為係將上述本發明之黏著組成物成形為薄片狀者。 The adhesive sheet of the present invention is characterized in that the adhesive composition of the present invention is formed into a sheet shape.
另外，本發明之電子儀器，其特徵為含有上述本發明之黏著薄片。 In addition, the electronic instrument of the present invention includes the adhesive sheet of the present invention.
另外，本發明之黏著組成物之製造方法，其特徵為包含調製上述本發明之黏著組成物前驅體的步驟、與聚合含有前述黏著組成物前驅體的前述(甲基)丙烯酸單體的步驟。 In addition, the method for producing an adhesive composition of the present invention includes a step of preparing the aforementioned adhesive composition precursor of the present invention and a step of polymerizing the (meth) acrylic monomer containing the aforementioned adhesive composition precursor.
另外，本發明之黏著薄片之製造方法，其特徵為包含調製上述本發明之黏著組成物前驅體的步驟、與聚合含有前述黏著組成物前驅體的前述(甲基)丙烯酸單體而成形為薄片狀的步驟。 In addition, the method for producing an adhesive sheet according to the present invention includes a step of preparing the aforementioned adhesive composition precursor of the present invention, and polymerizing the (meth) acrylic monomer containing the aforementioned adhesive composition precursor to form a sheet. Like steps.
如藉由本發明則可提供一種黏著薄片，其係熱傳導性高，具有難燃性，相較於先前係具有更大的黏著力。 According to the present invention, it is possible to provide an adhesive sheet, which has high thermal conductivity and flame resistance, and has a larger adhesive force than the previous system.
10‧‧‧著薄片 10‧‧‧ with flakes
11、13‧‧‧剝離薄膜 11, 13‧‧‧ peeling film
12‧‧‧黏著劑 12‧‧‧ Adhesive
[第1圖]1圖係表示本發明之黏著薄片之一例的模式剖面圖。 [FIG. 1] FIG. 1 is a schematic cross-sectional view showing an example of the adhesive sheet of the present invention.
本發明之發明者們，其係關於黏著劑之黏著力經過專心致力研討的結果，發現含有黏著劑的無機填料之形狀影響黏著力，進而完成本發明。 The inventors of the present invention are the result of intensive research on the adhesive force of the adhesive, and found that the shape of the inorganic filler containing the adhesive affects the adhesive force, and completed the present invention.
亦即，本發明之黏著組成物前驅體，其係含有(甲基)丙烯酸共聚物、與(甲基)丙烯酸單體、與板狀或鱗片狀之含水金屬化合物。另外，上述含水金屬化合物之含量相對於上述黏著組成物前驅體之全質量為30質量%以上70質量%以下，上述含水金屬化合物之平均粒徑為2μm以上50μm以下，上述含水金屬化合物之長寬比為5以上。更進一步，上述(甲基)丙烯酸單體之含量相對於上述(甲基)丙烯酸共聚物與上述(甲基)丙烯酸單體之合計質量為75質量%以上99質量%以下。 That is, the adhesive composition precursor of the present invention contains a (meth) acrylic copolymer, a (meth) acrylic monomer, and a plate-like or scale-like water-containing metal compound. In addition, the content of the water-containing metal compound is 30% by mass or more and 70% by mass or less based on the total mass of the adhesive composition precursor, the average particle diameter of the water-containing metal compound is 2 μm or more and 50 μm or less, and the length and width of the water-containing metal compound The ratio is 5 or more. Furthermore, content of the said (meth) acrylic monomer is 75 mass% or more and 99 mass% or less with respect to the total mass of the said (meth) acrylic copolymer and the said (meth) acrylic monomer.
本發明之黏著組成物前驅體，因為含有含水金屬化合物，所以可提供具有高熱傳導性的黏著劑。亦即，上述含水金屬化合物係具有高熱傳導性的無機填料，藉由使黏著劑含有上述含水金屬化合物，可賦與黏著劑高的熱傳導性。另外，在本發明中，所謂含水金屬化合物，定義為藉由加熱而放出水的金屬化合物。因此，藉由使黏著劑含有上述含水金屬化合物，可賦與黏著劑難燃性。 Since the adhesive composition precursor of the present invention contains a water-containing metal compound, it can provide an adhesive having high thermal conductivity. That is, the water-containing metal compound is an inorganic filler having a high thermal conductivity, and when the adhesive contains the water-containing metal compound, a high thermal conductivity can be imparted to the adhesive. In addition, in the present invention, a hydrous metal compound is defined as a metal compound that releases water by heating. Therefore, by including the above-mentioned water-containing metal compound in the adhesive, it is possible to impart flame retardancy to the adhesive.
上述含水金屬化合物之含量有相對於上述黏 著組成物前驅體之全質量而設定為30質量%以上70質量%以下的必要，35質量%以上65質量%以下為較理想。若上述含水金屬化合物之含量相對於上述黏著組成物前驅體之全質量而低於30質量%，則黏著劑之熱傳導性及難燃性低下，若上述含水金屬化合物之含量相對於上述黏著組成物前驅體之全質量而超過70質量%，則黏著劑之黏著力低下，黏著劑之柔軟性下降。若黏著劑之柔軟性下降，則向接合構件之追隨性下降而不理想。 The content of the above-mentioned water-containing metal compound is It is necessary to set the total mass of the composition precursor to 30% by mass or more and 70% by mass or less, and preferably 35% by mass or more and 65% by mass or less. If the content of the water-containing metal compound is less than 30% by mass relative to the total mass of the adhesive composition precursor, the thermal conductivity and flame retardancy of the adhesive are low. If the content of the water-containing metal compound is relative to the adhesive composition, When the total mass of the precursor exceeds 70% by mass, the adhesive force of the adhesive is low, and the softness of the adhesive is decreased. If the flexibility of the adhesive is reduced, the followability to the bonding member is reduced, which is not desirable.
另外，上述含水金屬化合物具有板狀或鱗片狀之形狀，上述含水金屬化合物之平均粒徑為2μm以上50μm以下，上述含水金屬化合物之長寬比為5以上者。因此，相較於先前之使用了粒狀之無機填料的黏著劑，可得較大的黏著力。 In addition, the hydrous metal compound has a plate-like or scaly shape, an average particle diameter of the hydrous metal compound is 2 μm or more and 50 μm or less, and an aspect ratio of the hydrous metal compound is 5 or more. Therefore, compared with the previous adhesive using the granular inorganic filler, a larger adhesive force can be obtained.
更進一步，本發明之黏著組成物前驅體，其係含有(甲基)丙烯酸共聚物、與(甲基)丙烯酸單體，藉由使上述(甲基)丙烯酸單體聚合，產生黏著力。因而，本發明之黏著組成物前驅體本身，其係不具有黏著力、或是只有小的黏著力者。 Furthermore, the adhesive composition precursor of the present invention contains a (meth) acrylic copolymer and a (meth) acrylic monomer, and the (meth) acrylic monomer is polymerized to generate an adhesive force. Therefore, the precursor of the adhesive composition of the present invention does not have adhesive force or has only a small adhesive force.
另外，上述(甲基)丙烯酸單體之含量相對於上述(甲基)丙烯酸共聚物與上述(甲基)丙烯酸單體之合計質量，有設定為75質量%以上99質量%以下的必要。若上述(甲基)丙烯酸單體之含量低於75質量%，則本發明之黏著組成物前驅體之流動性下降，若上述(甲基)丙烯酸單體之含量超過99質量%，則本發明之黏著組成物前驅體之 流動性變得過高，變得難以形成使用了本發明之黏著組成物前驅體的黏著薄片。 In addition, it is necessary that the content of the (meth) acrylic monomer is set to 75% by mass or more and 99% by mass or less with respect to the total mass of the (meth) acrylic copolymer and the (meth) acrylic monomer. If the content of the (meth) acrylic monomer is less than 75% by mass, the fluidity of the precursor of the adhesive composition of the present invention is reduced. If the content of the (meth) acrylic monomer is more than 99% by mass, the present invention Precursors The fluidity becomes too high, and it becomes difficult to form an adhesive sheet using the adhesive composition precursor of the present invention.
