CN110809394A - Electromagnetic wave shielding film and manufacturing method thereof, and printed wiring board with electromagnetic wave shielding film and manufacturing method thereof - Google Patents

Electromagnetic wave shielding film and manufacturing method thereof, and printed wiring board with electromagnetic wave shielding film and manufacturing method thereof Download PDF

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CN110809394A
CN110809394A CN201910624218.7A CN201910624218A CN110809394A CN 110809394 A CN110809394 A CN 110809394A CN 201910624218 A CN201910624218 A CN 201910624218A CN 110809394 A CN110809394 A CN 110809394A
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film
electromagnetic wave
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wave shielding
shielding film
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吉田一义
权田贵司
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Shin Etsu Polymer Co Ltd
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073Shielding materials
    • H05K9/0081Electromagnetic shielding materials, e.g. EMI, RFI shielding
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Abstract

本发明涉及电磁波屏蔽膜及其制造方法、以及带有电磁波屏蔽膜的印刷线路板及其制造方法。提供一种绝缘树脂层与导电层的粘接力充分提高的电磁波屏蔽膜、及其制造方法。本发明的电磁波屏蔽膜(1)具有绝缘树脂层(10)和与绝缘树脂层(10)邻接的包含金属的导电层(20),绝缘树脂层(10)含有芳香族聚醚酮和聚醚酰亚胺。上述芳香族聚醚酮可以是聚醚醚酮或聚醚酮酮。上述聚醚酰亚胺可以是玻璃化转变温度为200℃以上,具有特定的化学式所示的重复单元的聚醚酰亚胺。

Figure 201910624218

The present invention relates to an electromagnetic wave shielding film and a manufacturing method thereof, as well as a printed wiring board with the electromagnetic wave shielding film and a manufacturing method thereof. Provided are an electromagnetic wave shielding film in which the adhesion between an insulating resin layer and a conductive layer is sufficiently improved, and a method for producing the same. The electromagnetic wave shielding film (1) of the present invention has an insulating resin layer (10) and a conductive layer (20) containing a metal adjacent to the insulating resin layer (10), and the insulating resin layer (10) contains aromatic polyether ketone and polyether imide. The above-mentioned aromatic polyetherketone may be polyetheretherketone or polyetherketoneketone. The above-mentioned polyetherimide may be a polyetherimide having a glass transition temperature of 200° C. or higher and a repeating unit represented by a specific chemical formula.

Figure 201910624218

Description

电磁波屏蔽膜及其制造方法、以及带有电磁波屏蔽膜的印刷 线路板及其制造方法Electromagnetic wave shielding film, method for producing the same, and printing with electromagnetic wave shielding film Circuit board and method of making the same

技术领域technical field

本发明涉及电磁波屏蔽膜及其制造方法、以及带有电磁波屏蔽膜的印刷线路板及其制造方法。The present invention relates to an electromagnetic wave shielding film and a manufacturing method thereof, as well as a printed wiring board with the electromagnetic wave shielding film and a manufacturing method thereof.

背景技术Background technique

为了屏蔽由印刷线路板产生的电磁噪声和来自外部的电磁噪声,有时隔着绝缘膜(Coverlay Film;覆盖膜)在印刷线路板的表面设置包括绝缘树脂层和与该绝缘树脂层邻接的导电层的电磁波屏蔽膜(例如,参照专利文献1)。In order to shield electromagnetic noise generated by the printed wiring board and electromagnetic noise from the outside, an insulating resin layer and a conductive layer adjacent to the insulating resin layer are sometimes provided on the surface of the printed wiring board through an insulating film (coverlay film). The electromagnetic wave shielding film (for example, refer to Patent Document 1).

电磁波屏蔽膜例如如下制造:在载体膜的单面涂布包含热固性树脂、固化剂和溶剂的涂料,使其干燥形成绝缘树脂层,在绝缘树脂层的表面设置导电层,从而制造。导电层由金属薄膜层和粘接剂层(例如导电性粘接剂层)中的至少一者形成。The electromagnetic wave shielding film is produced, for example, by applying a coating containing a thermosetting resin, a curing agent and a solvent to one side of a carrier film, drying it to form an insulating resin layer, and providing a conductive layer on the surface of the insulating resin layer. The conductive layer is formed of at least one of a metal thin film layer and an adhesive layer (eg, a conductive adhesive layer).

现有技术文献prior art literature

专利文献Patent Literature

专利文献1:日本特开2016-86120号公报Patent Document 1: Japanese Patent Laid-Open No. 2016-86120

发明内容SUMMARY OF THE INVENTION

发明所要解决的技术问题The technical problem to be solved by the invention

就由热固性树脂形成的以往的绝缘树脂层而言,对包含金属的导电层的粘接性低。特别是在导电层具有金属薄膜层、且金属薄膜层与绝缘树脂层接触的情况下,粘接性特别低。因此,在以往的电磁波屏蔽膜中,绝缘树脂层与导电层的粘接力弱,在处理电磁波屏蔽膜的过程中可能发生层间剥离。例如,当从绝缘树脂层剥离载体膜时,绝缘树脂层有时与载体膜一起从导电层剥离。A conventional insulating resin layer formed of a thermosetting resin has low adhesiveness to a conductive layer containing a metal. In particular, when the conductive layer has a metal thin film layer and the metal thin film layer is in contact with the insulating resin layer, the adhesiveness is particularly low. Therefore, in the conventional electromagnetic wave shielding film, the adhesive force between the insulating resin layer and the conductive layer is weak, and interlayer peeling may occur in the process of handling the electromagnetic wave shielding film. For example, when the carrier film is peeled off from the insulating resin layer, the insulating resin layer is sometimes peeled off from the conductive layer together with the carrier film.

本发明的目的在于,提供可以充分提高包含金属的导电层与绝缘树脂层的粘接力的电磁波屏蔽膜及其制造方法。The objective of this invention is to provide the electromagnetic wave shielding film which can fully improve the adhesive force of the conductive layer containing a metal, and an insulating resin layer, and its manufacturing method.

用于解决问题的技术方案technical solutions for problem solving

本发明包含以下的方式。The present invention includes the following aspects.

[1]一种电磁波屏蔽膜,其具有绝缘树脂层、和与上述绝缘树脂层邻接的包含金属的导电层,上述绝缘树脂层含有芳香族聚醚酮和聚醚酰亚胺。[1] An electromagnetic wave shielding film comprising an insulating resin layer containing an aromatic polyetherketone and a polyetherimide, and a conductive layer containing a metal adjacent to the insulating resin layer.

[2]根据[1]所述的电磁波屏蔽膜,其中,上述芳香族聚醚酮为聚醚醚酮或聚醚酮酮。[2] The electromagnetic wave shielding film according to [1], wherein the aromatic polyetherketone is polyetheretherketone or polyetherketoneketone.

[3]根据[1]或[2]所述的电磁波屏蔽膜,其中,上述聚醚酰亚胺的玻璃化转变温度为200℃以上,具有下述化学式(A)所示的重复单元;[3] The electromagnetic wave shielding film according to [1] or [2], wherein the polyetherimide has a glass transition temperature of 200° C. or higher, and has a repeating unit represented by the following chemical formula (A);

[化1][hua 1]

Figure BDA0002126515510000021
Figure BDA0002126515510000021

[4]根据[1]~[3]中任一项所述的电磁波屏蔽膜,其中,相对于上述绝缘树脂层的总质量,上述芳香族聚醚酮的含量为5质量%以上且95质量%以下,上述聚醚酰亚胺的含量为5质量%以上且95质量%以下。[4] The electromagnetic wave shielding film according to any one of [1] to [3], wherein the content of the aromatic polyetherketone is 5 mass % or more and 95 mass % with respect to the total mass of the insulating resin layer % or less, and content of the said polyetherimide is 5 mass % or more and 95 mass % or less.

[5]根据[1]~[4]中任一项所述的电磁波屏蔽膜,其中,上述绝缘树脂层的厚度为2μm以上且10μm以下。[5] The electromagnetic wave shielding film according to any one of [1] to [4], wherein the insulating resin layer has a thickness of 2 μm or more and 10 μm or less.

[6]根据[1]~[5]中任一项所述的电磁波屏蔽膜,其中,上述导电层为金属蒸镀层。[6] The electromagnetic wave shielding film according to any one of [1] to [5], wherein the conductive layer is a metal vapor deposition layer.

[7]根据[6]所述的电磁波屏蔽膜,其中,上述金属蒸镀层为银蒸镀层或铜蒸镀层。[7] The electromagnetic wave shielding film according to [6], wherein the metal vapor deposition layer is a silver vapor deposition layer or a copper vapor deposition layer.

[8]根据[1]~[7]中任一项所述的电磁波屏蔽膜,其中,在上述绝缘树脂层的与上述导电层的相反侧的面上还具有载体膜。[8] The electromagnetic wave shielding film according to any one of [1] to [7], further comprising a carrier film on the surface of the insulating resin layer opposite to the conductive layer.

[9]一种带有电磁波屏蔽膜的印刷线路板,其具有:印刷线路板,其在基板的至少单面设有印刷电路;绝缘膜,其与上述印刷线路板的设有上述印刷电路的一侧的面邻接;和,[1]~[8]中任一项所述的电磁波屏蔽膜,其以使上述导电层与上述绝缘膜邻接的方式设置。[9] A printed wiring board with an electromagnetic wave shielding film, comprising: a printed wiring board provided with a printed circuit on at least one side of a substrate; one side is adjacent to each other; and, the electromagnetic wave shielding film according to any one of [1] to [8], which is provided so that the conductive layer and the insulating film are adjacent to each other.

[10]一种电磁波屏蔽膜的制造方法,其包含下述步骤:将芳香族聚醚酮与聚醚酰亚胺的混合树脂成型为膜状,形成绝缘树脂层,在上述绝缘树脂层的一面侧形成导电层。[10] A method for producing an electromagnetic wave shielding film, comprising the steps of: molding a mixed resin of aromatic polyetherketone and polyetherimide into a film shape, forming an insulating resin layer, and forming an insulating resin layer on one side of the insulating resin layer. A conductive layer is formed on the side.

[11]一种带有电磁波屏蔽膜的印刷线路板的制造方法,其包含下述步骤:将在基板的至少单面设有印刷电路的印刷线路板和[1]~[8]中任一项所述的电磁波屏蔽膜隔着绝缘膜进行压接。[11] A method for producing a printed wiring board with an electromagnetic wave shielding film, comprising the steps of: combining a printed wiring board with a printed circuit on at least one side of a substrate and any one of [1] to [8] The electromagnetic wave shielding film described in the item is crimped with an insulating film interposed therebetween.

发明的效果effect of invention

本发明的电磁波屏蔽膜可以充分提高包含金属的导电层与绝缘树脂层的粘接力。The electromagnetic wave shielding film of this invention can fully improve the adhesive force of the conductive layer containing a metal, and an insulating resin layer.

根据本发明的电磁波屏蔽膜的制造方法,可以容易地制造上述电磁波屏蔽膜。According to the manufacturing method of the electromagnetic wave shielding film of this invention, the said electromagnetic wave shielding film can be manufactured easily.

在本发明的带有电磁波屏蔽膜的印刷线路板中,包含金属的导电层与绝缘树脂层的粘接力足够高。In the printed wiring board with the electromagnetic wave shielding film of the present invention, the adhesion between the conductive layer containing metal and the insulating resin layer is sufficiently high.

根据本发明的带有电磁波屏蔽膜的印刷线路板的制造方法,可以容易地制造上述带有电磁波屏蔽膜的印刷线路板。According to the manufacturing method of the printed wiring board with an electromagnetic wave shielding film of this invention, the said printed wiring board with an electromagnetic wave shielding film can be manufactured easily.

附图说明Description of drawings

图1是示出本发明的电磁波屏蔽膜的第一实施方式的剖视图。FIG. 1 is a cross-sectional view showing a first embodiment of the electromagnetic wave shielding film of the present invention.

图2是示出本发明的电磁波屏蔽膜的第二实施方式的剖视图。2 is a cross-sectional view showing a second embodiment of the electromagnetic wave shielding film of the present invention.

图3是示出本发明的电磁波屏蔽膜的第三实施方式的剖视图。3 is a cross-sectional view showing a third embodiment of the electromagnetic wave shielding film of the present invention.

图4是示出本发明的带有电磁波屏蔽膜的印刷线路板的一个实施方式的剖视图。4 is a cross-sectional view showing one embodiment of the electromagnetic wave shielding film-equipped printed wiring board of the present invention.

图5是示出图4的带有电磁波屏蔽膜的印刷线路板的制造工序的剖视图。5 is a cross-sectional view illustrating a manufacturing process of the electromagnetic wave shielding film-equipped printed wiring board of FIG. 4 .

具体实施方式Detailed ways

以下术语的定义适用于本说明书和权利要求书的全部范围。The definitions of the following terms apply to the full scope of this specification and claims.

“各向同性导电性粘接剂层”是指在厚度方向和面方向具有导电性的导电性粘接剂层。The "isotropic conductive adhesive layer" refers to a conductive adhesive layer having conductivity in the thickness direction and the surface direction.

“各向异性导电性粘接剂层”是指在厚度方向具有导电性且在面方向不具有导电性的导电性粘接剂层。The "anisotropic conductive adhesive layer" means a conductive adhesive layer that has conductivity in the thickness direction and does not have conductivity in the surface direction.

“在面方向不具有导电性的导电性粘接剂层”是指表面电阻为1×104Ω以上的导电性粘接剂层。The "conductive adhesive layer without conductivity in the plane direction" refers to a conductive adhesive layer having a surface resistance of 1×10 4 Ω or more.

粒子的平均粒径是如下得到的值:从粒子的显微镜图像中随机选择30个粒子,测定每个粒子的最小直径和最大直径,并将最小直径和最大直径的中值作为一个粒子的粒径,对测得的30个粒子的粒径进行算术平均,由此得到粒子的平均粒径。导电性粒子的平均粒径也同样。The average particle diameter of the particles is a value obtained by randomly selecting 30 particles from a microscope image of the particles, measuring the minimum diameter and the maximum diameter of each particle, and taking the median value of the minimum diameter and the maximum diameter as the particle diameter of one particle , the average particle diameter of the particles is obtained by arithmetically averaging the particle diameters of the 30 particles measured. The same applies to the average particle diameter of the conductive particles.

使用显微镜观察测定对象的剖面,测定5处的厚度并取平均,得到的值即为膜(脱模膜、绝缘膜等)、涂膜(绝缘树脂层、导电性粘接剂层等)、金属薄膜层等的厚度。The cross section of the object to be measured is observed with a microscope, the thickness of 5 places is measured and averaged, and the obtained value is the film (release film, insulating film, etc.), coating film (insulating resin layer, conductive adhesive layer, etc.), metal Thickness of film layers, etc.

