CN101613517A - Resin prepreg composition glue solution, heat dissipation film and manufacturing method thereof - Google Patents
Resin prepreg composition glue solution, heat dissipation film and manufacturing method thereof Download PDFInfo
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- 239000003292 glue Substances 0.000 title claims abstract description 67
- 229920005989 resin Polymers 0.000 title claims abstract description 43
- 239000011347 resin Substances 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 230000017525 heat dissipation Effects 0.000 title abstract description 41
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000003822 epoxy resin Substances 0.000 claims description 34
- 229920000647 polyepoxide Polymers 0.000 claims description 34
- 239000003365 glass fiber Substances 0.000 claims description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- -1 phenol aldehyde Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims 4
- 239000003351 stiffener Substances 0.000 claims 3
- 230000000996 additive effect Effects 0.000 claims 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims 1
- 229910017083 AlN Inorganic materials 0.000 claims 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims 1
- 239000011812 mixed powder Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 37
- 239000004848 polyfunctional curative Substances 0.000 description 29
- 239000004744 fabric Substances 0.000 description 18
- 239000010409 thin film Substances 0.000 description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
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- 229910010271 silicon carbide Inorganic materials 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 239000005011 phenolic resin Substances 0.000 description 1
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- Reinforced Plastic Materials (AREA)
Abstract
Description
技术领域 technical field
本发明涉及一种硬化剂、树脂预浸体组成胶液、散热胶片及其制造方法，特别涉及一种具有高导热效率的硬化剂、树脂预浸体组成胶液、散热胶片及其制造方法。The invention relates to a curing agent, resin prepreg composition glue, heat dissipation film and a manufacturing method thereof, in particular to a hardener with high thermal conductivity, resin prepreg composition glue, heat dissipation film and a manufacturing method thereof.
背景技术 Background technique
目前电路板所应用的层面及领域相当广泛，一般电子产品内的电子组件都插设在电路板中，而现今的电路板为了符合高功率及高热量的组件的应用范围，故在电路板的散热功效上进行开发及研究，以提高电路板的散热效率及高功率。At present, circuit boards are used in a wide range of levels and fields. Generally, electronic components in electronic products are inserted into circuit boards. In order to meet the application range of high-power and high-heat components, current circuit boards are placed in the circuit board. Development and research are carried out on the heat dissipation effect to improve the heat dissipation efficiency and high power of the circuit board.
在传统的电路板构造上，由于插设于其上的电子组件数量及消耗功率较低，电子组件所产生的热量大都可通过电路板中的铜箔层进行热传导并向外散热，将热直接散逸至环境，利用空气的对流达成电子组件温度的控制。然而随着信息量及运算速度的提高，现今电路板上所布设的电子组件功率高且数量又多，伴随而来的问题便是所消耗的电功率增加，导致在局部耗电组件上产生大量的热，致使电路板温度升高，直接或间接影响组件的功能及产品的可靠度。In the traditional circuit board structure, due to the low number of electronic components inserted on it and the low power consumption, most of the heat generated by the electronic components can be conducted through the copper foil layer in the circuit board and dissipated outward, dissipating the heat directly Dissipate to the environment, and use air convection to control the temperature of electronic components. However, with the increase of the amount of information and the speed of calculation, the electronic components arranged on the current circuit board have high power and a large number. Heat, causing the temperature of the circuit board to rise, directly or indirectly affect the function of the component and the reliability of the product.
为了避免电路板的聚热现象使组件功能无法正常运作，电路板的制作技术不断演进，例如提升耐热性及高热传导等议题的发展，其中一种广为应用的电路板散热技术是将单层或多层印刷电路板利用一绝缘散热贴合层与散热金属板(如铝板)进行压合(贴合)，利用铝板的良好散热效果以散逸电子组件所产生的热。In order to avoid the phenomenon of heat accumulation on the circuit board and make the function of the components unable to function normally, the production technology of the circuit board is constantly evolving, such as the development of issues such as improving heat resistance and high heat conduction. One of the widely used heat dissipation technologies for circuit boards is The multi-layer or multi-layer printed circuit board uses an insulating and heat-dissipating bonding layer to press (laminate) with a heat-dissipating metal plate (such as an aluminum plate), and utilizes the good heat dissipation effect of the aluminum plate to dissipate the heat generated by electronic components.