以下，詳細地說明有關本發明之黏著組成物前驅體之各成分。 Hereinafter, each component of the adhesive composition precursor of the present invention will be described in detail.
如上所述，本發明之板狀或鱗片狀之含水金屬化合物，其係藉由加熱而放出水的金屬化合物，特別是氫氧化鋁或水鋁石為理想。因為這些成分係具有高的熱傳導性、難燃性及電氣絕緣性。本發明之黏著組成物前驅體，亦可均含有氫氧化鋁及水鋁礦。本發明之黏著組成物前驅體，因為含有上述含水金屬化合物，所以可提供具有高的熱傳導性與難燃性的黏著劑。 As described above, the plate-like or scale-like water-containing metal compound of the present invention is preferably a metal compound that releases water by heating, and is particularly preferably aluminum hydroxide or gibbsite. This is because these components have high thermal conductivity, flame resistance, and electrical insulation. The adhesive composition precursors of the present invention may all contain aluminum hydroxide and gibbsite. Since the adhesive composition precursor of the present invention contains the aforementioned water-containing metal compound, it can provide an adhesive having high thermal conductivity and flame retardancy.
上述含水金屬化合物之平均粒徑係2μm以上50μm以下為理想，2μm以上10μm以下為較理想。若上述含水金屬化合物之平均粒徑低於2μm，則黏著劑之黏著力低下，若上述含水金屬化合物之平均粒徑超過50μm，則黏著劑之表面起伏變大，黏著劑之黏著力下降。在本發明中上述含水金屬化合物之平均粒徑，其係以掃描式電子顯微鏡(SEM)或是穿透型電子顯微鏡(TEM)觀察上述含水金屬化合物之粒子，設為測定100個粒子之長軸徑，作為該算術平均值而求出者。 The average particle diameter of the hydrous metal compound is preferably 2 μm or more and 50 μm or less, and more preferably 2 μm or more and 10 μm or less. If the average particle diameter of the water-containing metal compound is less than 2 μm, the adhesive force of the adhesive is low. If the average particle diameter of the water-containing metal compound is more than 50 μm, the surface undulation of the adhesive becomes large, and the adhesive force of the adhesive decreases. In the present invention, the average particle diameter of the water-containing metal compound is measured by scanning electron microscope (SEM) or transmission electron microscope (TEM), and the long axis of 100 particles is measured. The diameter is calculated as the arithmetic mean.
上述含水金屬化合物之長寬比係5以上為理想，8以上為較理想，10以上為更理想。若上述長寬比低 於5，則上述含水金屬化合物之粒子形狀類似粒狀，所以黏著劑之黏著力下降。在本發明中上述含水金屬化合物之長寬比，其係設為以SEM或TEM觀察上述含水金屬化合物之粒子，將上述含水金屬化合物之厚度方向之長度設為t，該板面之最大長度設為d，關於100個粒子各自求出以d/t所算出的值，作為該算術平均值所求出者。 The aspect ratio of the water-containing metal compound is preferably 5 or more, 8 or more is more preferable, and 10 or more is more preferable. If the above aspect ratio is low At 5, the particle shape of the above-mentioned water-containing metal compound is similar to a granular shape, so the adhesive force of the adhesive decreases. In the present invention, the aspect ratio of the water-containing metal compound is set to observe the particles of the water-containing metal compound by SEM or TEM, the length in the thickness direction of the water-containing metal compound is set to t, and the maximum length of the plate surface is set to It is d, and the value calculated by d / t is calculated about each of 100 particles, and it is set as the one calculated | required by this arithmetic mean.
在本發明中，其係在上述長寬比為5以上的情況，設為板狀之粒子，在上述長寬比為15以上之情況，設為鱗片狀之粒子。 In the present invention, the particles are plate-like particles when the aspect ratio is 5 or more, and are scaly particles when the aspect ratio is 15 or more.
上述含水金屬化合物之含量相對於上述黏著組成物前驅體之全質量，有設定為30質量%以上70質量%以下的必要，但以黏著劑之難燃性為在以JIS K7201-2所規定的氧指數中可達成21以上的方式調整為理想。 It is necessary to set the content of the water-containing metal compound to 30% by mass or more and 70% by mass or less with respect to the total mass of the precursor of the adhesive composition. However, the flame retardancy of the adhesive is specified in JIS K7201-2. It is desirable to adjust the oxygen index to 21 or more.
本發明之黏著組成物前驅體所含的含水金屬化合物之含量，例如可藉由熱分析法而測定。亦即，將上述黏著組成物前驅體加熱至500℃附近，測定殘渣(抽去水的金屬化合物)之質量，由該殘渣之質量求出上述黏著組成物前驅體所含的含水金屬化合物之質量，由該含水金屬化合物之質量可求出黏著組成物前驅體所含的含水金屬化合物之含有率。 The content of the water-containing metal compound contained in the adhesive composition precursor of the present invention can be measured by, for example, a thermal analysis method. That is, the above-mentioned adhesive composition precursor is heated to around 500 ° C., and the mass of the residue (metal compound with water removed) is measured, and the mass of the water-containing metal compound contained in the above-mentioned adhesive composition precursor is obtained from the mass of the residue. From the mass of the water-containing metal compound, the content rate of the water-containing metal compound contained in the precursor of the adhesive composition can be determined.
本發明之黏著組成物前驅體所含的(甲基)丙烯酸共聚物，其係將(甲基)丙烯酸單體設為單體成分的聚合物。作 為成為上述單體成分的(甲基)丙烯酸單體，例如可舉出(甲基)丙烯酸、(甲基)丙烯酸酯或該衍生物。作為上述(甲基)丙烯酸酯，例如可使用具有碳數為1~18之烷基的(甲基)丙烯酸酯，具體而言，可使用丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸2乙基己酯、甲基丙烯酸2乙基己酯、丙烯酸異冰片基酯、丙烯酸癸酯、丙烯酸硬脂醯基酯等。成為上述單體成分的(甲基)丙烯酸單體，可使用1種或2種以上。 The (meth) acrylic copolymer contained in the adhesive composition precursor of the present invention is a polymer having a (meth) acrylic monomer as a monomer component. Make Examples of the (meth) acrylic monomer to be the monomer component include (meth) acrylic acid, (meth) acrylic acid esters, and derivatives thereof. As the (meth) acrylate, for example, a (meth) acrylate having an alkyl group having 1 to 18 carbon atoms can be used, and specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2ethylhexyl acrylate, 2ethylhexyl methacrylate, isobornyl acrylate, decyl acrylate Esters, stearyl acrylate and the like. The (meth) acrylic monomer which becomes the said monomer component can use 1 type or 2 or more types.