关于储能模量,由施加给测定对象的应力和检测到的应变算出,使用以温度或时间的函数形式输出的动态粘弹性测定装置,作为粘弹性特性之一来测定。The storage modulus was calculated from the stress applied to the measurement object and the detected strain, and was measured as one of the viscoelastic properties using a dynamic viscoelasticity measuring device that outputs as a function of temperature or time.

关于拉伸模量,基于JIS K7127通过使用拉伸试验机的测定来求出。为在弹性限度内、测定对象所承受的拉伸应力除以测定对象所产生的应变而得的值,与杨氏模量含义相同。The tensile modulus was determined by measurement using a tensile tester based on JIS K7127. It is a value obtained by dividing the tensile stress received by the measurement object by the strain generated by the measurement object within the elastic limit, and has the same meaning as Young's modulus.

导电性粒子的10%抗压强度由使用微小压缩试验机的测定结果通过下述式(α)求得。The 10% compressive strength of the electroconductive particles was determined by the following formula (α) from the measurement results using a micro-compression tester.

C(x)=2.48P/πd2 (α)C(x)=2.48P/πd 2 (α)

其中,C(x)为10%抗压强度(MPa),P为粒径10%位移时的试验力(N),d为粒径(mm)。Among them, C(x) is the 10% compressive strength (MPa), P is the test force (N) when the particle size is displaced by 10%, and d is the particle size (mm).

表面电阻是指如下测得的电阻:使用在石英玻璃上蒸镀金而形成的两根薄膜金属电极(长度10mm、宽度5mm、电极间距离10mm),将被测定物放置在该电极上,从被测定物上方以0.049N的载荷按压被测定物的10mm×20mm的区域,并以1mA以下的测定电流测定的电极之间的电阻。Surface resistance refers to the resistance measured as follows: using two thin-film metal electrodes (length 10mm, width 5mm, distance between electrodes 10mm) formed by vapor deposition of gold on quartz glass, the object to be measured is placed on the electrodes, The resistance between the electrodes was measured by pressing a 10 mm×20 mm area of the object to be measured above the object to be measured with a load of 0.049 N, and measuring the resistance between the electrodes with a measurement current of 1 mA or less.

为了方便说明,图1~图5中的尺寸比与实际尺寸比不同。For convenience of description, the size ratios in FIGS. 1 to 5 are different from the actual size ratios.

<电磁波屏蔽膜><Electromagnetic wave shielding film>

本发明的第一方式为一种电磁波屏蔽膜,其具有绝缘树脂层和与上述绝缘树脂层邻接的包含金属的导电层,上述绝缘树脂层含有芳香族聚醚酮和聚醚酰亚胺。A first aspect of the present invention is an electromagnetic wave shielding film including an insulating resin layer containing an aromatic polyether ketone and a polyetherimide, and a conductive layer containing a metal adjacent to the insulating resin layer.

图1是示出第一实施方式的电磁波屏蔽膜1的剖视图,图2是示出第二实施方式的电磁波屏蔽膜1的剖视图,图3是示出第三实施方式的电磁波屏蔽膜1的剖视图。1 is a cross-sectional view showing the electromagnetic wave shielding film 1 according to the first embodiment, FIG. 2 is a cross-sectional view showing the electromagnetic wave shielding film 1 according to the second embodiment, and FIG. 3 is a cross-sectional view showing the electromagnetic wave shielding film 1 according to the third embodiment. .

第一实施方式、第二实施方式和第三实施方式的电磁波屏蔽膜1均具有绝缘树脂层10、与绝缘树脂层10邻接的导电层20、与绝缘树脂层10的与导电层20相反一侧邻接的载体膜30、以及与导电层20的与绝缘树脂层10相反一侧邻接的脱模膜40。The electromagnetic wave shielding films 1 of the first embodiment, the second embodiment, and the third embodiment all have an insulating resin layer 10 , a conductive layer 20 adjacent to the insulating resin layer 10 , and the opposite side of the insulating resin layer 10 to the conductive layer 20 . The adjacent carrier film 30 and the release film 40 adjacent to the side opposite to the insulating resin layer 10 of the conductive layer 20 are provided.

在第一实施方式的电磁波屏蔽膜1中,导电层20具有与绝缘树脂层10邻接的金属薄膜层22、以及与脱模膜40邻接的各向异性导电性粘接剂层24。In the electromagnetic wave shielding film 1 of the first embodiment, the conductive layer 20 includes the metal thin film layer 22 adjacent to the insulating resin layer 10 and the anisotropic conductive adhesive layer 24 adjacent to the release film 40 .

在第二实施方式的电磁波屏蔽膜1中,导电层20具有与绝缘树脂层10邻接的金属薄膜层22、以及与脱模膜40邻接的各向同性导电性粘接剂层26。In the electromagnetic wave shielding film 1 of the second embodiment, the conductive layer 20 includes the metal thin film layer 22 adjacent to the insulating resin layer 10 and the isotropic conductive adhesive layer 26 adjacent to the release film 40 .

在第三实施方式的电磁波屏蔽膜1中,导电层20包含各向同性导电性粘接剂层26。In the electromagnetic wave shielding film 1 of the third embodiment, the conductive layer 20 includes the isotropic conductive adhesive layer 26 .

(绝缘树脂层)(insulating resin layer)

在将电磁波屏蔽膜1贴合于设置在柔性印刷线路板表面的绝缘膜的表面上并剥离载体膜30之后,绝缘树脂层10成为导电层20的保护层。After the electromagnetic wave shielding film 1 is attached to the surface of the insulating film provided on the surface of the flexible printed wiring board and the carrier film 30 is peeled off, the insulating resin layer 10 becomes a protective layer of the conductive layer 20 .

绝缘树脂层10含有芳香族聚醚酮和聚醚酰亚胺。The insulating resin layer 10 contains aromatic polyetherketone and polyetherimide.

芳香族聚醚酮是具有介由醚键将苯环彼此键合的结构、和介由酮基将苯环彼此键合的结构的聚合物。The aromatic polyether ketone is a polymer having a structure in which benzene rings are bonded to each other via ether bonds, and a structure in which benzene rings are bonded to each other via a ketone group.

聚醚酰亚胺是具有介由醚键将芳香环彼此键合的结构、和介由酰亚胺键将芳香环彼此键合的结构的聚合物。The polyetherimide is a polymer having a structure in which aromatic rings are bonded to each other through ether bonds, and a structure in which aromatic rings are bonded to each other through imide bonds.

作为芳香族聚醚酮,可列举例如:具有化学式(1)所示的化学结构的聚醚醚酮(PEEK)、具有化学式(2)所示的化学结构的聚醚酮(PEK)、具有化学式(3)所示的化学结构的聚醚酮酮(PEKK)、具有化学式(4)所示的化学结构的聚醚醚酮酮(PEEKK)、具有化学式(5)所示的化学结构的聚醚酮醚酮酮(PEKEKK)。绝缘树脂层10中所含的芳香族聚醚酮可以是单独一种,也可以是两种以上。Examples of the aromatic polyether ketone include polyether ether ketone (PEEK) having a chemical structure represented by chemical formula (1), polyether ketone (PEK) having a chemical structure represented by chemical formula (2), Polyetherketoneketone (PEKK) having a chemical structure represented by chemical formula (3), polyetheretherketoneketone (PEEKK) having a chemical structure represented by chemical formula (4), and polyether having a chemical structure represented by chemical formula (5) Ketone ether ketone ketone (PEKEKK). The aromatic polyether ketone contained in the insulating resin layer 10 may be one kind alone or two or more kinds.

另外,芳香族聚醚酮可以是具有化学式(1)~(5)所示的化学结构中的2种以上化学结构的共聚物。In addition, the aromatic polyether ketone may be a copolymer having two or more chemical structures among the chemical structures represented by chemical formulae (1) to (5).

化学式(1)~(5)所示的芳香族聚醚酮的两末端为氢原子。Both ends of the aromatic polyether ketone represented by chemical formulae (1) to (5) are hydrogen atoms.

[化2][hua 2]

Figure BDA0002126515510000071
Figure BDA0002126515510000071

上述芳香族聚醚酮中,从容易形成绝缘树脂层10的角度和更进一步提高对金属薄膜层22的粘接性方面出发,优选PEEK。Among the above-mentioned aromatic polyetherketones, PEEK is preferable from the viewpoint of easy formation of the insulating resin layer 10 and further improvement of the adhesiveness to the metal thin film layer 22 .

从机械特性的观点出发,上述化学式(1)~(5)各化学式中的n优选为10以上,更优选为20以上。另一方面,从可以容易地制造芳香族聚醚酮方面出发,n优选为5000以下,更优选为1000以下。即,优选为10以上且5000以下,更优选为20以上且1000以下。From the viewpoint of mechanical properties, n in each of the chemical formulae (1) to (5) above is preferably 10 or more, and more preferably 20 or more. On the other hand, since the aromatic polyether ketone can be easily produced, n is preferably 5000 or less, and more preferably 1000 or less. That is, 10 or more and 5000 or less are preferable, and 20 or more and 1000 or less are more preferable.

在不损害本发明的效果的范围内,芳香族聚醚酮可以是与醚砜等其它能够共聚的单体的嵌段共聚物、无规共聚物或改性体。The aromatic polyether ketone may be a block copolymer, a random copolymer, or a modified product of other copolymerizable monomers such as ether sulfone within the range not impairing the effects of the present invention.

芳香族聚醚酮中,上述化学式(1)~(5)中的任一者所示的聚醚酮的重复单元的比例相对于芳香族聚醚酮100摩尔%为50摩尔%以上且100摩尔%以下,更优选为70摩尔%以上且100摩尔%以下,进一步优选为80摩尔%以上且100摩尔%以下,最优选为100摩尔%。芳香族聚醚酮中,如果上述芳香族聚醚酮的重复单元的比例为上述下限值以上,则可以进一步增强绝缘树脂层10与导电层20的粘接力。In the aromatic polyether ketone, the ratio of the repeating unit of the polyether ketone represented by any one of the above-mentioned chemical formulae (1) to (5) is 50 mol % or more and 100 mol with respect to 100 mol % of the aromatic polyether ketone % or less, more preferably 70 mol % or more and 100 mol % or less, further preferably 80 mol % or more and 100 mol % or less, and most preferably 100 mol %. In the aromatic polyether ketone, when the ratio of the repeating unit of the said aromatic polyether ketone is more than the said lower limit, the adhesive force of the insulating resin layer 10 and the conductive layer 20 can be further strengthened.

芳香族聚醚酮的制造方法例如公开于日本特开昭50-27897号公报、日本特开昭51-119797号公报、日本特开昭52-38000号公报、日本特开昭54-90296号公报、日本特公昭55-23574号公报、日本特公昭56-2091号公报。Methods for producing aromatic polyetherketones are disclosed in, for example, JP 50-27897 A, JP 51-119797 A, JP 52-38000 A, and JP 54-90296 A , Japanese Patent Publication No. 55-23574, Japanese Patent Publication No. 56-2091.

作为PEEK的市售品的例子,可列举例如:Victrex公司制的Victrex Peek系列(制品名)、Daicel Evonik公司制的Vestakeep系列(制品名)、Solvay Specialty Polymers公司制的KetaSpire聚醚醚酮系列(制品名)。Examples of commercial products of PEEK include Victrex Peek series (product name) manufactured by Victrex, Vestakeep series (product name) manufactured by Daicel Evonik, KetaSpire polyetheretherketone series (product name) manufactured by Solvay Specialty Polymers product name).

作为构成绝缘树脂层10的聚醚酰亚胺(PEI),优选例如玻璃化转变温度为200℃以上的PEI。作为玻璃化转变温度为200℃以上的PEI,可列举例如具有下述化学式(A)所示的重复单元的PEI。As the polyetherimide (PEI) constituting the insulating resin layer 10 , for example, PEI having a glass transition temperature of 200° C. or higher is preferable. As PEI whose glass transition temperature is 200 degreeC or more, PEI which has a repeating unit represented by following chemical formula (A) is mentioned, for example.

[化3][hua 3]

Figure BDA0002126515510000081
Figure BDA0002126515510000081

在不损害本发明的效果的范围内,可以向具有上述化学式(A)所示的重复单元的PEI中添加具有下述化学式(B)所示的重复单元的PEI。PEI having a repeating unit represented by the following chemical formula (B) may be added to PEI having a repeating unit represented by the above-mentioned chemical formula (A) within a range not impairing the effects of the present invention.

[化4][hua 4]

Figure BDA0002126515510000091
Figure BDA0002126515510000091

作为具有上述化学式(A)的重复单元的PEI的具体例,可列举ULTEM 1010-1000-NB、ULTEM 9011-1000-NB〔均为SABIC INNOVATIVE PLASTICS公司,制品名〕等。作为具有上述化学式(A)的重复单元的PEI的制造方法,可列举例如使4,4'-异丙叉基双(对亚苯基氧基)二邻苯二甲酸酐与间苯二胺进行缩聚的公知方法。As a specific example of PEI which has the repeating unit of the said chemical formula (A), ULTEM 1010-1000-NB, ULTEM 9011-1000-NB [all SABIC INNOVATIVE PLASTICS company, a product name] etc. are mentioned. As a manufacturing method of PEI which has the repeating unit of the said chemical formula (A), for example, 4,4'-isopropylidene bis (p-phenyleneoxy) diphthalic anhydride and m-phenylenediamine are mentioned. known methods of polycondensation.

作为具有上述化学式(B)的重复单元的PEI的具体例,可列举ULTEM CRS5001-1000-NB〔SABIC INNOVATIVE PLASTICS公司制品名〕。作为具有上述化学式(B)的重复单元的PEI的制造方法,可列举例如使4,4'-异丙叉基双(对亚苯基氧基)二邻苯二甲酸与对苯二胺进行缩聚的公知方法。As a specific example of PEI which has the repeating unit of the said chemical formula (B), ULTEM CRS5001-1000-NB [SABIC INNOVATIVE PLASTICS company product name] is mentioned. As a method for producing PEI having a repeating unit of the above-mentioned chemical formula (B), for example, polycondensation of 4,4'-isopropylidenebis(p-phenyleneoxy)diphthalic acid and p-phenylenediamine can be mentioned. known method.

构成绝缘树脂层10的聚醚酰亚胺可以是与酰胺基、酯基、磺酰基、硅氧烷基等其它能够共聚的其它单体的嵌段共聚物、无规共聚物、改性体。其包括例如作为聚醚酰亚胺砜共聚物的玻璃化转变温度为238℃的ULTEM XH6050-1000〔SABIC INNOVATIVE PLASTICS公司制品名〕、聚醚酰亚胺/硅氧烷共聚物ULTEM STM1700-1000〔SABIC INNOVATIVE PLASTICS公司制品名〕等。The polyetherimide constituting the insulating resin layer 10 may be a block copolymer, a random copolymer, or a modified product of other copolymerizable monomers such as an amide group, an ester group, a sulfonyl group, and a siloxane group. These include, for example, ULTEM XH6050-1000 [SABIC INNOVATIVE PLASTICS Co., Ltd. trade name] with a glass transition temperature of 238°C as a polyetherimide sulfone copolymer, and a polyetherimide/siloxane copolymer ULTEM STM1700-1000 [ SABIC INNOVATIVE PLASTICS company product name] and so on.