其中所谓的绝缘散热贴合层，除提供印刷电路板与散热金属板的贴合固定之外，更重要需提供良好的热传导的效果。此绝缘散热贴合层可以是一种半固化环氧树脂胶片，利用热压合程序将印刷电路板、绝缘散热贴合层与散热金属板充分贴合，而该半固化环氧树脂胶片系将玻璃纤维布浸渍于一环氧树脂预浸体组成胶液，并进行干燥等后续工艺而形成一种薄型散热胶片。Among them, the so-called insulating and heat-dissipating bonding layer, in addition to providing bonding and fixing the printed circuit board and the heat-dissipating metal plate, is more important to provide a good heat conduction effect. The insulating and heat-dissipating bonding layer can be a semi-cured epoxy resin film, and the printed circuit board, the insulating and heat-dissipating bonding layer and the heat-dissipating metal plate are fully bonded by using a thermocompression process, and the semi-cured epoxy resin film is The glass fiber cloth is impregnated with an epoxy resin prepreg to form a glue solution, and then dried and other subsequent processes are performed to form a thin heat dissipation film.
常用的环氧树脂预浸体组成胶液，例如中华民国专利公开号第200611927号，利用高比例成份的无机散热填充料混入上述环氧树脂预浸体组成胶液，故使玻璃纤维布在经过浸渍之后所制成的薄型散热胶片具有良好的散热效果，然而对于常用的环氧树脂材料及与其配合的硬化剂、促进剂、添加剂等调配组成需加以调整，才得以应用于该高比例含量的无机散热填充料，否则将导致所制成的薄型散热胶片产生易剥落及耐热性不佳的问题，上述问题的发生原因大部分均在于硬化剂的选用不当所导致。举例来说，常用的环氧树脂预浸体组成胶液中之环氧树脂一般采用苯酚或酚醛类环氧树脂，如双酚A型环氧树脂，因此搭配的硬化剂多会采二氰胺类(Dicy)或苯酚(PN phenolic)类硬化剂。然而为了提升散热薄型胶片的散热功能，该环氧树脂预浸体组成胶液成分采用大量的无机散热填充料粉体，因此造成相对单位内的交联树脂成分用量将被大幅地降低，使所浸渍形成的散热薄型胶片部分树脂的特性造成减损，例如采用二氰胺类硬化剂的环氧树脂预浸体组成胶液所制成的散热薄型胶片的耐热性降低，易产生爆板的问题；另一方面采用酚醛环氧脂硬化剂的环氧树脂预浸体组成胶液所制成的散热薄型胶片的附着能力降低，因此添加较多硬化剂含量的环氧树脂预浸体组成胶液所制成的散热薄型胶片的韧性会降低，反之若添加不足，散热薄型胶片会难以固化，亦即上述的硬化剂可能导致散热薄型胶片产生易爆板或附着性不佳的问题，故均不适用于散热薄型胶片的制作。Commonly used epoxy resin prepregs to form glue, such as the Republic of China Patent Publication No. 200611927, use a high proportion of inorganic heat-dissipating fillers to mix the above epoxy resin prepregs to form glue, so the glass fiber cloth after passing The thin heat dissipation film made after impregnation has a good heat dissipation effect. However, the commonly used epoxy resin materials and their hardeners, accelerators, additives and other formulations need to be adjusted before they can be applied to this high proportion. Inorganic heat-dissipating fillers, otherwise, the thin heat-dissipating film produced will have problems of easy peeling and poor heat resistance. Most of the above problems are caused by improper selection of hardeners. For example, the epoxy resin in the commonly used epoxy resin prepreg is generally made of phenol or novolac epoxy resin, such as bisphenol A epoxy resin, so dicyandiamide is often used as the hardener. Dicy or PN phenol hardener. However, in order to improve the heat dissipation function of the heat dissipation thin film, the glue composition of the epoxy resin prepreg uses a large amount of inorganic heat dissipation filler powder, so the amount of crosslinking resin component in the relative unit will be greatly reduced, so that all Part of the resin properties of the heat-dissipating thin film formed by impregnation is degraded. For example, the heat-resistance of the heat-dissipating thin film made of epoxy resin prepreg composed of a dicyanamide hardener is reduced, and the problem of cracking is likely to occur. ; On the other hand, the adhesion ability of the heat-dissipating thin film made of the epoxy resin prepreg composed of novolac epoxy hardener is reduced, so the epoxy resin prepreg with more hardener content is added to form the glue The toughness of the heat-dissipating thin film will be reduced. On the contrary, if the addition is insufficient, the heat-dissipating thin film will be difficult to cure. That is, the above-mentioned hardener may cause the heat-dissipating thin film to produce explosive plates or poor adhesion. Therefore, it is not suitable It is suitable for the production of heat-dissipating thin films.