本發明之黏著組成物前驅體所含的(甲基)丙烯酸共聚物，係具有官能基為理想。藉由上述(甲基)丙烯酸共聚物具有官能基之情事，所以與上述含水金屬化合物之結合力提高，黏著力提高。作為上述官能基係可舉出羥基、羧基、胺基、取代胺基、環氧基等。其中，羧基等之酸性官能基為較理想。具有羧基等之酸性官能基的(甲基)丙烯酸共聚物，與上述含水金屬化合物之結合力就更提高。 The (meth) acrylic copolymer contained in the adhesive composition precursor of the present invention preferably has a functional group. Since the (meth) acrylic copolymer has a functional group, the binding force with the water-containing metal compound is improved, and the adhesive force is improved. Examples of the functional group include a hydroxyl group, a carboxyl group, an amine group, a substituted amine group, and an epoxy group. Among them, an acidic functional group such as a carboxyl group is preferable. The (meth) acrylic acid copolymer having an acidic functional group such as a carboxyl group has a higher binding force with the aforementioned water-containing metal compound.
為了在本發明之黏著組成物前驅體所含的(甲基)丙烯酸共聚物賦與官能基，其係於成為該單體成分的上述(甲基)丙烯酸單體中，包含具有官能基的(甲基)丙烯酸單體為佳。作為具有上述官能基的(甲基)丙烯酸單體，例如可舉出丙烯酸、甲基丙烯酸、丙烯酸2羥乙基酯、丙烯酸2羥丙基酯、丙烯酸2羥丁基酯、丙烯酸β羧乙基酯、丙烯醯胺、N,N-二甲基丙烯醯胺等。具有上述官 能基的(甲基)丙烯酸單體亦可使用1種或2種以上。 In order to impart a functional group to the (meth) acrylic copolymer contained in the adhesive composition precursor of the present invention, it is based on the (meth) acrylic monomer which becomes the monomer component, and contains ( A meth) acrylic monomer is preferred. Examples of the (meth) acrylic monomer having the functional group include acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, and β-carboxyethyl acrylate. Esters, acrylamide, N, N-dimethylacrylamide and the like. Have the above official The energy-based (meth) acrylic monomer may be used alone or in combination of two or more.
為了確保上述官能基之效果，具有上述官能基的(甲基)丙烯酸單體之含量相對於成為上述單體成分的上述(甲基)丙烯酸單體之全質量為1質量%以上30質量%以下為理想，1~15質量%為較理想。 In order to ensure the effect of the functional group, the content of the (meth) acrylic monomer having the functional group is 1% by mass or more and 30% by mass or less based on the total mass of the (meth) acrylic monomer as the monomer component. Ideally, 1 to 15% by mass is ideal.
作為本發明之黏著組成物前驅體所含的(甲基)丙烯酸單體，其係可合適地使用先前周知者，但特別理想為使用與成為前述之本發明之黏著組成物前驅體所含的(甲基)丙烯酸共聚物之單體成分的(甲基)丙烯酸單體同樣之單體。作為本發明之黏著組成物前驅體所含的(甲基)丙烯酸單體，包含具有官能基的(甲基)丙烯酸單體亦為理想，特別是包含具有酸性官能基的(甲基)丙烯酸單體為較理想。藉由上述(甲基)丙烯酸單體具有官能基之情事，上述含水金屬化合物與上述(甲基)丙烯酸單體結合，在上述黏著組成物前驅體中之上述含水金屬化合物之濕潤性提高，可謀求上述黏著組成物前驅體之組成之均質化。 As the (meth) acrylic acid monomer contained in the adhesive composition precursor of the present invention, a conventionally known one can be suitably used, but it is particularly preferable to use and become the precursor contained in the adhesive composition precursor of the present invention. The (meth) acrylic monomer which is a monomer component of a (meth) acrylic copolymer is the same monomer. As the (meth) acrylic monomer contained in the precursor of the adhesive composition of the present invention, it is also desirable to include a (meth) acrylic monomer having a functional group, especially to include a (meth) acrylic monomer having an acidic functional group. The body is ideal. When the (meth) acrylic monomer has a functional group, the water-containing metal compound is combined with the (meth) acrylic monomer, and the wettability of the water-containing metal compound in the precursor of the adhesive composition is improved. The composition of the precursor of the adhesive composition is sought to be homogenized.
為了確保上述官能基之效果，具有上述官能基的(甲基)丙烯酸單體之含量相對於上述黏著組成物前驅體所含的(甲基)丙烯酸單體之全質量為1質量%以上30質量%以下為理想，1~15質量%為較理想。 In order to ensure the effect of the functional group, the content of the (meth) acrylic monomer having the functional group is 1% by mass or more and 30% by mass relative to the total mass of the (meth) acrylic monomer contained in the precursor of the adhesive composition. % Or less is ideal, and 1 to 15% by mass is ideal.
本發明之黏著組成物前驅體所含的上述(甲基)丙烯酸共聚物、與上述(甲基)丙烯酸單體，其係可各自分別準備，但由最初使用含有上述(甲基)丙烯酸共聚物與上述(甲基)丙烯酸單體的市售之丙烯酸漿料係簡便而為理想。作為上述丙烯酸漿料，例如可舉出綜研化學公司製之無溶劑型丙烯酸黏著劑"SK Dyne syrup series"、東亞合成公司製之UV硬化型黏著劑"ARONTACK UVA series"等。 The (meth) acrylic acid copolymer and the (meth) acrylic acid monomer contained in the adhesive composition precursor of the present invention can be prepared separately, but the (meth) acrylic acid copolymer is used from the beginning. A commercially available acrylic slurry with the aforementioned (meth) acrylic monomer is simple and desirable. Examples of the acrylic slurry include a solventless acrylic adhesive "SK Dyne syrup series" manufactured by Soken Chemical Co., Ltd., and a UV-curable adhesive "ARONTACK UVA series" manufactured by Toa Kosei Corporation.
於上述丙烯酸漿料，為了調整本發明之黏著組成物前驅體之黏度或特性，亦可更增加(甲基)丙烯酸單體。作為追加的(甲基)丙烯酸單體，其係可使用與前述的本發明之黏著組成物前驅體所含的(甲基)丙烯酸單體同樣之單體。 In the above-mentioned acrylic slurry, in order to adjust the viscosity or characteristics of the adhesive composition precursor of the present invention, a (meth) acrylic monomer may be further added. As the additional (meth) acrylic monomer, a monomer similar to the (meth) acrylic monomer contained in the aforementioned adhesive composition precursor of the present invention can be used.
若將上述含水金屬化合物與上述丙烯酸漿料混合，就有增黏之情事。此係被認為是因上述含水金屬化合物與上述丙烯酸漿料中之(甲基)丙烯酸共聚物之相互作用而生。因此，於本發明之黏著組成物前驅體為了抑制增黏現象，亦可添加分散劑。作為上述分散劑係與上述(甲基)丙烯酸共聚物及上述(甲基)丙烯酸單體之親和性為良好的高分子系分散劑為理想。作為上述高分子系分散劑，例如可舉出丙烯酸系、乙烯基系、聚酯系、聚胺基甲酸酯系、聚醚系、環氧系、聚苯乙烯系、胺系等之高分子化合物。上述分散劑係可單獨使用1種，亦可混合2種以上而使用。 When the above-mentioned water-containing metal compound is mixed with the above-mentioned acrylic slurry, the viscosity is increased. This is considered to be due to the interaction between the above-mentioned water-containing metal compound and the (meth) acrylic acid copolymer in the above-mentioned acrylic slurry. Therefore, a dispersant may be added to the precursor of the adhesive composition of the present invention in order to suppress the thickening phenomenon. The dispersant is preferably a polymer-based dispersant having good affinity with the (meth) acrylic copolymer and the (meth) acrylic monomer. Examples of the polymer-based dispersant include polymers such as acrylic-based, vinyl-based, polyester-based, polyurethane-based, polyether-based, epoxy-based, polystyrene-based, and amine-based polymers. Compound. These dispersants may be used alone or in combination of two or more.