由于具有上述化学式(A)的重复单元的PEI与具有上述化学式(1)的重复单元的PEEK的相容性非常优异,因此优选由将这些组合而成的混合树脂来形成绝缘树脂层10。Since PEI having the repeating unit of the above-mentioned chemical formula (A) and PEEK having the repeating unit of the above-mentioned chemical formula (1) are very excellent in compatibility, it is preferable to form the insulating resin layer 10 from a mixed resin in which these are combined.

在构成绝缘树脂层10的树脂成分中,具有上述化学式(1)所示的重复单元的PEEK和具有上述化学式(A)所示的重复单元且玻璃化转变温度为200℃以上的PEI优选为:以组成质量比率计,PEEK为5质量%以上且95质量%以下,并且聚醚酰亚胺树脂为5质量%以上且95质量%以下。这里,更优选PEEK为10质量%以上且90质量%以下,并且聚醚酰亚胺树脂为10质量%以上且90质量%以下,进一步优选PEEK为20质量%以上且80质量%以下,并且聚醚酰亚胺树脂为20质量%以上且80质量%以下。Among the resin components constituting the insulating resin layer 10, PEEK having the repeating unit represented by the above chemical formula (1) and PEI having the repeating unit represented by the above chemical formula (A) and having a glass transition temperature of 200° C. or higher are preferably: In terms of composition mass ratio, PEEK is 5 mass % or more and 95 mass % or less, and polyetherimide resin is 5 mass % or more and 95 mass % or less. Here, it is more preferable that PEEK is 10 mass % or more and 90 mass % or less, and the polyetherimide resin is 10 mass % or more and 90 mass % or less, and it is more preferable that PEEK is 20 mass % or more and 80 mass % or less, and the polyetherimide resin is more preferably 20 mass % or more and 80 mass % or less. The etherimide resin is 20% by mass or more and 80% by mass or less.

当为上述范围的下限值以上时,耐热性更进一步优异,当为上述范围的上限值以下时,绝缘树脂层10对导电层20的粘接性更进一步优异。When it is more than the lower limit of the said range, the heat resistance is further excellent, and when it is below the upper limit of the said range, the adhesiveness of the insulating resin layer 10 with respect to the conductive layer 20 is more excellent.

构成绝缘树脂层10的树脂的玻璃化转变温度(玻璃化转变温度:Tg)根据上述PEEK和上述PEI的混合比率而改变。有PEI相对于PEEK的比例越高则绝缘树脂层10的Tg越高的倾向。如果上述树脂的Tg高,则不易受到制造电磁波屏蔽膜时的加热处理的影响、使用时的高温环境的影响,因此是优选的。作为上述树脂的Tg,优选为140~210℃,更优选为165~205℃,进一步优选为170~200℃。当为上述范围的下限值以上时,可以防止由于制造电磁波屏蔽膜时的加热处理而导致在绝缘树脂层10的表面产生褶皱、波纹、局部熔融等。当为上述范围的上限值以下时,可以进一步提高对金属薄膜22的粘接性。The glass transition temperature (glass transition temperature: Tg) of the resin constituting the insulating resin layer 10 varies according to the mixing ratio of the above-mentioned PEEK and the above-mentioned PEI. The higher the ratio of PEI to PEEK, the higher the Tg of the insulating resin layer 10 tends to be. When the Tg of the above-mentioned resin is high, it is less susceptible to the influence of the heat treatment at the time of producing the electromagnetic wave shielding film and the influence of the high temperature environment at the time of use, which is preferable. As Tg of the said resin, 140-210 degreeC is preferable, 165-205 degreeC is more preferable, and 170-200 degreeC is still more preferable. When it is more than the lower limit of the said range, generation|occurrence|production of wrinkles, waves, local melting, etc. on the surface of the insulating resin layer 10 by heat processing at the time of manufacture of an electromagnetic wave shielding film can be prevented. Adhesion to the metal thin film 22 can be further improved as it is below the upper limit of the said range.

作为由芳香族聚醚酮与PEI的混合树脂形成绝缘树脂层10的方法,可列举例如下述方法:将芳香族聚醚酮和PEI通过挤出成型机熔融混炼,从而制备成型材料,由该成型材料连续挤出成型出绝缘树脂层。以下对芳香族聚醚酮为PEEK的情况进行说明,在PEEK以外的芳香族聚醚酮的情况下,也可以同样地进行。As a method of forming the insulating resin layer 10 from a mixed resin of aromatic polyether ketone and PEI, for example, a method of melt-kneading aromatic polyether ketone and PEI with an extruder to prepare a molding material, The molding material is continuously extruded to form an insulating resin layer. Hereinafter, the case where the aromatic polyether ketone is PEEK will be described, but the same can be done in the case of an aromatic polyether ketone other than PEEK.

PEEK和PEI的制备方法可以列举例如下述方法:(a)将PEEK和PEI的颗粒分别在0~50℃的条件下搅拌混合后,进行熔融混炼,从而制备成型材料的方法;(b)向熔融的PEEK中添加PEI,将这些熔融混炼,从而制备成型材料;或者,向熔融的PEI中添加PEEK,将这些熔融混炼,从而制备成型材料。从提高分散性的观点出发,优选(a)的方法。The preparation methods of PEEK and PEI include, for example, the following methods: (a) a method for preparing a molding material by stirring and mixing PEEK and PEI particles at 0 to 50° C., respectively, followed by melt-kneading; (b) PEI is added to molten PEEK, and these are melt-kneaded to prepare a molding material; or, PEEK is added to molten PEI, and these are melt-kneaded to prepare a molding material. From the viewpoint of improving dispersibility, the method of (a) is preferred.

对上述(a)的制备方法进一步进行说明。在进行PEEK和PEI的搅拌混合时,使用转鼓式混合机、亨舍尔混合机、V型混合机、诺塔(Nauta)混合机、带式搅拌机、万能搅拌混合机等。另外,将上述搅拌混合物用包含混合辊、加压捏合机、单螺杆挤出成型机、双螺杆挤出成型机、三螺杆挤出成型机、四螺杆挤出成型机、八螺杆挤出成型机等多螺杆挤出成型机等的熔融混炼机进行熔融、混炼,从而可以对PEEK和PEI进行分散。The production method of the above (a) will be further described. For the stirring and mixing of PEEK and PEI, a drum mixer, a Henschel mixer, a V-type mixer, a Nauta mixer, a ribbon mixer, a universal mixer, or the like are used. In addition, the above-mentioned agitated mixture was mixed with a mixing roll, a pressure kneader, a single-screw extruder, a twin-screw extruder, a three-screw extruder, a four-screw extruder, and an eight-screw extruder. PEEK and PEI can be dispersed by melting and kneading in a melt-kneader such as a multi-screw extruder.

对PEEK和PEI进行熔融混炼的温度可以为PEEK的熔点以上或PEI的玻璃化转变温度以上且450℃以下,优选为350℃以上且430℃以下。当熔融混炼温度为上述范围的下限值以上时,可以对PEEK和PEI进行更均匀地分散。当为上述范围的上限值以下时,可以抑制PEEK或PEI因为热而分解。The temperature at which PEEK and PEI are melt-kneaded may be the melting point of PEEK or higher or the glass transition temperature of PEI or higher and 450°C or lower, preferably 350°C or higher and 430°C or lower. When the melt-kneading temperature is equal to or higher than the lower limit value of the above range, PEEK and PEI can be more uniformly dispersed. When it is below the upper limit of the said range, thermal decomposition of PEEK or PEI can be suppressed.

对上述(b)的制备方法进一步进行说明。将PEEK或PEI中的任一者用包含混合辊、加压捏合机、单螺杆挤出成型机、二螺杆挤出成型机、三螺杆挤出成型机、四螺杆挤出成型机、八螺杆挤出成型机等多螺杆挤出成型机等的熔融混炼机进行熔融后,添加未熔融的另一树脂并进行熔融、混炼,从而可以进行分散。该熔融混炼的温度优选与上述(a)同样的温度范围。The production method of the above (b) will be further described. Any one of PEEK or PEI is prepared by mixing rollers, pressure kneaders, single-screw extruders, two-screw extruders, three-screw extruders, four-screw extruders, and eight-screw extruders. After being melted from a melt-kneading machine such as a multi-screw extruder such as a molding machine, another unmelted resin can be added, melted, and kneaded, thereby enabling dispersion. The temperature of this melt-kneading is preferably the same temperature range as the above (a).

使用由PEEK和PEI的混合树脂构成的混合树脂,通过熔融挤出成型法、压延成型法或流延成型法等公知的成型法,从而可以形成绝缘树脂层10。The insulating resin layer 10 can be formed by a known molding method such as a melt extrusion molding method, a calender molding method, or a tape casting method using a mixed resin composed of a mixed resin of PEEK and PEI.

绝缘树脂层10中,除了芳香族聚醚酮和PEI以外还可以包含其他树脂。作为其它树脂,可列举例如聚酰亚胺(PI)、聚酰胺酰亚胺(PAI)、聚酰胺6T(PA6T)、改性聚酰胺6T(改性PA6T)、聚酰胺9T(PA9T)、聚酰胺10T(PA10T)、聚酰胺11T(PA11T)、聚酰胺6(PA6)、聚酰胺66(PA66)、聚酰胺46(PA46)、聚砜(PSU)、聚醚砜(PES)、聚苯砜(PPSU)、聚苯硫醚(PPS)、聚苯硫醚酮、聚苯硫醚砜、聚苯硫醚酮砜、液晶聚合物(LCP)等。The insulating resin layer 10 may contain other resins in addition to the aromatic polyether ketone and PEI. Examples of other resins include polyimide (PI), polyamideimide (PAI), polyamide 6T (PA6T), modified polyamide 6T (modified PA6T), polyamide 9T (PA9T), polyamide Amide 10T (PA10T), Polyamide 11T (PA11T), Polyamide 6 (PA6), Polyamide 66 (PA66), Polyamide 46 (PA46), Polysulfone (PSU), Polyethersulfone (PES), Polyphenylsulfone (PPSU), polyphenylene sulfide (PPS), polyphenylene sulfide ketone, polyphenylene sulfide sulfone, polyphenylene sulfide ketone sulfone, liquid crystal polymer (LCP), and the like.

相对于绝缘树脂层10的总质量,优选芳香族聚醚酮的含量为5质量%以上且95质量%以下,并且PEI的含量为5质量%以上且95质量%以下。另外,更优选芳香族聚醚酮的含量为10质量%以上且90质量%以下,并且PEI的含量为10质量%以上、90质量%以下。With respect to the total mass of the insulating resin layer 10 , the content of the aromatic polyetherketone is preferably 5% by mass or more and 95% by mass or less, and the content of PEI is preferably 5% by mass or more and 95% by mass or less. Moreover, it is more preferable that the content of the aromatic polyether ketone is 10 mass % or more and 90 mass % or less, and the PEI content is 10 mass % or more and 90 mass % or less.

当为上述范围的下限值以上时,耐热性更进一步优异,当为上述范围的上限值以下时,绝缘树脂层10对导电层20的粘接性更进一步优异。When it is more than the lower limit of the said range, the heat resistance is further excellent, and when it is below the upper limit of the said range, the adhesiveness of the insulating resin layer 10 with respect to the conductive layer 20 is more excellent.

如果绝缘树脂层10的160℃下的拉伸模量高,则不易受到制造电磁波屏蔽膜时的加热处理的影响、使用时的高温环境的影响,因此是优选的。作为上述拉伸模量,优选为1000N/mm2~5000N/mm2,更优选为1500N/mm2~4000N/mm2,进一步优选为2000N/mm2~3000N/mm2。当为上述范围的下限值以上时,可以防止由于制造电磁波屏蔽膜时的加热处理而导致在绝缘树脂层10中产生褶皱、波纹、局部断裂等。为上述范围的上限值以下时,与其它层的拉伸模量的平衡更良好,可以进一步提高对金属薄膜22的粘接性。When the tensile modulus at 160° C. of the insulating resin layer 10 is high, it is less likely to be affected by the heat treatment at the time of production of the electromagnetic wave shielding film or by the high temperature environment at the time of use, which is preferable. The tensile modulus is preferably 1000 N/mm 2 to 5000 N/mm 2 , more preferably 1500 N/mm 2 to 4000 N/mm 2 , and still more preferably 2000 N/mm 2 to 3000 N/mm 2 . When it is more than the lower limit of the said range, generation|occurrence|production of a wrinkle, a waviness, a local break, etc. in the insulating resin layer 10 by heat processing at the time of manufacture of an electromagnetic wave shielding film can be prevented. When it is below the upper limit of the said range, the balance of the tensile modulus with other layers becomes more favorable, and the adhesiveness with respect to the metal thin film 22 can be improved more.

为了隐蔽印刷线路板的印刷电路或赋予带有电磁波屏蔽膜的印刷线路板设计性,绝缘树脂层10可以包含着色剂(颜料、染料等)和填料中的任意一者或两者。The insulating resin layer 10 may contain any one or both of colorants (pigments, dyes, etc.) and fillers in order to conceal the printed circuit of the printed wiring board or to impart designability to the printed wiring board with the electromagnetic wave shielding film.

作为着色剂和填料中的任意一者或两者,从耐候性、耐热性、隐蔽性方面考虑,优选颜料或填料,从印刷电路的隐蔽性、设计性方面考虑,更优选黑色颜料、或黑色颜料与其它颜料或填料的组合。As either or both of the colorant and filler, from the viewpoint of weather resistance, heat resistance, and concealment, a pigment or a filler is preferable, and from the viewpoint of concealment and design property of a printed circuit, a black pigment, or Combinations of black pigments with other pigments or fillers.

在不损害本发明的特性的范围内,绝缘树脂层10可以包含抗氧化剂、光稳定剂、紫外线稳定剂、增塑剂、润滑剂、阻燃剂、抗静电剂、耐热性改进剂、无机填充剂、有机填充剂等添加剂。The insulating resin layer 10 may contain antioxidants, light stabilizers, ultraviolet stabilizers, plasticizers, lubricants, flame retardants, antistatic agents, heat resistance improvers, inorganic Additives such as fillers and organic fillers.

从电绝缘性方面考虑,绝缘树脂层10的表面电阻优选为1×106Ω以上。从实用方面考虑,绝缘树脂层10的表面电阻优选为1×1019Ω以下。From the viewpoint of electrical insulating properties, the surface resistance of the insulating resin layer 10 is preferably 1×10 6 Ω or more. From a practical standpoint, the surface resistance of the insulating resin layer 10 is preferably 1×10 19 Ω or less.