缘是，本发明人有感上述缺失可以改善，提出一种设计合理且有效改善上述缺失的本发明。The reason is that the inventor feels that the above-mentioned deficiency can be improved, and proposes an invention with a reasonable design and can effectively improve the above-mentioned deficiency.
发明内容 Contents of the invention
本发明的主要目的，在于提供一种硬化剂及具有该硬化剂的环氧树脂预浸体组成胶液，该硬化剂的添加，可使所制成的散热胶片兼顾耐热性及附着性，且该硬化剂的结构具有极性，故可将混入该胶液中的无机粉体均匀地分散于该环氧树脂预浸体组成胶液中。The main purpose of the present invention is to provide a curing agent and an epoxy resin prepreg with the curing agent to form a glue. The addition of the curing agent can make the heat-dissipating film made take into account both heat resistance and adhesion. And the structure of the hardener is polar, so the inorganic powder mixed in the glue can be evenly dispersed in the epoxy resin prepreg composition glue.
本发明的再一目的，为对上述的环氧树脂预浸体组成胶液加以改良以提升玻璃纤维布浸渍于该环氧树脂预浸体组成胶液所制成的散热胶片可以有更佳的散热效果及良好的加工性。Another object of the present invention is to improve the above-mentioned epoxy resin prepreg composition glue to improve the heat dissipation film made by impregnating glass fiber cloth in the epoxy resin prepreg composition glue. Heat dissipation effect and good processability.
本发明还提供一种树脂预浸体组成胶液，其特征在于，由组分(A)：环氧树脂；以及组分(B)：如式(I)所示之硬化剂所组成。The present invention also provides a resin prepreg composition glue, which is characterized in that it consists of component (A): epoxy resin; and component (B): a hardener as shown in formula (I).
式(I)Formula (I)
其中R为CH2、O或SO2。wherein R is CH 2 , O or SO 2 .
本发明还提供一种散热胶片的制作方法，其特征在于，包括如下步骤：步骤一：提供一玻璃纤维布；以及步骤二：浸渍(dipping)该玻璃纤维布于上述的树脂预浸体组成胶液中，并经固化、干燥等步骤后，即可形成一种具有高耐热性、高附着性及高导热效率的散热胶片。The present invention also provides a manufacturing method of a heat dissipation film, which is characterized in that it comprises the following steps: step 1: providing a glass fiber cloth; and step 2: dipping the glass fiber cloth into the above resin prepreg to form a glue Liquid, and after curing, drying and other steps, a heat dissipation film with high heat resistance, high adhesion and high thermal conductivity can be formed.
本发明具有以下有益的效果：本发明提出的硬化剂，可使生产的散热胶片兼顾耐热性及附着性，同时该硬化剂的结构具有极性，故可将无机粉体均匀地分散于该具有该硬化剂的环氧树脂预浸体组成胶液中，故应用上述的环氧树脂预浸体组成胶液所制作的散热胶片能具有更好的树脂特性，且在散热的功效上更具有较好的导热效率。The present invention has the following beneficial effects: the hardening agent proposed by the present invention can make the heat-dissipating film produced take into account both heat resistance and adhesion, and at the same time the structure of the hardening agent is polar, so the inorganic powder can be evenly dispersed in the In the epoxy resin prepreg composition glue with this hardener, so the heat dissipation film made by using the above epoxy resin prepreg composition glue can have better resin characteristics, and has more effective in heat dissipation. Better heat conduction efficiency.
为使能更进一步了解本发明之特征及技术内容，请参阅以下有关本发明的详细说明与附图，然而所附图式仅提供参考与说明用，并非用来对本发明加以限制者。In order to further understand the features and technical content of the present invention, please refer to the following detailed description and drawings related to the present invention. However, the attached drawings are only for reference and illustration, and are not used to limit the present invention.