上述分散劑係為了提高分散機能所以具有官能基為理想。作為上述官能基，其係可舉出羧基、磷酸基、磺酸基、羧酸酯基、磷酸酯基、磺酸酯基、羥基、胺基、四級銨鹼、醯胺基等，但上述分散劑係具有酸性官能基與鹼性官能基之雙方的兩性分散劑為較理想。 The dispersant is preferably a functional group in order to improve the dispersing function. Examples of the functional group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a carboxylic acid ester group, a phosphoric acid ester group, a sulfonic acid ester group, a hydroxyl group, an amine group, a quaternary ammonium base, and a sulfonium amino group. The dispersant is preferably an amphoteric dispersant having both an acidic functional group and a basic functional group.
上述分散劑之酸度係將其酸價作為基準而決定，上述分散劑之鹼度係將其胺價作為基準而決定。以使用酸價為20mg KOH/g以上的分散劑，可防止上述黏著組成物前驅體之增黏現象。另外，使用胺價為5mg KOH/g以上的分散劑，可防止黏著劑之保存時之黏著力之變化。此係可認為上述分散劑之酸性官能基為覆蓋上述含水金屬化合物之鹼性活性部位，抑制上述含水金屬化合物與上述(甲基)丙烯酸共聚物之相互作用，所以防止了上述黏著組成物前驅體之增黏現象。另外，可認為上述分散劑中之鹼性官能基係與上述(甲基)丙烯酸共聚物中之酸性官能基相互作用，抑制上述分散劑轉移至上述黏著組成物之界面，所以防止了黏著劑保存時之黏著力變化。 The acidity of the dispersant is determined based on its acid value, and the alkalinity of the dispersant is determined based on its amine value. The use of a dispersant having an acid value of 20 mg KOH / g or more can prevent the thickening phenomenon of the above-mentioned adhesive composition precursor. In addition, the use of a dispersant with an amine value of 5 mg KOH / g or more can prevent a change in the adhesive force during storage of the adhesive. This system can be considered that the acidic functional group of the dispersant covers the basic active site of the hydrous metal compound and inhibits the interaction between the hydrous metal compound and the (meth) acrylic copolymer, so the precursor of the adhesive composition is prevented. Thickening phenomenon. In addition, it is considered that the basic functional group in the dispersant interacts with the acidic functional group in the (meth) acrylic acid copolymer to inhibit the dispersant from being transferred to the interface of the adhesive composition, thereby preventing the storage of the adhesive. Adhesion changes with time.
上述分散劑之含量係相對於上述含水金屬化合物100質量份，設為0.1~15質量份為理想，0.3~10質量份為較理想。在上述分散劑之含量未達0.1質量份係無法得到充分的分散性，若上述分散劑之含量超過15質量份，則在高溫下之接著性容易下降，會擔心對於黏著力或保持力之影響。 The content of the dispersant is preferably 0.1 to 15 parts by mass, and more preferably 0.3 to 10 parts by mass based on 100 parts by mass of the water-containing metal compound. If the content of the dispersant is less than 0.1 parts by mass, sufficient dispersibility cannot be obtained. If the content of the dispersant exceeds 15 parts by mass, the adhesiveness at high temperatures tends to decrease, and there is concern about the effect on adhesion or retention. .
本發明之黏著組成物前驅體，其係更含有光聚合起始劑為理想。作為上述光聚合起始劑，例如可使用苯乙酮類、二苯基酮類、縮酮類、蒽醌類、塞噸酮類、偶氮化合物、過氧化物、2,3-二烷基二酮化合物、二硫醚化合物、秋蘭姆化合物、氟胺化合物等。這些光聚合起始劑係至少使用一種為佳。上述光聚合起始劑之使用量係無特別限定，但相對於樹脂成分的(甲基)丙烯酸共聚物與(甲基)丙烯酸單體之合計100質量份，設為0.01~3質量份為佳，0.1~2質量份為理想。 The adhesive composition precursor of the present invention preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, diphenylketones, ketals, anthraquinones, xanthones, azo compounds, peroxides, and 2,3-dialkyl groups. Diketone compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, and the like. Preferably, at least one of these photopolymerization initiators is used. The amount of the photopolymerization initiator used is not particularly limited, but is preferably 0.01 to 3 parts by mass based on 100 parts by mass of the total of the (meth) acrylic copolymer and (meth) acrylic monomer in the resin component. , 0.1 ~ 2 parts by mass is ideal.
本發明之黏著組成物前驅體，其係更含有交聯劑為佳。作為上述交聯劑，例如可舉出1,6-己二醇二丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三丙烯二(甲基)丙烯酸酯、二季戊四醇六丙烯酸酯等之多官能(甲基)丙烯酸酯單體。上述交聯劑之添加量，其係相對於為樹脂成分的(甲基)丙烯酸共聚物與(甲基)丙烯酸單體之合計100質量份，設為0.05~5質量份即可。 The adhesive composition precursor of the present invention preferably contains a crosslinking agent. Examples of the cross-linking agent include 1,6-hexanediol diacrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, and neopentyl glycol di (methyl). Multifunctional (meth) acrylate monomers such as acrylate, trimethylolpropane tri (meth) acrylate, tripropylene di (meth) acrylate, dipentaerythritol hexaacrylate, and the like. The addition amount of the said crosslinking agent is 0.05-5 mass parts with respect to 100 mass parts of the total of (meth) acrylic copolymer and (meth) acrylic monomer which are resin components.
於本發明之黏著組成物前驅體，其係按照必要而添加 增黏劑為佳。作為上述增黏劑，例如可舉出萜烯系樹脂、萜烯酚樹脂、松香系樹脂、石油系樹脂(C5系石油樹脂、C9系石油樹脂)、酚系樹脂、香豆酮-茚樹脂、脂環族系石油樹脂、脂環族系氫化石油樹脂、苯乙烯系樹脂、二環戊二烯樹脂等。上述增黏劑之調配量，其係相對於為樹脂成分的上述(甲基)丙烯酸共聚物與上述(甲基)丙烯酸單體之合計100質量份，設為2~200質量份為理想。 The adhesive composition precursor in the present invention is added as necessary Tackifiers are preferred. Examples of the tackifier include terpene resins, terpene phenol resins, rosin resins, petroleum resins (C5 petroleum resins, C9 petroleum resins), phenol resins, coumarone-indene resins, Alicyclic petroleum resin, alicyclic hydrogenated petroleum resin, styrene resin, dicyclopentadiene resin, etc. The blending amount of the tackifier is preferably 2 to 200 parts by mass based on 100 parts by mass of the total of the (meth) acrylic copolymer and the (meth) acrylic monomer which are resin components.
本發明之黏著組成物前驅體之製造方法係無特別限定，例如混合上述各成分，將各固形成分充分地分散即可。上述混合方法係無特別限定，例如可使用分散機、均質機、帶式混合機、槳葉混合機、行星式混合機、輥軋機、捏合機、球磨機、砂磨機、超音波分散機等而進行混合。 The method for producing the adhesive composition precursor of the present invention is not particularly limited, and for example, the above-mentioned respective components are mixed, and each solid component may be sufficiently dispersed. The above-mentioned mixing method is not particularly limited, and for example, a disperser, a homogenizer, a belt mixer, a paddle mixer, a planetary mixer, a roll mill, a kneader, a ball mill, a sand mill, an ultrasonic disperser, and the like can be used. Mix.