绝缘树脂层10的厚度优选为2.0μm以上且30μm以下,更优选为3.0μm以上且10μm以下。如果绝缘树脂层10的厚度为上述范围的下限值以上,则绝缘树脂层10可以充分发挥作为保护层的功能。如果绝缘树脂层10的厚度为上述范围的上限值以下,则可以减薄电磁波屏蔽膜1。The thickness of the insulating resin layer 10 is preferably 2.0 μm or more and 30 μm or less, and more preferably 3.0 μm or more and 10 μm or less. If the thickness of the insulating resin layer 10 is equal to or more than the lower limit value of the above-mentioned range, the insulating resin layer 10 can sufficiently function as a protective layer. If the thickness of the insulating resin layer 10 is equal to or less than the upper limit of the above-mentioned range, the electromagnetic wave shielding film 1 can be thinned.

(导电层)(conductive layer)

导电层至少具有包含金属的导电性粘接剂层。金属可以为薄膜状,也可以为粒子状,还可以为其它形状。The conductive layer has at least a metal-containing conductive adhesive layer. The metal may be in the form of a film, may be in the form of particles, or may be in other shapes.

具体而言,如上所述,第一实施方式中的导电层20具有与绝缘树脂层10邻接的金属薄膜层22和与脱模膜40邻接的各向异性导电性粘接剂层24。Specifically, as described above, the conductive layer 20 in the first embodiment includes the metal thin film layer 22 adjacent to the insulating resin layer 10 and the anisotropic conductive adhesive layer 24 adjacent to the release film 40 .

第二实施方式中的导电层20具有与绝缘树脂层10邻接的金属薄膜层22和与脱模膜40邻接的各向同性导电性粘接剂层26。The conductive layer 20 in the second embodiment has the metal thin film layer 22 adjacent to the insulating resin layer 10 and the isotropic conductive adhesive layer 26 adjacent to the release film 40 .

第三实施方式中的导电层20包含各向同性导电性粘接剂层26。The conductive layer 20 in the third embodiment includes an isotropic conductive adhesive layer 26 .

作为导电层20,从电磁波屏蔽性足够高的方面考虑,优选具有金属薄膜层22和各向异性导电性粘接剂层24或各向同性导电性粘接剂层26。即,优选导电层20具有金属薄膜层和导电性粘接剂层这两层。The conductive layer 20 preferably has a metal thin film layer 22 and an anisotropic conductive adhesive layer 24 or an isotropic conductive adhesive layer 26 from the viewpoint of sufficiently high electromagnetic wave shielding properties. That is, the conductive layer 20 preferably has two layers, the metal thin film layer and the conductive adhesive layer.

[金属薄膜层][Metal thin film layer]

金属薄膜层22是包含金属的薄膜的层。金属薄膜层22以沿面方向展开的方式形成,因此在面方向具有导电性,作为电磁波屏蔽层等起作用。The metal thin film layer 22 is a layer containing a thin film of metal. Since the metal thin film layer 22 is formed so as to spread in the plane direction, it has conductivity in the plane direction, and functions as an electromagnetic wave shielding layer or the like.

作为金属薄膜层22,可列举:通过物理蒸镀(真空蒸镀、溅射、离子束蒸镀、电子束蒸镀等)或化学蒸镀形成的蒸镀膜、通过镀敷形成的镀敷膜、金属箔等。在面方向的导电性优异方面,导电层20优选为蒸镀膜、镀敷膜。在可以减薄导电层20、且即使厚度较小面方向的导电性也优异、且可以利用干法工艺简便形成方面,导电层20更优选为蒸镀膜,进一步优选为由物理蒸镀形成的蒸镀膜。Examples of the metal thin film layer 22 include a vapor-deposited film formed by physical vapor deposition (vacuum vapor deposition, sputtering, ion beam vapor deposition, electron beam vapor deposition, etc.) or chemical vapor deposition, a plated film formed by plating, Metal foil, etc. The conductive layer 20 is preferably a vapor-deposited film or a plated film from the viewpoint of excellent conductivity in the plane direction. The conductive layer 20 is more preferably a vapor-deposited film, more preferably a vapor-deposited film formed by physical vapor deposition, since the conductive layer 20 can be thinned, has excellent electrical conductivity in the plane direction even with a small thickness, and can be easily formed by a dry process. Coating.

作为构成金属薄膜层22的金属,可列举:铝、银、铜、金、导电性陶瓷等,从电导率方面考虑,优选银或铜。Examples of the metal constituting the metal thin film layer 22 include aluminum, silver, copper, gold, conductive ceramics, and the like, and silver or copper is preferable from the viewpoint of electrical conductivity.

在金属薄膜层22中,从电磁波屏蔽性高,且容易形成金属薄膜层方面,优选金属蒸镀层,更优选银蒸镀层或铜蒸镀层。Among the metal thin film layers 22, a metal vapor-deposited layer is preferable, and a silver vapor-deposited layer or a copper vapor-deposited layer is more preferable because the electromagnetic wave shielding property is high and the metal thin film layer is easily formed.

金属薄膜层22的表面电阻优选为0.001Ω以上、1Ω以下,更优选为0.001Ω以上、0.5Ω以下。如果金属薄膜层22的表面电阻在上述范围的下限值以上,则可以充分减薄金属薄膜层22。如果金属薄膜层22的表面电阻在上述范围的上限值以下,则可以充分起到电磁波屏蔽层的作用。The surface resistance of the metal thin film layer 22 is preferably 0.001Ω or more and 1Ω or less, and more preferably 0.001Ω or more and 0.5Ω or less. If the sheet resistance of the metal thin film layer 22 is equal to or more than the lower limit value of the above-mentioned range, the metal thin film layer 22 can be sufficiently thinned. If the surface resistance of the metal thin film layer 22 is equal to or less than the upper limit of the above-mentioned range, the function of the electromagnetic wave shielding layer can be sufficiently exerted.

金属薄膜层22的厚度优选为0.01μm以上且5μm以下,更优选为0.05μm以上且3μm以下。如果金属薄膜层22的厚度为0.01μm以上,则面方向的导电性更加良好。如果金属薄膜层22的厚度为0.05μm以上,则电磁噪声的屏蔽效果更加良好。如果金属薄膜层22的厚度在上述范围的上限值以下,则可以减薄电磁波屏蔽膜1。另外,电磁波屏蔽膜1的生产率、挠性变得良好。The thickness of the metal thin film layer 22 is preferably 0.01 μm or more and 5 μm or less, and more preferably 0.05 μm or more and 3 μm or less. When the thickness of the metal thin film layer 22 is 0.01 μm or more, the electrical conductivity in the plane direction is further improved. When the thickness of the metal thin film layer 22 is 0.05 μm or more, the shielding effect of electromagnetic noise is further improved. If the thickness of the metal thin film layer 22 is equal to or less than the upper limit of the above-mentioned range, the electromagnetic wave shielding film 1 can be thinned. In addition, the productivity and flexibility of the electromagnetic wave shielding film 1 are improved.

[黑化层][blackened layer]

银蒸镀层和铜蒸镀层等金属薄膜层22的光反射性高,具有金属光泽。为了抑制该金属光泽,导电层20可以在金属薄膜层22的绝缘树脂层10侧的面上具有黑化层。例如,在将电磁波屏蔽膜1用于显示器用柔性印刷线路板的情况下,为了防止金属薄膜层22的光泽影响显示器的可见性,优选在金属薄膜层22和绝缘树脂层10之间设置黑化层。The metal thin film layer 22 such as the silver vapor deposition layer and the copper vapor deposition layer has high light reflectivity and metallic luster. In order to suppress this metallic luster, the conductive layer 20 may have a blackened layer on the surface of the metal thin film layer 22 on the insulating resin layer 10 side. For example, when the electromagnetic wave shielding film 1 is used in a flexible printed wiring board for a display, in order to prevent the gloss of the metal thin film layer 22 from affecting the visibility of the display, it is preferable to provide blackening between the metal thin film layer 22 and the insulating resin layer 10 Floor.

黑化层为由吸光材料构成且具有防光反射性的黑色层。具体而言,黑化层优选JISZ8781-5中规定的亮度L为5以下。具有亮度L的值越小则黑色度越大、越可以抑制光反射的倾向。The blackened layer is a black layer made of a light absorbing material and having anti-light reflection properties. Specifically, the blackened layer preferably has a luminance L * defined in JISZ8781-5 of 5 or less. The smaller the value of the luminance L * , the greater the blackness and the tendency to suppress light reflection.

黑化层由例如下述(i)~(iii)中的任一吸光材料构成。The blackened layer is composed of, for example, any one of the light-absorbing materials in the following (i) to (iii).

(i)银的氧化物或铜的氧化物(i) Silver oxide or copper oxide

(ii)选自由氮化铜、氧化铜、氮化镍和氧化镍组成的组中的至少一种(ii) at least one selected from the group consisting of copper nitride, copper oxide, nickel nitride, and nickel oxide

(iii)锌、铜和锌的合金、银和锌的合金中的任意一种(iii) any one of zinc, copper and zinc alloy, silver and zinc alloy

在黑化层由上述(i)构成的情况下,可列举:通过蒸镀或镀敷来形成包含银的氧化物或铜的氧化物的层的方法。作为蒸镀法,可使用例如真空蒸镀法、溅射法等公知的蒸镀法。When the blackened layer is composed of the above (i), a method of forming a layer containing an oxide of silver or an oxide of copper by vapor deposition or plating is exemplified. As a vapor deposition method, a well-known vapor deposition method, such as a vacuum vapor deposition method and a sputtering method, can be used, for example.

在黑化层由上述(ii)构成的情况下,可列举:由蒸镀或镀敷形成包含选自由氮化铜、氧化铜、氮化镍和氧化镍组成的组中的至少一种的层的方法。When the blackened layer is composed of the above (ii), a layer containing at least one selected from the group consisting of copper nitride, copper oxide, nickel nitride, and nickel oxide is formed by vapor deposition or plating. Methods.

在黑化层由上述(iii)构成的情况下,可列举:通过蒸镀或镀敷形成包含锌、铜和锌的合金、银和锌的合金中的任意一种的层的方法。When the blackened layer is composed of the above-mentioned (iii), a method of forming a layer including any one of zinc, copper and zinc alloy, and silver and zinc alloy by vapor deposition or plating is exemplified.

作为黑化层的厚度,没有特别限制,优选为5nm以上且20μm以下,更优选为10nm以上且1μm以下。如果黑化层的厚度为上述下限值以上,则可以充分抑制光反射;如果为上述上限值以下,则可以容易地形成黑化层。The thickness of the blackened layer is not particularly limited, but is preferably 5 nm or more and 20 μm or less, and more preferably 10 nm or more and 1 μm or less. When the thickness of the blackened layer is equal to or more than the above lower limit value, light reflection can be sufficiently suppressed, and if it is equal to or less than the above upper limit value, the blackened layer can be easily formed.

[各向异性导电性粘接剂层][Anisotropic Conductive Adhesive Layer]

第一实施方式中的各向异性导电性粘接剂层24在厚度方向具有导电性,在面方向不具有导电性,且具有粘接性。The anisotropic conductive adhesive layer 24 in the first embodiment has electrical conductivity in the thickness direction, but has no electrical conductivity in the surface direction, and has adhesiveness.

各向异性导电性粘接剂层24可以容易减薄导电性粘接剂层,可以减少后述导电性粒子的量,其结果,具有可以减薄电磁波屏蔽膜1、提高电磁波屏蔽膜1的挠性的优点。The anisotropic conductive adhesive layer 24 can easily reduce the thickness of the conductive adhesive layer, and can reduce the amount of conductive particles described later. As a result, the electromagnetic wave shielding film 1 can be thinned and the flexibility of the electromagnetic wave shielding film 1 can be improved. the advantages of sex.

作为各向异性导电性粘接剂层24,从固化后可以发挥耐热性方面考虑,优选热固性的导电性粘接剂层。热固性的各向异性导电性粘接剂层24可以为未固化状态,也可以为B阶化状态。The anisotropic conductive adhesive layer 24 is preferably a thermosetting conductive adhesive layer from the viewpoint of exhibiting heat resistance after curing. The thermosetting anisotropic conductive adhesive layer 24 may be in an uncured state or in a B-staged state.

热固性的各向异性导电性粘接剂层24包含例如热固性粘接剂24a和导电性粒子24b。各向异性导电性粘接剂层24可以根据需要包含阻燃剂。The thermosetting anisotropic conductive adhesive layer 24 contains, for example, a thermosetting adhesive 24a and conductive particles 24b. The anisotropic conductive adhesive layer 24 may contain a flame retardant as needed.

作为热固性粘接剂24a,可列举:环氧树脂、酚醛树脂、氨基树脂、醇酸树脂、聚氨基甲酸酯树脂、合成橡胶、紫外线固化丙烯酸酯树脂等。从耐热性优异方面考虑,优选环氧树脂。环氧树脂可以包含用于赋予挠性的橡胶成分(羧基改性丁腈橡胶、丙烯酸类橡胶等)、增粘剂等。As the thermosetting adhesive 24a, epoxy resin, phenol resin, amino resin, alkyd resin, polyurethane resin, synthetic rubber, ultraviolet curing acrylate resin, etc. are mentioned. From the viewpoint of being excellent in heat resistance, epoxy resins are preferred. The epoxy resin may contain a rubber component (carboxy-modified nitrile rubber, acrylic rubber, etc.) for imparting flexibility, a tackifier, and the like.

为了提高各向异性导电性粘接剂层24的强度、提高冲压特性,热固性粘接剂24a可以包含纤维素树脂、微纤维(玻璃纤维等)。上述热固性粘接剂可以根据需要在不损害本发明的效果的范围内包含其它成分。In order to increase the strength of the anisotropic conductive adhesive layer 24 and improve the punching properties, the thermosetting adhesive 24a may contain cellulose resin, microfibers (glass fibers, etc.). The said thermosetting adhesive may contain other components in the range which does not impair the effect of this invention as needed.

作为导电性粒子24b,可列举:金属(银、铂、金、铜、镍、钯、铝、焊料等)粒子、石墨粉、烧结碳粒子、经镀敷的烧结碳粒子等。作为导电性粒子24b,从使各向异性导电性粘接剂层24具有更为合适的硬度、可以进一步降低热压时各向异性导电性粘接剂层24的压力损失方面考虑,优选金属粒子,更优选铜粒子。Examples of the conductive particles 24b include metal (silver, platinum, gold, copper, nickel, palladium, aluminum, solder, etc.) particles, graphite powder, sintered carbon particles, plated sintered carbon particles, and the like. As the conductive particles 24b, metal particles are preferable because the anisotropic conductive adhesive layer 24 has a more suitable hardness and the pressure loss of the anisotropic conductive adhesive layer 24 during hot pressing can be further reduced. , more preferably copper particles.