具体实施方式 Detailed ways
请参阅式(I)，本发明提供一种硬化剂：Please refer to formula (I), the present invention provides a kind of curing agent:
式(I)Formula (I)
其中R可为CH2、O或SO2。Wherein R can be CH 2 , O or SO 2 .
该硬化剂的主成分结构分别含两个酰亚胺(imide)和胺(amine)的结构。一般来说，酰亚胺硬化剂因含有酰亚胺结构，且成杂环结构，因此具有耐软化，耐热冲击的功效，亦即其耐热性佳；再搭配上末端有胺官能基，故抗剥离能力(peel strength)也符合一般使用的规范，故上述的硬化剂所具有的混成结构可以同时兼具耐热与抗剥离的特性。此外该结构还具备不少C＝O基，或R可以为CH2、O或SO2使该硬化剂具备一定程度的极性，可提供对于高浓度无机粉体较好的分散效果。The main component structure of the hardener contains two structures of imide and amine respectively. Generally speaking, because imide hardener contains imide structure and forms a heterocyclic structure, it has the effect of softening resistance and thermal shock resistance, that is, it has good heat resistance; coupled with an amine functional group at the end, Therefore, the anti-peel strength (peel strength) also conforms to the standard of general use, so the hybrid structure of the above-mentioned hardener can simultaneously have the properties of heat resistance and anti-peeling. In addition, the structure also has a lot of C=O groups, or R can be CH 2 , O or SO 2 so that the hardener has a certain degree of polarity, which can provide a better dispersion effect for high-concentration inorganic powders.
另外，本发明更进一步提出一种应用式(I)的树脂预浸体组成胶液，即利用环氧树脂与上述的硬化剂所组成的聚合物胶液。换句话说，本发明提出一种由组分(A)：环氧树脂；以及组分(B)：式(I)所示的硬化剂所组成的树脂组合物的胶液，而该环氧树脂系为一种选自双酚A型环氧树脂(Bisphenol-A)、酚醛型环氧树脂(Novolac)、双酚A型酚醛环氧树脂、溴化环氧树脂及无卤环氧树脂中之树脂。再者，上述胶液中的组分(B)更进一步包括二氰胺类(Dicy)或苯酚(PN phenolic)类硬化剂，即上述式(I)的硬化剂可以掺混二氰胺类(Dicy)或苯酚(PN phenolic)类硬化剂来调配上述之树脂预浸体组成胶液；且该胶液中更可进一步含有组分(C)，其中组分(C)为无机粉体，该无机粉体系均匀的分散于该胶液之中。In addition, the present invention further proposes a resin prepreg compounded with formula (I), that is, a polymer glue composed of epoxy resin and the above-mentioned hardener. In other words, the present invention proposes a glue solution of a resin composition composed of component (A): epoxy resin; and component (B): a hardener represented by formula (I), and the epoxy The resin system is a type selected from bisphenol-A epoxy resin (Bisphenol-A), novolac epoxy resin (Novolac), bisphenol-A novolac epoxy resin, brominated epoxy resin and halogen-free epoxy resin of resin. Furthermore, the component (B) in the above-mentioned glue solution further includes dicyandiamides (Dicy) or phenol (PN phenolic) hardeners, that is, the hardeners of the above-mentioned formula (I) can be blended with dicyandiamides ( Dicy) or phenol (PN phenolic) hardener to prepare the above-mentioned resin prepreg composition glue; and the glue can further contain component (C), wherein component (C) is an inorganic powder, the The inorganic powder system is uniformly dispersed in the glue solution.