本發明之黏著組成物，其係將上述本發明之黏著組成物前驅體所含的(甲基)丙烯酸單體進行聚合而形成。藉由聚合上述(甲基)丙烯酸單體，而上述黏著組成物前驅體成為具有黏著力的黏著組成物，也就是黏著劑。本發明之黏著組成物，因為其係將上述本發明之黏著組成物前驅體所含的(甲基)丙烯酸單體進行聚合而形成，所以熱傳導性高，具有難燃性，較先前具有更大的黏著力。 The adhesive composition of the present invention is formed by polymerizing a (meth) acrylic monomer contained in the precursor of the adhesive composition of the present invention. By polymerizing the (meth) acrylic monomer, the precursor of the adhesive composition becomes an adhesive composition having an adhesive force, that is, an adhesive. The adhesive composition of the present invention is formed by polymerizing the (meth) acrylic monomer contained in the precursor of the adhesive composition of the present invention, so it has high thermal conductivity, flame resistance, and is larger than before. Adhesion.
因而，本發明之黏著組成物，其係可以一種製造方法來製造，該方法為具備調製上述本發明之黏著組 成物前驅體的步驟、與聚合上述黏著組成物前驅體所含的上述(甲基)丙烯酸單體的步驟。聚合上述(甲基)丙烯酸單體的方法係無特別限定，但可使用對上述黏著組成物前驅體照射紫外線等之電離輻射線的方法。 Therefore, the adhesive composition of the present invention can be manufactured by a manufacturing method that includes the above-mentioned adhesive group of the present invention. A step of forming a precursor, and a step of polymerizing the (meth) acrylic monomer contained in the adhesive composition precursor. The method of polymerizing the (meth) acrylic monomer is not particularly limited, but a method of irradiating an ionizing radiation such as ultraviolet rays to the precursor of the adhesive composition may be used.
作為上述電離輻射線，例如可使用紫外線、電子束、β線等，但由於可簡便地利用之故，大多使用紫外線。作為紫外線之光源，可使用高壓水銀燈、金屬鹵素燈、紫外線LED燈等。在作為上述電離輻射線使用紫外線的情況，於上述黏著組成物前驅體係含有光聚合起始劑為理想。 As the ionizing radiation, for example, ultraviolet rays, electron beams, beta rays, and the like can be used. However, since they can be easily used, ultraviolet rays are often used. As the ultraviolet light source, a high-pressure mercury lamp, a metal halide lamp, an ultraviolet LED lamp, or the like can be used. When ultraviolet rays are used as the ionizing radiation, it is preferable that a photopolymerization initiator is contained in the adhesive composition precursor system.
本發明之黏著薄片，其係將上述本發明之黏著組成物成形至薄片狀者。本發明之黏著薄片，因為其係將上述本發明之黏著組成物進行成形者，所以熱傳導性高，具有難燃性，較先前具有更大的黏著力。 The adhesive sheet of the present invention is formed by forming the adhesive composition of the present invention into a sheet form. Since the adhesive sheet of the present invention is formed by forming the adhesive composition of the present invention, it has high thermal conductivity, flame resistance, and greater adhesive force than before.
本發明之黏著薄片之厚度係未特別限定，例如可設為10~800μm。 The thickness of the adhesive sheet of the present invention is not particularly limited, and may be, for example, 10 to 800 μm.
本發明之黏著薄片，亦可於兩面更具備剝離基材。藉由具備上述剝離基材，而本發明之黏著薄片之操作變得容易。 The adhesive sheet of the present invention may further be provided with a release substrate on both sides. With the above-mentioned release substrate, the operation of the adhesive sheet of the present invention becomes easy.
另外，本發明之黏著薄片，其係可以一種製造方法來製造，該方法為具備調製上述本發明之黏著組成物前驅體的步驟、與聚合上述黏著組成物前驅體所含的上 述(甲基)丙烯酸單體而成形為薄片狀的步驟。 In addition, the adhesive sheet of the present invention can be manufactured by a manufacturing method including the steps of preparing the above-mentioned adhesive composition precursor of the present invention, and polymerizing the upper part contained in the above-mentioned adhesive composition precursor. The step of forming a (meth) acrylic monomer into a sheet shape is described.
上述聚合(甲基)丙烯酸單體而成形為薄片狀的方法係未特別限定，例如可使用於基材之上塗布上述黏著組成物前驅體而形成了塗膜之後，更於該塗膜之上配置基材，之後於上述塗膜通過上述基材，照射前述之紫外線等之電離輻射線的方法。於此時，作為上述基材如使用剝離基材，可簡便地得到附有剝離基材的黏著薄片。另外，在電離輻射線使用紫外線的情況，於上述基材之至少一方的紫外線之照射側係使用透明基材為理想。 The method of polymerizing the (meth) acrylic monomer to form a sheet is not particularly limited. For example, the method can be applied to a base material to form a coating film by coating the above-mentioned adhesive composition precursor, and then on the coating film. A method of arranging a substrate, and then passing the substrate through the substrate and irradiating the aforementioned ionizing radiation such as ultraviolet rays. At this time, if a release substrate is used as the substrate, an adhesive sheet with a release substrate can be easily obtained. In the case where ultraviolet rays are used for the ionizing radiation, it is preferable to use a transparent base material on the irradiation side of the ultraviolet rays on at least one of the base materials.
另外，塗布上述黏著組成物前驅體的方法，如為可形成平滑的塗膜的塗布方法則無特別限制，例如可舉出凹版輥法、微凹版輥法、微凹版塗佈法、縫模塗布法、噴霧法、旋轉法、刮刀法、接觸法、擠壓法、反輥法、浸漬法、棒式塗布法等。 The method for coating the precursor of the adhesive composition is not particularly limited as long as it is a coating method capable of forming a smooth coating film, and examples thereof include a gravure roll method, a microgravure roll method, a microgravure coating method, and a slot die coating method. Method, spray method, rotation method, doctor blade method, contact method, extrusion method, reverse roll method, dipping method, bar coating method, and the like.
作為上述基材係無特別限定，例如可使用由聚對苯二甲酸二乙酯、聚萘二甲酸乙二酯等之聚酯系樹脂、聚烯烴類、纖維素三乙酸酯等之纖維素系樹脂、尼龍、芳香族聚醯胺等之醯胺系樹脂、聚苯醚、聚碸醚等之聚醚系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚醯胺醯亞胺系樹脂、芳香族聚醯胺系樹脂、環烯烴聚合物類、紙等之材類所構成的薄膜或薄片。 The base material is not particularly limited, and for example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, celluloses such as polyolefins, and cellulose triacetate can be used. Resins, polyamide resins such as nylon, aromatic polyamines, polyether resins such as polyphenylene ethers, polyethers, polycarbonate resins, polyamine resins, polyimide resins, Films or sheets made of materials such as polyamidoamine imine-based resin, aromatic polyamidoamine-based resin, cycloolefin polymers, and paper.
另外，於上述基材賦與剝離性，其係於上述基材之至少單面形成由聚矽氧樹脂等所構成的離型層為佳。 In addition, it is preferable that the release property is imparted to the substrate, and a release layer made of a silicone resin or the like is formed on at least one side of the substrate.
接著，將本發明之黏著薄片根據圖面而說明。第1圖係表示本發明之黏著薄片之一例的模式剖面圖。在第1圖中，本發明之黏著薄片10係在剝離薄膜11及13之間具備薄片狀之黏著劑12。在使用黏著薄片10的情況，除去剝離薄膜11及13，將薄片狀之黏著劑12配置於接合構件之間而加壓等而接合即可。 Next, the adhesive sheet of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the adhesive sheet of the present invention. In FIG. 1, the adhesive sheet 10 of the present invention is provided with a sheet-shaped adhesive 12 between the release films 11 and 13. In the case of using the adhesive sheet 10, the release films 11 and 13 are removed, and the sheet-shaped adhesive 12 may be placed between the bonding members and then bonded by applying pressure or the like.