导电性粒子24b的10%抗压强度优选为30MPa以上且200MPa以下,更优选为50MPa以上且150MPa以下,进一步优选为70MPa以上且100MPa以下。如果导电性粒子的10%抗压强度在上述范围的下限值以上,则在热压时不会造成施加于金属薄膜层22的压力损失过大,各向异性导电性粘接剂层24经由绝缘膜的通孔与印刷线路板的印刷电路更可靠地电连接。如果导电性粒子24b的10%抗压强度为上述范围的上限值以下,则与金属薄膜层22的接触变得良好,电连接变得可靠。The 10% compressive strength of the conductive particles 24b is preferably 30 MPa or more and 200 MPa or less, more preferably 50 MPa or more and 150 MPa or less, and further preferably 70 MPa or more and 100 MPa or less. If the 10% compressive strength of the conductive particles is at least the lower limit of the above range, the pressure loss applied to the metal thin film layer 22 during hot pressing will not be too large, and the anisotropic conductive adhesive layer 24 will pass through the The through hole of the insulating film is more reliably electrically connected to the printed circuit of the printed wiring board. When the 10% compressive strength of the electroconductive particles 24b is equal to or less than the upper limit value of the above-mentioned range, the contact with the metal thin film layer 22 becomes favorable, and the electrical connection becomes reliable.

各向异性导电性粘接剂层24中的导电性粒子24b的平均粒径为2μm以上且26μm以下,更优选为4μm以上且16μm以下。如果导电性粒子24b的平均粒径为上述范围的下限值以上,则可以确保各向异性导电性粘接剂层24的厚度,可以得到充分的粘接强度。如果导电性粒子24b的平均粒径为上述范围的上限值以下,则可以确保各向异性导电性粘接剂层24的流动性,如下所示那样,在将各向异性导电性粘接剂层24压入绝缘膜的通孔时,可以利用导电性粘接剂充分填充绝缘膜的通孔内部。The average particle diameter of the conductive particles 24b in the anisotropic conductive adhesive layer 24 is 2 μm or more and 26 μm or less, and more preferably 4 μm or more and 16 μm or less. If the average particle diameter of the electroconductive particle 24b is more than the lower limit of the said range, the thickness of the anisotropic electroconductive adhesive bond layer 24 can be ensured, and sufficient adhesive strength can be obtained. When the average particle diameter of the conductive particles 24b is equal to or less than the upper limit of the above-mentioned range, the fluidity of the anisotropic conductive adhesive layer 24 can be ensured. When the layer 24 is pressed into the through hole of the insulating film, the inside of the through hole of the insulating film can be sufficiently filled with the conductive adhesive.

作为各向异性导电性粘接剂层24中的导电性粒子24b的比例,在各向异性导电性粘接剂层24的100体积%中,优选为1体积%以上且30体积%以下,更优选为2体积%以上且15体积%以下。如果导电性粒子24b的比例为上述范围的下限值以上,则各向异性导电性粘接剂层24的导电性变得良好。如果导电性粒子24b的比例为上述范围的上限值以下,则各向异性导电性粘接剂层24的粘接性,流动性(对绝缘膜的通孔的形状的随从性)变得良好。另外,电磁波屏蔽膜1的挠性变得良好。The ratio of the conductive particles 24b in the anisotropic conductive adhesive layer 24 is preferably 1% by volume or more and 30% by volume or less in 100% by volume of the anisotropic conductive adhesive layer 24, and more It is preferably not less than 2% by volume and not more than 15% by volume. The electroconductivity of the anisotropic conductive adhesive bond layer 24 becomes favorable as the ratio of the electroconductive particle 24b is more than the lower limit of the said range. When the ratio of the conductive particles 24b is equal to or less than the upper limit of the above-mentioned range, the adhesiveness and fluidity of the anisotropic conductive adhesive layer 24 (the conformability to the shape of the through-holes in the insulating film) will be favorable. . Moreover, the flexibility of the electromagnetic wave shielding film 1 becomes favorable.

各向异性导电性粘接剂层24的180℃下的储能模量优选为1×103Pa以上且5×107Pa以下,更优选为5×103Pa以上且1×107Pa以下。如果各向异性导电性粘接剂层24的180℃下的储能模量为上述范围的下限值以上,则各向异性导电性粘接剂层24具有更合适的硬度,可以降低热压时导电性粘接剂层上的压力损失。其结果,导电性粘接剂层和印刷线路板的印刷电路充分粘接,各向异性导电性粘接剂层24经由绝缘膜的通孔与印刷线路板的印刷电路更可靠地电连接。如果导电性粘接剂层在180℃下的储能模量为上述范围的上限值以下,则电磁波屏蔽膜1的挠性变得良好。其结果,电磁波屏蔽膜1容易沉入绝缘膜的通孔内,各向异性导电性粘接剂层24经由绝缘膜的通孔与印刷线路板的印刷电路更可靠地电连接。The storage modulus at 180° C. of the anisotropic conductive adhesive layer 24 is preferably 1×10 3 Pa or more and 5×10 7 Pa or less, and more preferably 5×10 3 Pa or more and 1×10 7 Pa the following. When the storage modulus at 180° C. of the anisotropic conductive adhesive layer 24 is equal to or more than the lower limit value of the above-mentioned range, the anisotropic conductive adhesive layer 24 has a more suitable hardness, and the hot pressing can be reduced. pressure loss on the conductive adhesive layer. As a result, the conductive adhesive layer and the printed circuit of the printed wiring board are sufficiently bonded, and the anisotropic conductive adhesive layer 24 is more reliably electrically connected to the printed circuit of the printed wiring board through the through holes of the insulating film. The flexibility of the electromagnetic wave shielding film 1 becomes favorable as the storage elastic modulus in 180 degreeC of a conductive adhesive layer is below the upper limit of the said range. As a result, the electromagnetic wave shielding film 1 easily sinks into the through holes of the insulating film, and the anisotropic conductive adhesive layer 24 is more reliably electrically connected to the printed circuit of the printed wiring board via the through holes of the insulating film.

各向异性导电性粘接剂层24的表面电阻优选为1×104Ω以上且1×1016Ω以下,更优选为1×106Ω以上且1×1014Ω以下。如果各向异性导电性粘接剂层24的表面电阻为上述范围的下限值以上,则可以将导电性粒子24b的含量控制得较低。The surface resistance of the anisotropic conductive adhesive layer 24 is preferably 1×10 4 Ω or more and 1×10 16 Ω or less, and more preferably 1×10 6 Ω or more and 1×10 14 Ω or less. If the surface resistance of the anisotropic conductive adhesive bond layer 24 is more than the lower limit of the said range, content of the electroconductive particle 24b can be controlled low.

如果各向异性导电性粘接剂层24的表面电阻为上述范围的上限值以下,则在实用方面,各向异性上没有问题。If the surface resistance of the anisotropic conductive adhesive layer 24 is equal to or less than the upper limit value of the above-mentioned range, there is no problem in terms of anisotropy in practical use.

各向异性导电性粘接剂层24的厚度优选为3μm以上且25μm以下,更优选为5μm以上且15μm以下。如果各向异性导电性粘接剂层24的厚度为上述范围的下限值以上,则可以确保各向异性导电性粘接剂层24的流动性(对绝缘膜的通孔的形状的随从性),可以利用导电性粘接剂充分填充绝缘膜的通孔内部。如果各向异性导电性粘接剂层24的厚度为上述范围的上限值以下,可以减薄电磁波屏蔽膜1。另外,电磁波屏蔽膜1的挠性变得良好。The thickness of the anisotropic conductive adhesive layer 24 is preferably 3 μm or more and 25 μm or less, and more preferably 5 μm or more and 15 μm or less. When the thickness of the anisotropic conductive adhesive layer 24 is equal to or more than the lower limit value of the above-mentioned range, the fluidity of the anisotropic conductive adhesive layer 24 (the conformability to the shape of the through hole of the insulating film) can be ensured ), the inside of the through hole of the insulating film can be sufficiently filled with the conductive adhesive. If the thickness of the anisotropic conductive adhesive layer 24 is equal to or less than the upper limit of the above-mentioned range, the electromagnetic wave shielding film 1 can be thinned. Moreover, the flexibility of the electromagnetic wave shielding film 1 becomes favorable.

[各向同性导电性粘接剂层][Isotropic Conductive Adhesive Layer]

第二实施方式或第三实施方式中的各向同性导电性粘接剂层26在厚度方向和面方向具有导电性,且具有粘接性。The isotropic conductive adhesive layer 26 in the second embodiment or the third embodiment has electrical conductivity in the thickness direction and the surface direction, and has adhesiveness.

各向同性导电性粘接剂层26具有可以进一步提高电磁波屏蔽膜1的电磁波屏蔽性的优点。The isotropic conductive adhesive layer 26 has an advantage that the electromagnetic wave shielding property of the electromagnetic wave shielding film 1 can be further improved.

作为各向同性导电性粘接剂层26,从固化后可以发挥耐热性方面考虑,优选热固性的导电性粘接剂层。热固性的各向同性导电性粘接剂层26可以为未固化状态,也可以为B阶化状态。As the isotropic conductive adhesive layer 26, a thermosetting conductive adhesive layer is preferable from the viewpoint of exhibiting heat resistance after curing. The thermosetting isotropic conductive adhesive layer 26 may be in an uncured state or in a B-staged state.

热固性的各向同性导电性粘接剂层26例如包含热固性粘接剂26a和导电性粒子26b。热固性的各向同性导电性粘接剂层26可以根据需要包含阻燃剂。The thermosetting isotropic conductive adhesive layer 26 contains, for example, a thermosetting adhesive 26a and conductive particles 26b. The thermosetting isotropic conductive adhesive layer 26 may contain a flame retardant as necessary.

各向同性导电性粘接剂层26所含的热固性粘接剂26a的成分和导电性粒子26b的材质与各向异性导电性粘接剂层24所含的热固性粘接剂24a的成分和导电性粒子24b的材质相同。The components of the thermosetting adhesive 26a contained in the isotropic conductive adhesive layer 26 and the material of the conductive particles 26b, and the components of the thermosetting adhesive 24a contained in the anisotropic conductive adhesive layer 24 and conductive particles The material of the sexual particles 24b is the same.

各向同性导电性粘接剂层26中的导电性粒子26b的平均粒径优选为0.1μm以上且10μm以下,更优选为0.2μm以上且1μm以下。如果导电性粒子26b的平均粒径为上述范围的下限值以上,则导电性粒子26b的接触点数增加,可以稳定地提高三维方向的导通性。如果导电性粒子26b的平均粒径为上述范围的上限值以下,则可以确保各向同性导电性粘接剂层26的流动性(对绝缘膜的通孔的形状的随从性),可以利用导电性粘接剂充分填充绝缘膜的通孔内部。The average particle diameter of the conductive particles 26b in the isotropic conductive adhesive layer 26 is preferably 0.1 μm or more and 10 μm or less, and more preferably 0.2 μm or more and 1 μm or less. If the average particle diameter of the electroconductive particle 26b is more than the lower limit of the said range, the number of contact points of the electroconductive particle 26b will increase, and the conductivity in a three-dimensional direction can be improved stably. When the average particle diameter of the conductive particles 26b is equal to or less than the upper limit of the above-mentioned range, the fluidity of the isotropic conductive adhesive layer 26 (the conformability to the shape of the through hole in the insulating film) can be ensured, and it is possible to use The conductive adhesive sufficiently fills the inside of the through hole of the insulating film.

作为各向同性导电性粘接剂层26中的导电性粒子26b的比例,在各向同性导电性粘接剂层26的100体积%中,优选为50体积%以上且80体积%以下,更优选为60体积%以上且70体积%以下。如果导电性粒子26b的比例为上述范围的下限值以上,则各向同性导电性粘接剂层26的导电性变得良好。如果导电性粒子26b的比例为上述范围的上限值以下,则各向同性导电性粘接剂层26的粘接性、流动性(对绝缘膜的通孔的形状的随从性)变得良好。另外,电磁波屏蔽膜1的挠性变得良好。The ratio of the conductive particles 26b in the isotropic conductive adhesive layer 26 is preferably 50% by volume or more and 80% by volume or less in 100% by volume of the isotropic conductive adhesive layer 26, and more preferably Preferably it is 60 volume% or more and 70 volume% or less. The electroconductivity of the isotropic conductive adhesive bond layer 26 becomes favorable as the ratio of the electroconductive particle 26b is more than the lower limit of the said range. If the ratio of the conductive particles 26b is equal to or less than the upper limit of the above-mentioned range, the adhesiveness and fluidity of the isotropic conductive adhesive layer 26 (the conformability to the shape of the through-hole of the insulating film) will be favorable. . Moreover, the flexibility of the electromagnetic wave shielding film 1 becomes favorable.

各向同性导电性粘接剂层26在180℃下的储能模量优选1×103Pa以上且5×107Pa以下,更优选5×103Pa以上且1×107Pa以下。上述范围优选的理由与各向异性导电性粘接剂层24相同。The storage elastic modulus at 180° C. of the isotropic conductive adhesive layer 26 is preferably 1×10 3 Pa or more and 5×10 7 Pa or less, and more preferably 5×10 3 Pa or more and 1×10 7 Pa or less. The reason why the above-mentioned range is preferable is the same as that of the anisotropic conductive adhesive layer 24 .

各向同性导电性粘接剂层26的表面电阻优选为0.05Ω以上且2.0Ω以下,更优选为0.1Ω以上且1.0Ω以下。如果各向同性导电性粘接剂层26的表面电阻为上述范围的下限值以上,则可以将导电性粒子26b的含量控制得较低,导电性粘接剂的粘度不会过高,涂布性变得更为良好。另外,可以进一步确保各向同性导电性粘接剂层26的流动性(对绝缘膜的通孔的形状的随从性)。如果各向同性导电性粘接剂层26的表面电阻为上述范围的上限值以下,则各向同性导电性粘接剂层26的整面具有均匀的导电性。The surface resistance of the isotropic conductive adhesive layer 26 is preferably 0.05Ω or more and 2.0Ω or less, and more preferably 0.1Ω or more and 1.0Ω or less. If the surface resistance of the isotropic conductive adhesive layer 26 is equal to or more than the lower limit value of the above-mentioned range, the content of the conductive particles 26b can be controlled to be low, the viscosity of the conductive adhesive is not too high, and the coating Cloth properties became better. In addition, the fluidity of the isotropic conductive adhesive layer 26 (the compliance with the shape of the through hole of the insulating film) can be further ensured. When the surface resistance of the isotropic conductive adhesive layer 26 is equal to or less than the upper limit of the above-mentioned range, the entire surface of the isotropic conductive adhesive layer 26 has uniform conductivity.