本发明更进一步提出一种使用上述胶液以制造散热胶片的方法。该方法应用上述由组分(A)：环氧树脂；以及组分(B)：式(I)所示之硬化剂所组成的树脂组合物的胶液，并将一玻璃纤维布浸渍(dipping)于该胶液中。且该胶液中更可进一步含有组分(C)，其中组分(C)为无机粉体，例如碳化硅粉体(SiC)、氧化铝粉体、氮化硼粉体、氮化铝粉体、或上述任两种或两种以上混合而成的粉体等，但不以上述为限，该无机粉体可视为一种无机散热填充料，其可附着于玻璃纤维布上，而在后续压合的层合板中即可做为一快速导热的媒介，尤其该胶液中所含有的式(I)所示的硬化剂，通过C＝O基，或R可以为CH2、O或SO2的结构所提供的极性可以使上述无机粉体均匀分散于胶液之中，故当玻璃纤维布含浸于该胶液中时可以均匀的将该无机粉体均匀地披覆于玻璃纤维布之上。另外，该胶液的粘度则控制在2000厘泊(centi-poise，cps)以下，以使该胶液更符合应用于浸渍该玻璃纤维布的上胶机构。而在上述步骤之后更进一步包括一固化干燥步骤。另外在玻璃纤维布浸渍(dipping)于该胶液的步骤中，最佳地提供一均匀步骤，以使无机粉体能更加均匀的分布于树脂预浸体组成胶液之中。The present invention further proposes a method of using the above-mentioned glue solution to manufacture a heat dissipation film. This method uses above-mentioned by component (A): epoxy resin; And component (B): the glue solution of the resin composition that the curing agent shown in formula (I) forms, and a glass fiber cloth impregnated (dipping ) in the glue solution. And the glue can further contain component (C), wherein component (C) is an inorganic powder, such as silicon carbide powder (SiC), alumina powder, boron nitride powder, aluminum nitride powder body, or a powder made by mixing any two or more of the above, but not limited to the above, the inorganic powder can be regarded as an inorganic heat-dissipating filler, which can be attached to the glass fiber cloth, and It can be used as a rapid heat conduction medium in the subsequent laminated board, especially the hardener shown in the formula (I) contained in the glue, through the C=O group, or R can be CH 2 , O Or the polarity provided by the structure of SO2 can make the above-mentioned inorganic powder evenly dispersed in the glue, so when the glass fiber cloth is impregnated in the glue, the inorganic powder can be evenly coated on the glass on fiber cloth. In addition, the viscosity of the glue solution is controlled below 2000 centi-poise (cps), so that the glue solution is more suitable for the gluing mechanism used for impregnating the glass fiber cloth. After the above steps, a curing and drying step is further included. In addition, in the step of dipping the glass fiber cloth in the glue solution, it is best to provide a uniform step so that the inorganic powder can be more evenly distributed in the glue solution composed of the resin prepreg.
综上所述，本发明所提出的由组分(A)：环氧树脂；以及组分(B)：式(I)所示的硬化剂所组成的树脂预浸体组成胶液系可应用在浸渍玻璃纤维布以形成散热胶片的制造方法，而该胶液可以根据实际应用的情况加以调整，如该组分(B)除了式(I)所示的硬化剂之外更混合二氰胺类(Dicy)或苯酚(PN phenolic)类硬化剂，或是加以调整粘度等等参数。In summary, the present invention proposes by component (A): epoxy resin; In impregnating glass fiber cloth to form the manufacturing method of heat dissipation film, and this glue solution can be adjusted according to the situation of actual application, as this component (B) mixes dicyandiamide in addition to the hardening agent shown in formula (I) Class (Dicy) or phenol (PN phenolic) hardener, or to adjust the viscosity and other parameters.
以下，本发明将针对玻璃纤维布浸渍于上述之树脂预浸体组成胶液所制成的散热胶片进行特性测试。请参考表1：Hereinafter, the present invention will conduct a performance test on the heat dissipation film made of glass fiber cloth impregnated with the above-mentioned resin prepreg composition glue. Please refer to Table 1:
表1Table 1
由表1可知，本具体实施例是利用双酚A型环氧树脂(固含量90％)占25.9％、上述之式(I)所示的硬化剂占24％与50％的无机碳化硅粉体(SiC)以及其它组分(D)的添加物，如促进剂、溶剂及分散剂等所组成的树脂预浸体组成胶液进行玻璃纤维布之浸渍步骤。双酚A型环氧树脂由双酚A(Bisphenol A)与环氧氯丙烷(Epichlorohydrin)在氢氧化钠(NaOH)的环境中反应而得，其结构上具有的特性在于该分子末端的环氧基具有高反应性，双酚主链的对称性高，具刚直结构，故强韧性及高温特性优良；主链上的醚结合，可适度地旋转，故具可挠性。