本發明之黏著薄片之黏著力係以90°剝離試驗所生的黏著力為5N/10mm以上為理想。若上述黏著力未達5N/10mm，則會擔心例如產生發熱的電子零件等、與散熱器、散熱鰭片等之散熱構件之間產生剝離。 The adhesive force of the adhesive sheet of the present invention is preferably an adhesive force generated by a 90 ° peel test of 5N / 10mm or more. If the above-mentioned adhesive force is less than 5N / 10mm, there is a concern that, for example, peeling may occur between electronic components and the like that generate heat and heat-radiating members such as heat sinks and heat-radiating fins.
本發明之黏著薄片之熱傳導率，為了充分顯現傳熱性，所以為0.5W/m‧K以上為理想。另外，上述黏著薄片之難燃性，其係為了抑制在大氣中之燃燒所以依JIS K7201-2所規定的氧指數為21以上為理想。 The thermal conductivity of the adhesive sheet of the present invention is preferably 0.5 W / m · K or more in order to sufficiently exhibit heat transfer properties. In addition, the flame retardancy of the above-mentioned adhesive sheet is preferably an oxygen index of 21 or more in accordance with JIS K7201-2 in order to suppress combustion in the atmosphere.
本發明之電子儀器，其係具備上述本發明之黏著薄片，藉由上述黏著薄片，接合發熱的電子零件等、與散熱器、散熱鰭片等之散熱構件。本發明之電子儀器，其係因為使用本發明之黏著薄片而接合發熱構件與散熱構件，所以可抑制上述電子儀器之發熱。 The electronic device of the present invention includes the above-mentioned adhesive sheet of the present invention, and through the above-mentioned adhesive sheet, heat-generating electronic parts and the like, and a heat-radiating member such as a heat sink and a heat-radiating fin are joined. Since the electronic device of the present invention uses the adhesive sheet of the present invention to join the heat generating member and the heat radiating member, it is possible to suppress the heat generation of the electronic device.
以下，藉由實施例而詳細地說明本發明。但 是，本發明係不被以下之實施例所限定。另外，在以下之實施例中，「份」係意味著「質量份」。 Hereinafter, the present invention will be described in detail through examples. but However, the present invention is not limited to the following examples. In the following examples, "part" means "mass part".
首先，將以下之成分(1)~(6)放入不銹鋼製之燒杯，在水冷下用分散機攪拌而混合而調製混合液。 First, the following components (1) to (6) are put into a stainless steel beaker, and they are stirred and mixed with a disperser under water cooling to prepare a mixed solution.
(1)丙烯酸漿料(綜研化學公司製，商品名"SK Dyne syrup B"、2乙基己基丙烯酸酯：90質量份/丙烯酸9質量份/2羥乙基丙烯酸酯：1質量份所成的部分共聚物)：58.39份 (1) Acrylic slurry (manufactured by Soken Chemical Co., Ltd., trade name "SK Dyne syrup B", 2 ethylhexyl acrylate: 90 parts by mass / 9 parts by mass of acrylic acid / 2 hydroxyethyl acrylate: 1 part by mass Partial copolymer): 58.39 parts
(2)2乙基己基丙烯酸酯：52.55份 (2) 2 ethylhexyl acrylate: 52.55 parts
(3)丙烯酸：5.84份 (3) Acrylic acid: 5.84 parts
(4)交聯劑(三羥甲基丙烷三丙烯酸酯)：0.29份 (4) Crosslinking agent (trimethylolpropane triacrylate): 0.29 parts
(5)分散劑(BYK-Chemie公司製，商品名"DISPERBYK 145"，兩性分散劑)：2.34份 (5) Dispersant (manufactured by BYK-Chemie, trade name "DISPERBYK 145", amphoteric dispersant): 2.34 parts
(6)光聚合起始劑[雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物]：0.58份 (6) Photopolymerization initiator [bis (2,4,6-trimethylbenzylidene) phenylphosphine oxide]: 0.58 parts
接著，於上述混合液調配下述成分(7)，更進一步攪拌15分鐘而得到黏著劑前驅體(黏著組成物前驅體)。 Next, the following component (7) was prepared in the above-mentioned mixed solution, and further stirred for 15 minutes to obtain an adhesive precursor (adhesive composition precursor).
(7)含水金屬化合物(板狀水鋁石，平均粒徑4μm，長寬比10)：100份 (7) Hydrous metal compound (plate-type gibbsite, average particle diameter 4 μm, aspect ratio 10): 100 parts
在厚度38μm之離型聚對苯二甲酸二乙酯(PET)薄膜(中本Packs公司製，商品名"NS-38+A")之上，塗布上述黏著劑前驅體而形成塗膜之後，於該塗膜上，疊上厚度50μm之離型PET薄膜(中本Packs公司製，商品名"NS-50-ZW)之後，以缺角輪塗佈機進行塗膜之厚度之調整，之後照射紫外線照射而進行上述塗膜之硬化處理，製作了附有離型PET薄膜的黏著薄片。在上述缺角輪塗佈機之厚度調整，其係將支撐輥與刀輥之間隙間隔以硬化處理後之黏著薄片之厚度成為250μm之方式來進行。上述紫外線照射，其係使用在波長365nm具有峰值的黑光而將累積光量設為300mJ/cm2，更進一步使用高壓水銀燈而將累積光量成為250mJ/cm2之方式進行。 The above-mentioned adhesive precursor was applied on a release polyethylene terephthalate (PET) film (manufactured by Nakamoto Packs, trade name "NS-38 + A") with a thickness of 38 μm to form a coating film. On this coating film, a release PET film (manufactured by Nakamoto Packs, trade name "NS-50-ZW") with a thickness of 50 μm was stacked, and then the thickness of the coating film was adjusted by a notch wheel coater and then irradiated The coating film was hardened by ultraviolet irradiation, and an adhesive sheet with a release PET film was produced. In the thickness adjustment of the notch wheel coating machine, the gap between the support roller and the knife roller was adjusted after the hardening treatment. The thickness of the adhesive sheet is 250 μm. The above-mentioned ultraviolet irradiation uses black light with a peak at a wavelength of 365 nm to set the cumulative light amount to 300 mJ / cm 2 , and further uses a high-pressure mercury lamp to set the cumulative light amount to 250 mJ / cm 2 way.
除了將含水金屬化合物變更為板狀水鋁石(平均粒徑：2μm、長寬比：10)100份以外，其係與實施例1以同樣方式進行而製作附有離型PET薄膜的黏著薄片。 A pressure-sensitive adhesive sheet with a release PET film was produced in the same manner as in Example 1 except that the hydrous metal compound was changed to 100 parts of plate-shaped gibbsite (average particle diameter: 2 μm, aspect ratio: 10). .
首先，將以下之成分(1)~(6)放入不銹鋼製之燒杯，在水冷下用分散機攪拌而混合而調製混合液。 First, the following components (1) to (6) are put into a stainless steel beaker, and they are stirred and mixed with a disperser under water cooling to prepare a mixed solution.