各向同性导电性粘接剂层26的厚度优选为5μm以上且20μm以下,更优选为7μm以上且17μm以下。如果各向同性导电性粘接剂层26的厚度为上述范围的下限值以上,则各向同性导电性粘接剂层26的导电性变得良好,可以充分起到电磁波屏蔽层的作用。另外,可以确保各向同性导电性粘接剂层26的流动性(对绝缘膜的通孔的形状的随从性),可以利用导电性粘接剂充分填充绝缘膜的通孔内部,也可以确保耐折性,即使反复弯折,各向同性导电性粘接剂层26也不会断裂。The thickness of the isotropic conductive adhesive layer 26 is preferably 5 μm or more and 20 μm or less, and more preferably 7 μm or more and 17 μm or less. When the thickness of the isotropic conductive adhesive layer 26 is equal to or more than the lower limit value of the above-mentioned range, the conductivity of the isotropic conductive adhesive layer 26 becomes good, and the function of the electromagnetic wave shielding layer can be sufficiently exerted. In addition, the fluidity of the isotropic conductive adhesive layer 26 (the compliance with the shape of the through hole in the insulating film) can be ensured, the inside of the through hole in the insulating film can be sufficiently filled with the conductive adhesive, and the In terms of folding endurance, the isotropic conductive adhesive layer 26 does not break even when it is repeatedly folded.

如果各向同性导电性粘接剂层26的厚度为上述范围的上限值以下,则可以减薄电磁波屏蔽膜1。另外,电磁波屏蔽膜1的挠性变得良好。If the thickness of the isotropic conductive adhesive layer 26 is equal to or less than the upper limit of the above-mentioned range, the electromagnetic wave shielding film 1 can be thinned. Moreover, the flexibility of the electromagnetic wave shielding film 1 becomes favorable.

(载体膜)(carrier film)

载体膜30是增强和保护绝缘树脂层10和导电层20的支撑体,使电磁波屏蔽膜1的操作性良好。特别是,在使用较薄的膜、具体而言使用厚度为3μm以上且10μm以下的膜作为绝缘树脂层10的情况下,通过具有载体膜30,可以防止绝缘树脂层10断裂。The carrier film 30 is a support that reinforces and protects the insulating resin layer 10 and the conductive layer 20 , making the electromagnetic wave shielding film 1 good in handleability. In particular, when a thin film, specifically a film having a thickness of 3 μm or more and 10 μm or less is used as the insulating resin layer 10 , the insulating resin layer 10 can be prevented from breaking by having the carrier film 30 .

在将电磁波屏蔽膜1贴到印刷线路板等上之后,从绝缘树脂层10剥离载体膜30。After the electromagnetic wave shielding film 1 is attached to a printed wiring board or the like, the carrier film 30 is peeled off from the insulating resin layer 10 .

本实施方式中使用的载体膜30具有载体膜主体32和设置在载体膜主体32的绝缘树脂层10一侧的表面上的粘合剂层34。The carrier film 30 used in this embodiment has a carrier film main body 32 and an adhesive layer 34 provided on the surface of the carrier film main body 32 on the insulating resin layer 10 side.

作为载体膜主体32的树脂材料,可列举:聚对苯二甲酸乙二醇酯(下面,有时也称为“PET”。)、聚萘二甲酸乙二醇酯、聚间苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚烯烃、聚乙酸酯、聚碳酸酯、聚苯硫醚、聚酰胺、乙烯-乙酸乙烯酯共聚物、聚氯乙烯、聚偏二氯乙烯、合成橡胶、液晶聚合物等。作为树脂材料,从制造电磁波屏蔽膜1时的耐热性(尺寸稳定性)和价格方面考虑,优选PET。Examples of the resin material for the carrier film body 32 include polyethylene terephthalate (hereinafter, also referred to as "PET" in some cases), polyethylene naphthalate, and polyethylene isophthalate. Alcohol ester, polybutylene terephthalate, polyolefin, polyacetate, polycarbonate, polyphenylene sulfide, polyamide, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride , synthetic rubber, liquid crystal polymer, etc. As the resin material, PET is preferable from the viewpoints of heat resistance (dimensional stability) and price when the electromagnetic wave shielding film 1 is produced.

载体膜主体32可以包含着色剂(颜料、染料等)和填料中的任意一者或两者。The carrier film body 32 may contain either or both of colorants (pigments, dyes, etc.) and fillers.

作为着色剂和填料中的任意一者或两者,从可以明确与绝缘树脂层10区分开来,热压后容易发现载体膜30的剥离残留方面考虑,优选与绝缘树脂层10颜色不同的物质,更优选白色颜料、填料或白色颜料与其它颜料或填料的组合。As either or both of the colorant and the filler, it is preferable to use a colorant different from that of the insulating resin layer 10 because it can be clearly distinguished from the insulating resin layer 10 and the peeling residue of the carrier film 30 is easily found after hot pressing. , more preferably white pigments, fillers or combinations of white pigments with other pigments or fillers.

载体膜主体32的180℃下的储能模量优选为8×107Pa以上且5×109Pa以下,更优选1×108Pa以上且8×108Pa以下。如果载体膜主体32的180℃下的储能模量为上述范围的下限值以上,则载体膜30具有合适硬度,可以减少热压时载体膜30上的压力损失。如果载体膜主体32的180℃下的储能模量为上述范围的上限值以下,则载体膜30的柔软性变得良好。The storage modulus at 180° C. of the carrier film main body 32 is preferably 8×10 7 Pa or more and 5×10 9 Pa or less, and more preferably 1×10 8 Pa or more and 8×10 8 Pa or less. If the storage modulus of the carrier film main body 32 at 180° C. is equal to or higher than the lower limit of the above range, the carrier film 30 has suitable hardness and can reduce pressure loss on the carrier film 30 during hot pressing. The flexibility of the carrier film 30 becomes favorable as the storage elastic modulus in 180 degreeC of the carrier film main body 32 is below the upper limit of the said range.

载体膜主体32的厚度优选为3μm以上且75μm以下,更优选为12μm以上且50μm以下。如果载体膜主体32的厚度为上述范围的下限值以上,则电磁波屏蔽膜1的操作性变得良好。如果载体膜主体32的厚度为上述范围的上限值以下,则在绝缘膜的表面上热压电磁波屏蔽膜1的导电性粘接剂层(各向异性导电性粘接剂层24或各向同性导电性粘接剂层26)时,容易向导电性粘接剂层传导热量。The thickness of the carrier film main body 32 is preferably 3 μm or more and 75 μm or less, and more preferably 12 μm or more and 50 μm or less. The handleability of the electromagnetic wave shielding film 1 becomes favorable as the thickness of the carrier film main body 32 is more than the lower limit of the said range. When the thickness of the carrier film main body 32 is equal to or less than the upper limit of the above-mentioned range, the conductive adhesive layer (anisotropic conductive adhesive layer 24 or isotropic adhesive layer 24 or isotropic adhesive layer 24 of the electromagnetic wave shielding film 1) is thermally pressed on the surface of the insulating film. In the case of the same conductive adhesive layer 26), heat is easily conducted to the conductive adhesive layer.

粘合剂层34是例如在载体膜主体32的表面上涂布包含粘合剂的粘合剂组合物而形成的。通过使载体膜30具有粘合剂层34,在从导电性粘接剂层剥离脱模膜40时或在将电磁波屏蔽膜1通过热压贴到印刷线路板等上时,可以抑制载体膜30从绝缘树脂层10剥离。因此,载体膜30可以充分发挥作为保护膜的作用。The adhesive layer 34 is formed by applying, for example, an adhesive composition containing an adhesive on the surface of the carrier film body 32 . By providing the carrier film 30 with the adhesive layer 34, the carrier film 30 can be suppressed when the release film 40 is peeled from the conductive adhesive layer or when the electromagnetic wave shielding film 1 is attached to a printed wiring board or the like by thermocompression. peeled from the insulating resin layer 10 . Therefore, the carrier film 30 can fully function as a protective film.

作为粘合剂,优选赋予粘合剂层34适当粘合性的物质,其中,适当粘合性是指热压前载体膜30不易从绝缘树脂层10剥离,热压后可以将载体膜30从绝缘树脂层10剥离的程度。As the adhesive, a substance that imparts appropriate adhesiveness to the adhesive layer 34 is preferable. The appropriate adhesiveness means that the carrier film 30 is not easily peeled from the insulating resin layer 10 before hot pressing, and the carrier film 30 can be removed from the insulating resin layer 10 after hot pressing. The degree to which the insulating resin layer 10 is peeled off.

作为粘合剂,可列举:丙烯酸系粘合剂、氨基甲酸酯系粘合剂、有机硅系粘合剂、橡胶系粘合剂等。As an adhesive, an acrylic adhesive, a urethane adhesive, a silicone adhesive, a rubber adhesive etc. are mentioned.

粘合剂的玻璃化转变温度优选为-100℃以上且60℃以下,更优选为-60℃以上且40℃以下。The glass transition temperature of the binder is preferably -100°C or higher and 60°C or lower, and more preferably -60°C or higher and 40°C or lower.

载体膜30的厚度优选为25μm以上且125μm以下,更优选为38μm以上且100μm以下。如果载体膜30的厚度为上述范围的下限值以上,则电磁波屏蔽膜1的操作性变得良好。如果载体膜30的厚度为上述范围的上限值以下,则在绝缘膜的表面上热压电磁波屏蔽膜1的导电性粘接剂层时,容易向导电性粘接剂层传递热量。The thickness of the carrier film 30 is preferably 25 μm or more and 125 μm or less, and more preferably 38 μm or more and 100 μm or less. When the thickness of the carrier film 30 is equal to or more than the lower limit value of the above-mentioned range, the handleability of the electromagnetic wave shielding film 1 becomes favorable. When the thickness of the carrier film 30 is below the upper limit of the above-mentioned range, heat is easily transferred to the conductive adhesive layer when the conductive adhesive layer of the electromagnetic wave shielding film 1 is thermally pressed on the surface of the insulating film.

(脱模膜)(release film)

脱模膜40保护导电性粘接剂层(各向异性导电性粘接剂层24或各向同性导电性粘接剂层26),使电磁波屏蔽膜1的操作性良好。将电磁波屏蔽膜1贴到印刷线路板等上之前,脱模膜40被从导电性粘接剂层(各向异性导电性粘接剂层24或各向同性导电性粘接剂层26)上剥离。The release film 40 protects the conductive adhesive layer (the anisotropic conductive adhesive layer 24 or the isotropic conductive adhesive layer 26 ), and improves the handleability of the electromagnetic wave shielding film 1 . Before attaching the electromagnetic wave shielding film 1 to a printed wiring board or the like, the release film 40 is removed from the conductive adhesive layer (anisotropic conductive adhesive layer 24 or isotropic conductive adhesive layer 26 ). stripped.

脱模膜40例如具有脱模膜主体42和设置在脱模膜主体42的导电性粘接剂层一侧的表面上的脱模剂层44。The release film 40 has, for example, a release film body 42 and a release agent layer 44 provided on the surface of the release film body 42 on the side of the conductive adhesive layer.

作为脱模膜主体42的树脂材料,可列举与载体膜主体32的树脂材料相同的物质。As a resin material of the release film main body 42, the thing similar to the resin material of the carrier film main body 32 is mentioned.

脱模膜主体42可以包含着色剂、填料等。The release film body 42 may contain colorants, fillers, and the like.

脱模膜主体42的厚度优选为5μm以上且500μm以下,更优选为10μm以上且150μm以下,进一步优选25μm以上且100μm以下。The thickness of the release film main body 42 is preferably 5 μm or more and 500 μm or less, more preferably 10 μm or more and 150 μm or less, and further preferably 25 μm or more and 100 μm or less.

用脱模剂处理脱模膜主体42的表面,形成脱模剂层44。通过使脱模膜40具有脱模剂层44,在从导电性粘接剂层剥离脱模膜40时,容易剥离脱模膜40,导电性粘接剂层不易断裂。The surface of the release film main body 42 is processed with a release agent, and the release agent layer 44 is formed. By providing the release film 40 with the release agent layer 44, when the release film 40 is peeled off from the conductive adhesive layer, the release film 40 is easily peeled off, and the conductive adhesive layer is less likely to be broken.

作为脱模剂,使用公知的脱模剂即可。As a mold release agent, a well-known mold release agent may be used.

脱模剂层44的厚度优选为0.05μm以上且30μm以下,更优选为0.1μm以上且20μm以下。如果脱模剂层44的厚度在上述范围内,则更容易剥离脱模膜40。The thickness of the release agent layer 44 is preferably 0.05 μm or more and 30 μm or less, and more preferably 0.1 μm or more and 20 μm or less. If the thickness of the release agent layer 44 is within the above-mentioned range, the release film 40 will be more easily peeled off.

(电磁波屏蔽膜的厚度)(Thickness of electromagnetic wave shielding film)

电磁波屏蔽膜1的厚度(除载体膜30和脱模膜40以外)优选为3μm以上且50μm以下,更优选为5μm以上且30μm以下。如果不包含载体膜30和脱模膜40的电磁波屏蔽膜1的厚度为上述范围的下限值以上,则剥离载体膜30时,不易断裂。如果不包含载体膜30和脱模膜40的电磁波屏蔽膜1的厚度为上述范围的上限值以下,则可以减薄带有电磁波屏蔽膜的印刷线路板。The thickness of the electromagnetic wave shielding film 1 (excluding the carrier film 30 and the release film 40 ) is preferably 3 μm or more and 50 μm or less, and more preferably 5 μm or more and 30 μm or less. When the thickness of the electromagnetic wave shielding film 1 excluding the carrier film 30 and the release film 40 is equal to or more than the lower limit value of the above-mentioned range, the carrier film 30 will not be easily broken when peeled off. If the thickness of the electromagnetic wave shielding film 1 excluding the carrier film 30 and the release film 40 is equal to or less than the upper limit of the above-mentioned range, the printed wiring board with the electromagnetic wave shielding film can be thinned.

<电磁波屏蔽膜的制造方法><Manufacturing method of electromagnetic wave shielding film>

本发明的第二方式为电磁波屏蔽膜的制造方法,其具有下述工序:将芳香族聚醚酮与聚醚酰亚胺的混合树脂成型为膜状而形成绝缘树脂层的工序;和,在上述绝缘树脂层一个面上形成导电层的工序。A second aspect of the present invention is a method for producing an electromagnetic wave shielding film, comprising the steps of: forming a mixed resin of aromatic polyetherketone and polyetherimide into a film shape to form an insulating resin layer; and A step of forming a conductive layer on one surface of the insulating resin layer.

具体而言,作为制造第一实施方式的电磁波屏蔽膜的方法,可列举下述方法(A1)、方法(A2)。作为制造第二实施方式的电磁波屏蔽膜的方法,可列举下述方法(B1)、方法(B2)。作为制造第三实施方式的电磁波屏蔽膜的方法,可列举下述方法(C1)、方法(C2)。Specifically, as a method of manufacturing the electromagnetic wave shielding film of 1st Embodiment, the following method (A1) and method (A2) are mentioned. As a method of manufacturing the electromagnetic wave shielding film of 2nd Embodiment, the following method (B1) and method (B2) are mentioned. As a method of manufacturing the electromagnetic wave shielding film of 3rd Embodiment, the following method (C1) and method (C2) are mentioned.