从上表可得到以下结果：As can be seen from Table 1, this specific embodiment utilizes bisphenol A type epoxy resin (90% solid content) to account for 25.9%, and the hardening agent represented by the above-mentioned formula (I) accounts for 24% and 50% of inorganic silicon carbide powder The glass fiber cloth is impregnated with a resin prepreg composed of a resin prepreg (SiC) and additives of other components (D), such as accelerators, solvents, and dispersants. Bisphenol A type epoxy resin is obtained by the reaction of bisphenol A (Bisphenol A) and epichlorohydrin (Epichlorohydrin) in the environment of sodium hydroxide (NaOH), and its structural characteristic is that the epoxy at the end of the molecule The base has high reactivity, the bisphenol main chain has high symmetry and rigid structure, so it has excellent toughness and high temperature characteristics; the ether bond on the main chain can rotate moderately, so it is flexible. The following results can be obtained from the above table:
1、漂锡结果：耐热实验依据产业标准IPC-TM-650 Method 2.4.13.1，将散热胶片浸泡于288℃锡炉至爆板所需时间(分)，其中可得知通过本发明所提出的胶液进行玻璃纤维布浸渍作业之后制造的散热胶片具有较高的耐热性，故爆板所需的时间较长且符合测试规范。1. Tin bleaching results: the heat resistance experiment is based on the industry standard IPC-TM-650 Method 2.4.13.1, and the time (minutes) required to soak the heat dissipation film in a tin furnace at 288°C until it explodes, it can be known that the heat dissipation film proposed by the present invention The heat dissipation film produced after impregnating the glass fiber cloth with the glue solution has high heat resistance, so it takes a long time to explode the board and meets the test specifications.
2、P/S结果：剥离实验系依据IPC-TM-650 Method 2.4.8，双面贴覆1盎司(oz)铜箔热压合后，拉伸铜箔一端提供一向上拉力，判断断裂程度，数值越大则表示散热胶片对铜箔附着力越好。故上述实验可得知通过本发明所提出的树脂预浸体组成胶液进行玻璃纤维布浸渍作业之后所制造的散热胶片对于铜箔具有较好的附着能力。2. P/S results: The peeling test is based on IPC-TM-650 Method 2.4.8. After hot pressing of 1 oz copper foil on both sides, one end of the copper foil is stretched to provide an upward pulling force to judge the degree of fracture , the larger the value, the better the adhesion of the thermal film to the copper foil. Therefore, it can be seen from the above experiments that the heat dissipation film produced after impregnating the glass fiber cloth with the resin prepreg composition glue proposed by the present invention has better adhesion to copper foil.
3、粉体分散态：为调制表1所述组成的树脂预浸体组成胶液，量测每一组成的树脂预浸体组成胶液静置至澄清所需的时间，时间越长表示无机粉体的悬浮分散性越好。从上述实验可得知本发明所提出的树脂预浸体组成胶液具有最高的无机粉体的悬浮分散性，可以解决无机粉体于上胶槽内沉积的问题，进而提高浸渍玻璃纤维布所制成的散热胶片上的无机粉体的成膜均匀性。3. Powder dispersion state: In order to prepare the resin prepreg composition glue described in Table 1, measure the time required for each composition of the resin prepreg composition glue to stand until it is clarified. The longer the time, the inorganic The better the suspension and dispersibility of the powder. From the above experiments, it can be known that the resin prepreg composition glue proposed by the present invention has the highest suspension dispersibility of inorganic powder, which can solve the problem of inorganic powder deposition in the gluing tank, and then improve the impregnated glass fiber cloth. The film-forming uniformity of the inorganic powder on the heat-dissipating film made.
换句话说，从表1可以得知本发明所提出的硬化剂、含有该硬化剂的树脂预浸体组成胶液可应用于玻璃纤维度的浸渍工艺，而由该浸渍工艺所制作的散热胶片可以解决使用二氰胺类硬化剂所生产的散热胶片的耐热性低的问题，同时解决采用酚醛环氧脂硬化剂，如苯酚类硬化剂所生产的散热胶片的附着能力低的问题，而该硬化剂更为一种具有极性的分子结构，使得无机粉体可以相当均匀的分散于树脂预浸体组成胶液之中，使最终的散热胶片的表面披覆有均匀的无机粉体膜层。In other words, it can be known from Table 1 that the curing agent proposed by the present invention and the resin prepreg composition glue solution containing the curing agent can be applied to the glass fiber impregnation process, and the heat dissipation film produced by the impregnation process It can solve the problem of low heat resistance of heat dissipation film produced by using dicyandiamide hardener, and at the same time solve the problem of low adhesion of heat dissipation film produced by novolac epoxy hardener, such as phenol hardener. The hardener has a polar molecular structure, so that the inorganic powder can be uniformly dispersed in the resin prepreg composition glue, so that the surface of the final heat dissipation film is covered with a uniform inorganic powder film layer.