(1)丙烯酸漿料(綜研化學公司製，商品名"SK Dyne syrup B")：32.53份 (1) Acrylic slurry (manufactured by Soken Chemical Co., Ltd., trade name "SK Dyne" syrup B "): 32.53
(2)2乙基己基丙烯酸酯：19.52份 (2) 2 ethylhexyl acrylate: 19.52 parts
(3)丙烯酸：2.17份 (3) Acrylic acid: 2.17 parts
(4)交聯劑(三羥甲基丙烷三丙烯酸酯)：0.14份 (4) Crosslinking agent (trimethylolpropane triacrylate): 0.14 parts
(5)分散劑(BYK-Chemie公司製，商品名"DISPERBYK 145")：1.08份 (5) Dispersant (manufactured by BYK-Chemie, trade name "DISPERBYK 145"): 1.08 parts
(6)光聚合起始劑[雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物]：0.27份 (6) Photopolymerization initiator [bis (2,4,6-trimethylbenzylidene) phenylphosphine oxide]: 0.27 parts
接著，於上述混合液調配下述成分(7)，更進一步攪拌15分鐘而得到黏著劑前驅體(黏著組成物前驅體)。 Next, the following component (7) was prepared in the above-mentioned mixed solution, and further stirred for 15 minutes to obtain an adhesive precursor (adhesive composition precursor).
(7)含水金屬化合物(板狀水鋁石，平均粒徑2μm，長寬比10)：100份 (7) Water-containing metal compound (plate-shaped gibbsite, average particle diameter 2 μm, aspect ratio 10): 100 parts
除了使用了上述黏著劑前驅體以外，其係與實施例1以同樣方式進行而製作附有離型PET薄膜的黏著薄片。 A pressure-sensitive adhesive sheet with a release PET film was produced in the same manner as in Example 1 except that the above-mentioned adhesive precursor was used.
首先，將以下之成分(1)~(6)放入不銹鋼製之燒杯，在水冷下用分散機攪拌而混合而調製混合液。 First, the following components (1) to (6) are put into a stainless steel beaker, and they are stirred and mixed with a disperser under water cooling to prepare a mixed solution.
(1)丙烯酸漿料(綜研化學公司製，商品名"SK Dyue syrup B")：40.33份 (1) Acrylic slurry (manufactured by Soken Chemical Co., Ltd., trade name "SK Dyue syrup B"): 40.33 copies
(2)2乙基己基丙烯酸酯：24.20份 (2) 2 ethylhexyl acrylate: 24.20 parts
(3)丙烯酸：2.69份 (3) Acrylic acid: 2.69 parts
(4)交聯劑(三羥甲基丙烷三丙烯酸酯)：0.17份 (4) Crosslinking agent (trimethylolpropane triacrylate): 0.17 parts
(5)分散劑(BYK-Chemie公司製，商品名"DISPERBYK 145")：1.34份 (5) Dispersant (manufactured by BYK-Chemie, trade name "DISPERBYK 145"): 1.34 parts
(6)光聚合起始劑[雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物]：0.34份 (6) Photopolymerization initiator [bis (2,4,6-trimethylbenzylidene) phenylphosphine oxide]: 0.34 parts
接著，於上述混合液調配下述成分(7)，更進一步攪拌15分鐘而得到黏著劑前驅體(黏著組成物前驅體)。 Next, the following component (7) was prepared in the above-mentioned mixed solution, and further stirred for 15 minutes to obtain an adhesive precursor (adhesive composition precursor).
(7)含水金屬化合物(鱗片狀氫氧化鋁，平均粒徑8μm，長寬比15)：100份 (7) Water-containing metal compound (scaly aluminum hydroxide, average particle diameter 8 μm, aspect ratio 15): 100 parts
除了使用了上述黏著劑前驅體以外，其係與實施例1以同樣方式進行而製作附有離型PET薄膜的黏著薄片。 A pressure-sensitive adhesive sheet with a release PET film was produced in the same manner as in Example 1 except that the above-mentioned adhesive precursor was used.
除了將含水金屬化合物變更為粒狀水鋁石(平均粒徑1μm，長寬比1.2)：100份以外，其係與實施例1以同樣方式進行而製作附有離型PET薄膜的黏著薄片。 A pressure-sensitive adhesive sheet with a release PET film was produced in the same manner as in Example 1 except that the hydrous metal compound was changed to granular boehmite (average particle diameter: 1 μm, aspect ratio: 1.2): 100 parts.
除了將含水金屬化合物變更為板狀水鋁石(平均粒 徑：1μm、長寬比：10)：100份以外，其係與實施例3以同樣方式進行而製作附有離型PET薄膜的黏著薄片。 In addition to changing the hydrated metal Diameter: 1 μm, aspect ratio: 10): Except for 100 parts, it was performed in the same manner as in Example 3 to produce an adhesive sheet with a release PET film.
除了將含水金屬化合物變更為粒狀氫氧化鋁(平均粒徑：5μm、長寬比：1.4)：100份以外，其係與實施例4以同樣方式進行而製作附有離型PET薄膜的黏著薄片。 Except that the water-containing metal compound was changed to granular aluminum hydroxide (average particle diameter: 5 μm, aspect ratio: 1.4): 100 parts, it was carried out in the same manner as in Example 4 to produce an adhesive with a release PET film. Flakes.
首先，將以下之成分(1)~(6)放入不銹鋼製之燒杯，在水冷下用分散機攪拌而混合而調製混合液。 First, the following components (1) to (6) are put into a stainless steel beaker, and they are stirred and mixed with a disperser under water cooling to prepare a mixed solution.
(1)丙烯酸漿料(綜研化學公司製，商品名"SK Dyne syrup B")：195.45份 (1) Acrylic slurry (manufactured by Soken Chemical Co., Ltd., trade name "SK Dyne syrup B"): 195.45 parts
(2)2乙基己基丙烯酸酯：117.27份 (2) 2 ethylhexyl acrylate: 117.27 parts
(3)丙烯酸：13.03份 (3) Acrylic acid: 13.03 parts
(4)交聯劑(三羥甲基丙烷三丙烯酸酯)：0.81份 (4) Crosslinking agent (trimethylolpropane triacrylate): 0.81 parts
(5)分散劑(BYK-Chemie公司製，商品名"DISPERBYK 145")：6.52份 (5) Dispersant (manufactured by BYK-Chemie, trade name "DISPERBYK 145"): 6.52 parts
(6)光聚合起始劑[雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物]：1.63份 (6) Photopolymerization initiator [bis (2,4,6-trimethylbenzylidene) phenylphosphine oxide]: 1.63 parts
接著，於上述混合液調配下述成分(7)，更進一步攪拌15分鐘而得到黏著劑前驅體(黏著組成物前驅體)。 Next, the following component (7) was prepared in the above-mentioned mixed solution, and further stirred for 15 minutes to obtain an adhesive precursor (adhesive composition precursor).
(7)含水金屬化合物(鱗片狀氫氧化鋁，平均粒徑8μm，長寬比15)：100份 (7) Water-containing metal compound (scaly aluminum hydroxide, average particle diameter 8 μm, aspect ratio 15): 100 parts
除了使用了上述黏著劑前驅體以外，其係與實施例1以同樣方式進行而製作附有離型PET薄膜的黏著薄片。 A pressure-sensitive adhesive sheet with a release PET film was produced in the same manner as in Example 1 except that the above-mentioned adhesive precursor was used.
將實施例1~4及比較例1~4所製作的附有離型PET薄膜的黏著薄片之黏著力和熱傳導率，以下述之方式來進行評估。 The adhesive force and thermal conductivity of the release sheet with a release PET film produced in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated in the following manner.