方法(A1)为具有下述工序(A1-1)~(A1-4)的方法。The method (A1) is a method having the following steps (A1-1) to (A1-4).

工序(A1-1):将芳香族聚醚酮与聚醚酰亚胺的混合树脂成型为膜状,将所形成的绝缘树脂层10层叠在载体膜30上的工序。Step (A1-1): A step of forming a mixed resin of aromatic polyetherketone and polyetherimide into a film shape, and laminating the formed insulating resin layer 10 on the carrier film 30 .

工序(A1-2):在绝缘树脂层10的与载体膜30相反侧的面上形成金属薄膜层22的工序。Step (A1-2): A step of forming the metal thin film layer 22 on the surface of the insulating resin layer 10 on the opposite side to the carrier film 30 .

工序(A1-3):在金属薄膜层22的与绝缘树脂层10相反侧的面上形成各向异性导电性粘接剂层24的工序。Step (A1-3): A step of forming the anisotropic conductive adhesive layer 24 on the surface of the metal thin film layer 22 on the opposite side to the insulating resin layer 10 .

工序(A1-4):在各向异性导电性粘接剂层24的与金属薄膜层22相反侧的面上层叠脱模膜40的工序。Step (A1-4): A step of laminating the release film 40 on the surface of the anisotropic conductive adhesive layer 24 on the opposite side to the metal thin film layer 22 .

下面,对方法(A1)的各工序进行详细说明。Next, each step of the method (A1) will be described in detail.

在工序(A1-1)中,将芳香族聚醚酮与聚醚酰亚胺的混合树脂成型为膜状。作为其成型方法,可列举:熔融挤出成型法、压延成型法、流延法等,从简化设备的观点考虑,优选熔融挤出成型法。In step (A1-1), the mixed resin of aromatic polyetherketone and polyetherimide is formed into a film shape. As the molding method, a melt extrusion molding method, a calender molding method, a casting method, etc. can be mentioned, and the melt extrusion molding method is preferable from the viewpoint of simplifying the equipment.

在熔融挤出成型法中,使用熔融挤出成型机熔融混炼上述树脂,从设置在熔融挤出成型机的前端部的T模头连续挤出成带状,从而将上述树脂成型为膜状。熔融混炼时的优选温度如上所述。In the melt extrusion molding method, the above-mentioned resin is melt-kneaded using a melt-extrusion molding machine, and is continuously extruded into a belt shape from a T-die provided at the front end of the melt-extrusion molding machine, thereby molding the above-mentioned resin into a film shape . The preferable temperature at the time of melt-kneading is as described above.

提供给熔融挤出成型机的上述树脂的含水率优选为0ppm以上且5000ppm以下,更优选为0ppm以上且2000ppm以下。如果上述树脂的含水率为上述上限值以下,可以防止上述树脂发泡。The water content of the above-mentioned resin supplied to the melt extrusion molding machine is preferably 0 ppm or more and 5000 ppm or less, and more preferably 0 ppm or more and 2000 ppm or less. If the moisture content of the resin is equal to or less than the upper limit value, the resin can be prevented from foaming.

为了防止熔融混炼时上述树脂氧化劣化和氧交联,优选使熔融挤出成型机的供料口为惰性气体气氛。作为惰性气体,例如,可使用:氦气、氖气、氩气、氪气、氮气、二氧化碳气体等。In order to prevent the above-mentioned resin oxidative degradation and oxygen crosslinking during melt-kneading, it is preferable to make the feed port of the melt extrusion molding machine an inert gas atmosphere. As the inert gas, for example, helium gas, neon gas, argon gas, krypton gas, nitrogen gas, carbon dioxide gas and the like can be used.

从T模头挤出的熔融状态的膜优选紧贴金属辊而冷却。金属辊的温度优选低于上述树脂的熔点,更优选为结晶温度以下。如果金属辊的温度低于上述树脂的熔点,则可以防止膜断裂。The molten film extruded from the T die is preferably cooled against a metal roll. The temperature of the metal roll is preferably lower than the melting point of the above-mentioned resin, and more preferably lower than the crystallization temperature. If the temperature of the metal roll is lower than the melting point of the above-mentioned resin, the film can be prevented from breaking.

将如上得到的膜状绝缘树脂层10层叠在载体膜30的设有粘合剂层34的面上。The film-like insulating resin layer 10 obtained as described above is laminated on the surface of the carrier film 30 on which the adhesive layer 34 is provided.

在导电层20具有黑化层的情况下,通过蒸镀、镀敷等在如上得到的绝缘树脂层10上形成黑化层即可。When the conductive layer 20 has a blackened layer, the blackened layer may be formed on the insulating resin layer 10 obtained as described above by vapor deposition, plating, or the like.

作为工序(A1-2)中的金属薄膜层的形成方法,可列举:通过物理蒸镀、CVD(化学气相沉积)形成蒸镀膜的方法、通过镀敷形成镀敷膜的方法、粘贴金属箔的方法等。从可以形成面方向的导电性优异的金属薄膜层方面考虑,优选通过物理蒸镀、CVD形成蒸镀膜的方法、或通过镀敷形成镀敷膜的方法。从可以减薄金属薄膜层的厚度、且即使厚度较薄也可以形成面方向的导电性优异的金属薄膜层、且可以通过干法工艺简便地形成金属薄膜层方面考虑,更优选通过物理蒸镀、CVD形成蒸镀膜的方法,进一步优选通过物理蒸镀形成蒸镀膜的方法。Examples of the method of forming the metal thin film layer in the step (A1-2) include a method of forming a vapor-deposited film by physical vapor deposition, CVD (chemical vapor deposition), a method of forming a plated film by plating, and a method of affixing a metal foil. method etc. The method of forming a vapor-deposited film by physical vapor deposition, CVD, or the method of forming a plated film by plating is preferable because a metal thin film layer having excellent electrical conductivity in the plane direction can be formed. Since the thickness of the metal thin film layer can be reduced, a metal thin film layer having excellent electrical conductivity in the plane direction can be formed even if the thickness is thin, and the metal thin film layer can be easily formed by a dry process, physical vapor deposition is more preferable. 2. The method of forming the vapor-deposited film by CVD, and the method of forming the vapor-deposited film by physical vapor deposition is more preferable.

在工序(A1-3)中,在金属薄膜层22的与绝缘树脂层10相反侧的面上涂布导电性粘接剂涂料。导电性粘接剂涂料含有热固性粘接剂24a、导电性粒子24b和溶剂。通过使溶剂从所涂布的导电性粘接剂涂料中挥发,形成各向异性导电性粘接剂层24。In the step (A1-3), the conductive adhesive paint is applied on the surface of the metal thin film layer 22 on the opposite side to the insulating resin layer 10 . The conductive adhesive paint contains the thermosetting adhesive 24a, the conductive particles 24b, and a solvent. The anisotropic conductive adhesive layer 24 is formed by volatilizing the solvent from the applied conductive adhesive paint.

作为导电性粘接剂涂料所含的溶剂,例如,可列举:酯(乙酸丁酯、乙酸乙酯、乙酸甲酯、乙酸异丙酯、乙二醇单乙酸酯等)、酮(甲基乙基酮、甲基异丁基酮、丙酮、甲基异丁基酮、环己酮等)、醇(甲醇、乙醇、异丙醇、丁醇、丙二醇单甲醚、丙二醇等)等。Examples of the solvent contained in the conductive adhesive coating material include esters (butyl acetate, ethyl acetate, methyl acetate, isopropyl acetate, ethylene glycol monoacetate, etc.), ketones (methyl acetate, etc.) ethyl ketone, methyl isobutyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, etc.), alcohols (methanol, ethanol, isopropanol, butanol, propylene glycol monomethyl ether, propylene glycol, etc.) and the like.

作为导电性粘接剂的涂布方法,例如,可应用使用下述各种涂布机的方法:模涂机、凹版涂布机、辊式涂布机、帘式流涂机、旋转涂布机、刮棒涂布机、逆转辊涂布机、吻合式涂布机、喷注式刮出涂布机、棒式涂布机、气刀涂布机、刀式涂布机、刮刀涂布机、流延涂布机、丝网涂布机等各种涂布机。As a coating method of the conductive adhesive, for example, a method using the following various coaters can be applied: a die coater, a gravure coater, a roll coater, a curtain flow coater, and a spin coater. Machine, Bar Coater, Reverse Roll Coater, Match Coater, Jet Coater, Bar Coater, Air Knife Coater, Knife Coater, Blade Coater machine, casting coater, screen coater and other coating machines.

在工序(A1-4)中,以脱模剂层44与各向异性导电性粘接剂层24接触的方式,将脱模膜40层叠在各向异性导电性粘接剂层24的与金属薄膜层22相反侧的面上。In step (A1-4), the release film 40 is laminated on the anisotropic conductive adhesive layer 24 and the metal so that the release agent layer 44 is in contact with the anisotropic conductive adhesive layer 24 The surface on the opposite side of the thin film layer 22 .

将脱模膜40层叠在各向异性导电性粘接剂层24上之后,对包含载体膜30、绝缘树脂层10、金属薄膜层22、各向异性导电性粘接剂层24和脱模膜40的层叠体实施加压处理,以提高各层彼此之间的紧贴性。After laminating the release film 40 on the anisotropic conductive adhesive layer 24 , the layers containing the carrier film 30 , the insulating resin layer 10 , the metal thin film layer 22 , the anisotropic conductive adhesive layer 24 and the release film The laminated body of 40 is subjected to pressure treatment to improve the adhesion between the layers.

作为加压处理时的压力,优选0.1kPa以上且100kPa以下,更优选0.1kPa以上且20kPa以下,进一步优选1kPa以上且10kPa以下。The pressure at the time of pressurization is preferably 0.1 kPa or more and 100 kPa or less, more preferably 0.1 kPa or more and 20 kPa or less, and further preferably 1 kPa or more and 10 kPa or less.

可以在加压处理的同时进行加热。作为此时的加热温度,优选50℃以上且100℃以下。Heating may be performed simultaneously with the pressure treatment. The heating temperature at this time is preferably 50°C or higher and 100°C or lower.

方法(A2)为具有下述工序(A2-1)~(A2-4)的方法。The method (A2) is a method having the following steps (A2-1) to (A2-4).

工序(A2-1):将芳香族聚醚酮与聚醚酰亚胺的混合树脂成型为膜状,将所形成的绝缘树脂层10层叠在载体膜30上的工序。Step (A2-1): A step of forming a mixed resin of aromatic polyetherketone and polyetherimide into a film shape, and laminating the formed insulating resin layer 10 on the carrier film 30 .

工序(A2-2):在绝缘树脂层10的与载体膜30相反侧的面上形成金属薄膜层22、从而形成层叠体(I)的工序。Step (A2-2): A step of forming the laminated body (I) by forming the metal thin film layer 22 on the surface of the insulating resin layer 10 opposite to the carrier film 30 .

工序(A2-3):在脱模膜40上形成各向异性导电性粘接剂层24、从而形成层叠体(II)的工序。Process (A2-3): The process of forming the anisotropic conductive adhesive bond layer 24 on the release film 40, and forming the laminated body (II).

工序(A2-4):以层叠体(I)的金属薄膜层22与层叠体(II)的各向异性导电性粘接剂层24接触的方式贴合层叠体(I)和层叠体(II)的工序。Step (A2-4): Laminating the laminate (I) and the laminate (II) so that the metal thin film layer 22 of the laminate (I) and the anisotropic conductive adhesive layer 24 of the laminate (II) are in contact with each other ) process.

工序(A2-1)和工序(A2-2)与上述方法(A1)中的工序(A1-1)和工序(A1-2)相同。The step (A2-1) and the step (A2-2) are the same as the step (A1-1) and the step (A1-2) in the above-mentioned method (A1).

在工序(A2-3)中,在脱模膜40的设有脱模剂层44的面上涂布导电性粘接剂涂料。通过使溶剂从所涂布的导电性粘接剂涂料挥发,形成各向异性导电性粘接剂层24。导电性粘接剂涂料和涂布方法与上述方法(A)中的工序(A1-3)相同。In the step (A2-3), the conductive adhesive paint is applied on the surface of the release film 40 on which the release agent layer 44 is provided. The anisotropic conductive adhesive layer 24 is formed by volatilizing the solvent from the applied conductive adhesive paint. The conductive adhesive coating material and the coating method are the same as the step (A1-3) in the above-mentioned method (A).

工序(A2-4)中,贴合层叠体(I)和层叠体(II)时,可以实施加热处理,以提高层叠体(I)和层叠体(II)的紧贴性。加压条件与工序(A1-4)中的加压处理相同。另外,在工序(A2-4)中,也可以与工序(A1-4)同样地进行加热。In the step (A2-4), when the laminated body (I) and the laminated body (II) are bonded together, a heat treatment may be performed to improve the adhesion between the laminated body (I) and the laminated body (II). The pressurizing conditions are the same as the pressurizing treatment in the step (A1-4). In addition, in the step (A2-4), heating may be performed in the same manner as in the step (A1-4).

在方法(B1)中,将导电性粘接剂涂料变更为含有热固性粘接剂26a、导电性粒子26b和溶剂的涂料,由此形成各向同性导电性粘接剂层26,除此之外,与方法(A1)相同。In the method (B1), the isotropic conductive adhesive layer 26 is formed by changing the conductive adhesive coating material to a coating material containing the thermosetting adhesive 26a, the conductive particles 26b and the solvent , same as method (A1).

在方法(B2)中,将导电性粘接剂涂料变更为含有热固性粘接剂26a、导电性粒子26b和溶剂的涂料,由此形成各向同性导电性粘接剂层26,除此之外,与方法(A2)相同。In the method (B2), the isotropic conductive adhesive layer 26 is formed by changing the conductive adhesive coating material to a coating material containing the thermosetting adhesive 26a, the conductive particles 26b and the solvent , same as method (A2).

方法(C1)为具有下述工序(C1-1)~(C1-3)的方法。The method (C1) is a method having the following steps (C1-1) to (C1-3).

工序(C1-1):将芳香族聚醚酮与聚醚酰亚胺的混合树脂成型为膜状,将所形成的绝缘树脂层10层叠在载体膜30上的工序。Step (C1-1): A step of forming a mixed resin of aromatic polyetherketone and polyetherimide into a film shape, and laminating the formed insulating resin layer 10 on the carrier film 30 .

工序(C1-2):在绝缘树脂层10的与载体膜30相反侧的面上形成各向同性导电性粘接剂层26的工序。Step (C1-2): A step of forming the isotropic conductive adhesive layer 26 on the surface of the insulating resin layer 10 opposite to the carrier film 30 .