而表2则显示本发明所制作的散热胶片与其它胶片进行散热效率的评估。Table 2 shows the evaluation of the heat dissipation efficiency of the heat dissipation film produced by the present invention and other films.
表2Table 2
表2主要是进行热传导效率的实验数据，将上述三种胶片的一侧接触一个100℃的固定热源，并量测胶片的另一侧表面从45℃升温至65℃所需时间，时间越短表示热传导效率越好。其中可得知利用本发明所提出的硬化剂所制造的胶片具有最短的升温时间，即其可在最快的时间内进行散热的功效，而此一结果还说明本发明的硬化剂的极性可以使无机粉体均匀的分散于该树脂预浸体组成胶液之中的特性。Table 2 is mainly the experimental data of heat conduction efficiency. One side of the above-mentioned three types of film is contacted with a fixed heat source at 100°C, and the time required for the surface of the other side of the film to rise from 45°C to 65°C is measured. The shorter the time Indicates better heat transfer efficiency. Wherein it can be seen that the film made by the hardening agent proposed by the present invention has the shortest heating time, that is, it can dissipate heat in the fastest time, and this result also shows the polarity of the hardening agent of the present invention The property that the inorganic powder can be uniformly dispersed in the resin prepreg composition glue.
综上所述，本发明具有下列诸项优点：In summary, the present invention has the following advantages:
式(I)所示的硬化剂，可改善其所制成的散热胶片的耐热性及附着性，另外该硬化剂的结构具有极性，故可将无机粉体均匀地分散于该具有该硬化剂的环氧树脂预浸体组成胶液中。The hardening agent shown in formula (I) can improve the heat resistance and adhesion of the heat dissipation film made by it. In addition, the structure of the hardening agent has polarity, so the inorganic powder can be evenly dispersed in the Hardener epoxy prepregs make up the glue solution.
另一方面，本发明之环氧树脂预浸体组成胶液可应用于散热胶片的制作，以上述式(I)所示的硬化剂所调配的环氧树脂预浸体组成胶液可以提升玻璃纤维布浸渍于该环氧树脂预浸体组成胶液所制成的散热胶片的散热性及加工性。On the other hand, the epoxy resin prepreg composition glue of the present invention can be applied to the production of heat dissipation film, and the epoxy resin prepreg composition glue prepared with the hardener shown in the above formula (I) can lift the glass The heat dissipation and processability of the heat dissipation film made of fiber cloth impregnated with the epoxy resin prepreg to form a glue.
以上所述仅为本发明的优选实施例，不能限制本发明的专利保护范围，因此凡运用本发明说明书及图式内容所得到的等效变化，均同理皆包含于本发明的权利保护范围内。The above descriptions are only preferred embodiments of the present invention, and cannot limit the scope of patent protection of the present invention. Therefore, all equivalent changes obtained by using the description and drawings of the present invention are all included in the scope of protection of the present invention. Inside.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102378560A (en) * | 2010-08-18 | 2012-03-14 | 富葵精密组件(深圳)有限公司 | Film having electromagnetic shielding effect and manufacturing method thereof |
| CN102371739A (en) * | 2010-08-26 | 2012-03-14 | 富葵精密组件(深圳)有限公司 | Film and manufacturing method thereof |
| CN103814466A (en) * | 2011-09-26 | 2014-05-21 | 瓦尔达微创新有限责任公司 | Structurally stable active material for battery electrodes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102378560A (en) * | 2010-08-18 | 2012-03-14 | 富葵精密组件(深圳)有限公司 | Film having electromagnetic shielding effect and manufacturing method thereof |
| CN102378560B (en) * | 2010-08-18 | 2015-05-20 | 富葵精密组件(深圳)有限公司 | Film having electromagnetic shielding effect and manufacturing method thereof |
| CN102371739A (en) * | 2010-08-26 | 2012-03-14 | 富葵精密组件(深圳)有限公司 | Film and manufacturing method thereof |
| CN103814466A (en) * | 2011-09-26 | 2014-05-21 | 瓦尔达微创新有限责任公司 | Structurally stable active material for battery electrodes |
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