由已製作的附有離型PET薄膜的黏著薄片上完全剝離PET薄膜，將剝離PET薄膜後之黏著薄片，貼於厚度50μm之未進行離型處理的通常之PET薄膜，將該附有PET薄膜的黏著薄片切斷為寬25mm、長250mm而製作評估樣本，將該評估樣本之黏著薄片側貼於不銹鋼板，用質量2kg之輥以速度300mm/分而1次往復於評估樣本之上，將評估樣本壓接於不銹鋼板，放置24小時。之後，將評估樣本由不銹鋼板剝離的90°剝離試驗，以剝離速度300mm/分來進行，將測定出的剝離負重換算為10mm，設為黏著力之測定值。 The PET film was completely peeled from the prepared adhesive sheet with a release PET film, and the adhesive sheet after the PET film was peeled off was affixed to a normal PET film having a thickness of 50 μm without a release treatment. The adhesive sheet was cut to a width of 25mm and a length of 250mm to make an evaluation sample. The adhesive sheet side of the evaluation sample was affixed to a stainless steel plate. A roller with a mass of 2kg was used to reciprocate the evaluation sample at a speed of 300mm / min. The evaluation sample was crimped to a stainless steel plate and left for 24 hours. Thereafter, a 90 ° peel test in which the evaluation sample was peeled from the stainless steel plate was performed at a peel speed of 300 mm / min, and the measured peel load was converted to 10 mm to be a measured value of adhesion.
由已製作的附有離型PET薄膜的黏著薄片將PET薄膜全部剝離，將剝離PET薄膜後之黏著薄片，切斷為寬50mm、長150mm而製作評估樣本，將該評估樣本重疊5片而設為層積體，使用京都電子工業公司製之迅速熱導率計"QTM-500"，與薄膜測定用軟體組合而測定上述層積體之熱傳導率。於本測定之基準係使用矽樹脂、石英、氧化鋯。 The entire PET film was peeled from the prepared adhesive sheet with a release PET film, and the adhesive sheet after peeling the PET film was cut into a width of 50 mm and a length of 150 mm to prepare an evaluation sample. For the laminated body, a rapid thermal conductivity meter "QTM-500" manufactured by Kyoto Electronics Co., Ltd. was used in combination with a software for measuring thin films to measure the thermal conductivity of the laminated body. In this measurement, silicone resin, quartz, and zirconia were used.
將以上結果表示於表1。另外，於表1中，亦表示所使用的含水金屬化合物之種類、平均粒徑、長寬比及含有率。 The above results are shown in Table 1. In addition, Table 1 also shows the types, average particle diameters, aspect ratios, and content ratios of the hydrous metal compounds used.
由表1可了解，本發明之實施例1~4之黏著 薄片，其係黏著力大於5N/10mm，熱傳導率亦成為0.5W/m‧K以上，黏著力及熱傳導率均為高者。另一方面，可了解含水金屬化合物之平均粒徑低於2μm，該長寬比低於5的比較例1，其係黏著力及熱傳導率均低劣，在含水金屬化合物之平均粒徑低於2μm的比較例2，其係黏著力低劣，在含水金屬化合物之長寬比低於5的比較例3，其係黏著力低劣，在含水金屬化合物之含有率未達30質量%的比較例4，其係熱傳導率大幅地低於0.5W/m‧K。 As can be understood from Table 1, the adhesion of Examples 1 to 4 of the present invention The flakes have an adhesive force greater than 5N / 10mm and a thermal conductivity of more than 0.5W / m‧K. The adhesive force and thermal conductivity are both high. On the other hand, it can be understood that the average particle diameter of the hydrous metal compound is less than 2 μm, and the aspect ratio of Comparative Example 1 below 5 is inferior in adhesion and thermal conductivity, and the average particle diameter of the hydrous metal compound is less than 2 μm Comparative Example 2, which is inferior in adhesion, and Comparative Example 3 in which the aspect ratio of the hydrous metal compound is less than 5, is inferior in adhesion, and is in Comparative Example 4, whose content rate of the hydrous metal compound is less than 30% by mass. Its thermal conductivity is significantly lower than 0.5W / m‧K.
本發明係可提供黏著力及熱傳導性均優異的黏著薄片，可將發熱構件與散熱構件之間以大的黏著力、具有高的熱傳導性的同時進行接合，可提高具備發熱構件與散熱構件的電子儀器之散熱性能。 The present invention can provide an adhesive sheet having excellent adhesive force and thermal conductivity, and can simultaneously bond a heat generating member and a heat radiating member with high adhesive force and high thermal conductivity, thereby improving the performance of the heat-emitting member and the heat radiating member. Thermal performance of electronic instruments.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003002481A (en) * | 2001-06-19 | 2003-01-08 | Arai Pump Mfg Co Ltd | Rubber composition for carrying roller, carrying roller using the same, and manufacturing method for the same |
| CN102741372A (en) * | 2010-02-19 | 2012-10-17 | 日本瑞翁株式会社 | Thermally conductive pressure-sensitive adhesive composition,thermally conductive pressure-sensitive adhesive sheet,and electronic component |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11269438A (en) * | 1998-03-25 | 1999-10-05 | Dainippon Ink & Chem Inc | Heat-conductive flame-retardant pressure-sensitive adhesive and pressure-sensitive adhesive tape |
| TW200535205A (en) * | 2003-11-13 | 2005-11-01 | Lg Chemical Ltd | Adhesives having advanced flame-retardant property |
| JP2010114421A (en) | 2008-10-08 | 2010-05-20 | Hitachi Chem Co Ltd | Thermally conductive sheet and manufacturing method thereof |
| JP5651344B2 (en) * | 2010-02-04 | 2015-01-14 | 日東電工株式会社 | Thermally conductive double-sided adhesive sheet |
| JP2011178852A (en) * | 2010-02-26 | 2011-09-15 | Konishi Co Ltd | Two-pack separate coating-type rapid curing aqueous adhesive and adhesion method using the aqueous adhesive |
| JP2011241329A (en) * | 2010-05-19 | 2011-12-01 | Nitto Denko Corp | Heat-conductive self-adhesive sheet |
| JP2012064691A (en) * | 2010-09-15 | 2012-03-29 | Furukawa Electric Co Ltd:The | Thermal diffusion sheet |
| JP2012116885A (en) * | 2010-11-29 | 2012-06-21 | Nippon Zeon Co Ltd | Heat-conductive pressure-sensitive adhesive composition and heat-conductive pressure-sensitive adhesive sheet-like molding, their manufacturing method, and electronic component |
| JP5912337B2 (en) * | 2011-04-09 | 2016-04-27 | 日東電工株式会社 | Flame retardant thermal conductive adhesive sheet |
| CN103547644B (en) * | 2011-06-17 | 2016-05-04 | 日本瑞翁株式会社 | Thermal conductivity pressure-sensitive adhesive sheet-like formed body, its manufacture method and electronic equipment |
| JP6161875B2 (en) * | 2011-09-14 | 2017-07-12 | 株式会社日本触媒 | Thermally conductive material |
| JP5896201B2 (en) * | 2011-10-19 | 2016-03-30 | Dic株式会社 | Adhesive composition and adhesive tape |
| CN104093803A (en) * | 2012-02-02 | 2014-10-08 | 日东电工株式会社 | Flame-retardant heat-conductive adhesive sheet |
| JP6016949B2 (en) * | 2013-01-31 | 2016-10-26 | 株式会社寺岡製作所 | Flame-retardant pressure-sensitive adhesive composition, flame-retardant heat-conductive pressure-sensitive adhesive composition, and pressure-sensitive adhesive sheet |
| JP6712513B2 (en) * | 2016-08-17 | 2020-06-24 | 株式会社バルカー | Gasket including talc sheet |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003002481A (en) * | 2001-06-19 | 2003-01-08 | Arai Pump Mfg Co Ltd | Rubber composition for carrying roller, carrying roller using the same, and manufacturing method for the same |
| CN102741372A (en) * | 2010-02-19 | 2012-10-17 | 日本瑞翁株式会社 | Thermally conductive pressure-sensitive adhesive composition,thermally conductive pressure-sensitive adhesive sheet,and electronic component |
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