工序(C1-3):在各向同性导电性粘接剂层26的与绝缘树脂层10相反侧的面上层叠脱模膜40的工序。Step (C1-3): A step of laminating the release film 40 on the surface of the isotropic conductive adhesive layer 26 on the opposite side to the insulating resin layer 10 .

在方法(C1)中,省略金属薄膜层的形成,使用各向同性导电性粘接剂作为导电性粘接剂直接在绝缘树脂层10上形成各向同性导电性粘接剂层26,除此之外,与方法(A1)相同。In the method (C1), the formation of the metal thin film layer is omitted, and the isotropic conductive adhesive layer 26 is directly formed on the insulating resin layer 10 using an isotropic conductive adhesive as the conductive adhesive. Other than that, it is the same as method (A1).

方法(C2)为具有下述工序(C2-1)~(C2-3)的方法。The method (C2) is a method having the following steps (C2-1) to (C2-3).

工序(C2-1):将芳香族聚醚酮与聚醚酰亚胺的混合树脂成型为膜状,将所形成的绝缘树脂层10层叠在载体膜30上,从而形成层叠体(I)的工序。Step (C2-1): The mixed resin of aromatic polyetherketone and polyetherimide is formed into a film shape, and the formed insulating resin layer 10 is laminated on the carrier film 30 to form the laminated body (I). process.

工序(C2-2):在脱模膜40上形成各向同性导电性粘接剂层26,从而形成层叠体(II)的工序。Step (C2-2): The step of forming the isotropic conductive adhesive layer 26 on the release film 40 to form the laminate (II).

工序(C2-3):以层叠体(I)的绝缘树脂层10与层叠体(II)的各向同性导电性粘接剂层26接触的方式贴合层叠体(I)和层叠体(II)的工序。Step (C2-3): Laminating the laminate (I) and the laminate (II) so that the insulating resin layer 10 of the laminate (I) and the isotropic conductive adhesive layer 26 of the laminate (II) are in contact with each other ) process.

在方法(C2)中,省略金属薄膜层的形成,使用各向同性导电性粘接剂作为导电性粘接剂,在绝缘树脂层10上贴合各向同性导电性粘接剂层26,除此之外与方法(A2)相同。In the method (C2), the formation of the metal thin film layer is omitted, the isotropic conductive adhesive is used as the conductive adhesive, and the isotropic conductive adhesive layer 26 is pasted on the insulating resin layer 10, except Otherwise, it is the same as method (A2).

(作用效果)(Effect)

根据绝缘树脂层10含有芳香族聚醚酮与聚醚酰亚胺的混合树脂的本方式的电磁波屏蔽膜1,可以提高绝缘树脂层10对包含金属的导电层20的粘接力。因此,可以防止在电磁波屏蔽膜1的处理中绝缘树脂层10与导电层20发生层间剥离。特别是在导电层20具有金属薄膜层22的情况下可发挥该效果,使含有芳香族聚醚酮与聚醚酰亚胺的混合树脂的绝缘树脂层10以高粘接力与金属薄膜层22粘接。According to the electromagnetic wave shielding film 1 of this aspect in which the insulating resin layer 10 contains the mixed resin of aromatic polyetherketone and polyetherimide, the adhesive force of the insulating resin layer 10 to the conductive layer 20 containing metal can be improved. Therefore, it is possible to prevent interlayer peeling between the insulating resin layer 10 and the conductive layer 20 during the processing of the electromagnetic wave shielding film 1 . In particular, when the conductive layer 20 has the metal thin film layer 22, this effect is exhibited, and the insulating resin layer 10 containing the mixed resin of aromatic polyether ketone and polyetherimide can be strongly bonded to the metal thin film layer 22 with high adhesive force. bonding.

(其它实施方式)(Other Embodiments)

本方式的电磁波屏蔽膜不限定于上述实施方式。The electromagnetic wave shielding film of this embodiment is not limited to the above-mentioned embodiment.

例如,在各向异性导电性粘接剂层24或各向同性导电性粘接剂层26的表面粘合力较小的情况下,可以省略脱模膜40。For example, when the surface adhesive force of the anisotropic conductive adhesive layer 24 or the isotropic conductive adhesive layer 26 is small, the release film 40 may be omitted.

在绝缘树脂层10具有充分的柔软性、强度的情况下,可以省略载体膜30。When the insulating resin layer 10 has sufficient flexibility and strength, the carrier film 30 may be omitted.

在载体膜主体32为具有自粘合性的膜的情况下,载体膜30可以省略粘合剂层34。When the carrier film main body 32 is a self-adhesive film, the carrier film 30 may omit the adhesive layer 34 .

在仅靠脱模膜主体42即具有充分脱模性的情况下,脱模膜40可以省略脱模剂层44。When the release film main body 42 alone has sufficient releasability, the release film 40 can omit the release agent layer 44 .

<带有电磁波屏蔽膜的印刷线路板><Printed Wiring Board with Electromagnetic Wave Shielding Film>

本发明的第三方式为带有电磁波屏蔽膜的印刷线路板,其具有:印刷线路板,其在基板的至少单面设有印刷电路;绝缘膜,其与上述印刷线路板的设有上述印刷电路的一侧的表面邻接;和,上述方式的电磁波屏蔽膜,其以上述粘接剂层与上述绝缘膜邻接的方式设置。A third aspect of the present invention is a printed wiring board with an electromagnetic wave shielding film, comprising: a printed wiring board provided with a printed circuit on at least one side of a substrate; and an insulating film provided with the above printed wiring board The surface of one side of a circuit is adjacent; and the electromagnetic wave shielding film of the above-mentioned form is provided so that the above-mentioned adhesive bond layer may be adjacent to the above-mentioned insulating film.

图4是示出本方式的带有电磁波屏蔽膜的印刷线路板的一个实施方式的剖视图。FIG. 4 is a cross-sectional view showing one embodiment of the electromagnetic wave shielding film-equipped printed wiring board of the present embodiment.

带有电磁波屏蔽膜的印刷线路板2具备柔性印刷线路板50、绝缘膜60和第一实施方式的电磁波屏蔽膜1。The electromagnetic wave shielding film-attached printed wiring board 2 includes a flexible printed wiring board 50 , an insulating film 60 , and the electromagnetic wave shielding film 1 of the first embodiment.

柔性印刷线路板50在基膜52的至少单面设有印刷电路54。The flexible printed wiring board 50 is provided with the printed circuit 54 on at least one side of the base film 52 .

绝缘膜60设置在柔性印刷线路板50的设有印刷电路54一侧的表面上。The insulating film 60 is provided on the surface of the flexible printed wiring board 50 on the side where the printed circuit 54 is provided.

电磁波屏蔽膜1的各向异性导电性粘接剂层24粘接于绝缘膜60的表面,并固化。另外,各向异性导电性粘接剂层24经由绝缘膜60上所形成的通孔(未图示)与印刷电路54电连接。The anisotropic conductive adhesive layer 24 of the electromagnetic wave shielding film 1 is adhered to the surface of the insulating film 60 and cured. In addition, the anisotropic conductive adhesive layer 24 is electrically connected to the printed circuit 54 via a through hole (not shown) formed in the insulating film 60 .

在带有电磁波屏蔽膜的印刷线路板2中,脱模膜被从各向异性导电性粘接剂层24剥离。In the printed wiring board 2 with the electromagnetic wave shielding film, the mold release film is peeled off from the anisotropic conductive adhesive layer 24 .

当带有电磁波屏蔽膜的印刷线路板2中无需载体膜30时,载体膜30被从绝缘树脂层10剥离。When the carrier film 30 is unnecessary in the printed wiring board 2 with the electromagnetic wave shielding film, the carrier film 30 is peeled off from the insulating resin layer 10 .

在除具有通孔的部分以外的印刷电路54(信号电路、地线电路、地线层等)的附近,间隔着绝缘膜60和各向异性导电性粘接剂层24而对向配置电磁波屏蔽膜1的金属薄膜层22。In the vicinity of the printed circuit 54 (signal circuit, ground circuit, ground layer, etc.) other than the portion having the through hole, the electromagnetic wave shields are arranged to face each other with the insulating film 60 and the anisotropic conductive adhesive layer 24 interposed therebetween. Metal thin film layer 22 of film 1 .

除具有通孔的部分以外的印刷电路54与金属薄膜层22的间隔距离与绝缘膜60的厚度和各向异性导电性粘接剂层24的厚度的总和大致相等。间隔距离优选为30μm以上且200μm以下,更优选为60μm以上且200μm以下。如果间隔距离小于30μm,则信号电路的电阻降低,因此,为了具有100Ω等特性电阻,必需减小信号电路的线宽,且线宽的不稳定变为特性电阻的不稳定,电阻不匹配造成的反射共振噪音容易混入电信号。如果间隔距离大于200μm,则带有电磁波屏蔽膜的印刷线路板2变厚,挠性不足。The distance between the printed circuit 54 and the metal thin film layer 22 excluding the portion having the through hole is substantially equal to the sum of the thickness of the insulating film 60 and the thickness of the anisotropic conductive adhesive layer 24 . The separation distance is preferably 30 μm or more and 200 μm or less, and more preferably 60 μm or more and 200 μm or less. If the separation distance is less than 30 μm, the resistance of the signal circuit decreases. Therefore, in order to have a characteristic resistance such as 100Ω, the line width of the signal circuit must be reduced, and the instability of the line width becomes the instability of the characteristic resistance, which is caused by resistance mismatch. Reflected resonance noise is easily mixed into electrical signals. If the spacing distance is larger than 200 μm, the printed wiring board 2 with the electromagnetic wave shielding film becomes thick and the flexibility is insufficient.

(柔性印刷线路板)(Flexible Printed Circuit Board)

柔性印刷线路板50是利用公知的蚀刻法将覆铜层叠板的铜箔加工为所需图案而形成的印刷电路54的。The flexible printed wiring board 50 is a printed circuit 54 formed by processing the copper foil of the copper-clad laminate into a desired pattern by a known etching method.

作为覆铜层叠板,可列举:通过粘接剂层(未图示)在基膜52的单面或双面上粘贴有铜箔的板;在铜箔的表面上流延用于形成基膜52的树脂溶液等而成的板等。Examples of the copper-clad laminate include those in which copper foil is pasted on one side or both sides of the base film 52 through an adhesive layer (not shown); casting is used to form the base film 52 on the surface of the copper foil. of resin solution, etc.

作为粘接剂层的材料,可列举:环氧树脂、聚酯、聚酰亚胺、聚酰胺酰亚胺、聚酰胺、酚醛树脂、聚氨基甲酸酯树脂、丙烯酸类树脂、三聚氰胺树脂等。As a material of an adhesive bond layer, an epoxy resin, polyester, polyimide, polyamideimide, polyamide, phenol resin, polyurethane resin, acrylic resin, melamine resin, etc. are mentioned.

粘接剂层的厚度优选为0.5μm以上且30μm以下。The thickness of the adhesive bond layer is preferably 0.5 μm or more and 30 μm or less.

[基膜][Basement film]

作为基膜52,优选具有耐热性的膜,更优选聚酰亚胺膜、聚醚酰亚胺膜、聚苯硫醚膜、液晶聚合物膜,进一步优选聚酰亚胺膜。The base film 52 is preferably a film having heat resistance, more preferably a polyimide film, a polyetherimide film, a polyphenylene sulfide film, or a liquid crystal polymer film, and still more preferably a polyimide film.

从电绝缘性方面考虑,基膜52的表面电阻优选为1×106Ω以上。从实用方面考虑,基膜52的表面电阻优选为1×1019Ω以下。From the viewpoint of electrical insulating properties, the surface resistance of the base film 52 is preferably 1×10 6 Ω or more. From a practical point of view, the surface resistance of the base film 52 is preferably 1×10 19 Ω or less.

基膜52的厚度优选为5μm以上且200μm以下,从弯曲性方面考虑,更优选为6μm以上且50μm以下,更优选为10μm以上且25μm以下。The thickness of the base film 52 is preferably 5 μm or more and 200 μm or less, more preferably 6 μm or more and 50 μm or less, and more preferably 10 μm or more and 25 μm or less, from the viewpoint of flexibility.

[印刷电路][printed circuit]

作为构成印刷电路54的铜箔,可列举:压延铜箔、电解铜箔等,从弯曲性方面考虑,优选压延铜箔。印刷电路54可以用作例如信号电路、地线电路、地线层等。As a copper foil which comprises the printed circuit 54, a rolled copper foil, an electrolytic copper foil, etc. are mentioned, From a viewpoint of flexibility, a rolled copper foil is preferable. The printed circuit 54 can be used as, for example, a signal circuit, a ground circuit, a ground layer, or the like.

铜箔的厚度优选为1μm以上且50μm以下,更优选为18μm以上且35μm以下。The thickness of the copper foil is preferably 1 μm or more and 50 μm or less, and more preferably 18 μm or more and 35 μm or less.

印刷电路54的长度方向的端部(端子)不被绝缘膜60或电磁波屏蔽膜1覆盖而是露出,以连接焊料、连接接头、搭载部件等。Ends (terminals) in the longitudinal direction of the printed circuit 54 are exposed without being covered by the insulating film 60 or the electromagnetic wave shielding film 1 , and are connected to solder, connection tabs, mounting members, and the like.

(绝缘膜)(insulating film)

绝缘膜60(覆盖膜)是通过涂布粘接剂、粘贴粘接剂片等在绝缘膜主体(未图示)的单面上而形成有粘接剂层(未图示)的膜。The insulating film 60 (cover film) is a film in which an adhesive layer (not shown) is formed on one side of an insulating film main body (not shown) by applying an adhesive, sticking an adhesive sheet, or the like.

从电绝缘性方面考虑,绝缘膜主体的表面电阻优选1×106Ω以上。从实用方面考虑,绝缘膜主体的表面电阻优选1×1019Ω以下。From the viewpoint of electrical insulating properties, the surface resistance of the insulating film body is preferably 1×10 6 Ω or more. From a practical standpoint, the surface resistance of the insulating film body is preferably 1×10 19 Ω or less.

作为绝缘膜主体,优选具有耐热性的膜,更优选聚酰亚胺膜、聚醚酰亚胺膜、聚苯硫醚膜、液晶聚合物膜,进一步优选聚酰亚胺膜。As the insulating film main body, a film having heat resistance is preferable, a polyimide film, a polyetherimide film, a polyphenylene sulfide film, and a liquid crystal polymer film are more preferable, and a polyimide film is still more preferable.

绝缘膜主体的厚度优选1μm以上且100μm以下,从挠性方面考虑,更优选3μm以上且25μm以下。The thickness of the insulating film body is preferably 1 μm or more and 100 μm or less, and more preferably 3 μm or more and 25 μm or less in view of flexibility.

作为粘接剂层的材料,可列举:环氧树脂、聚酯、聚酰亚胺、聚酰胺酰亚胺、聚酰胺、酚醛树脂、聚氨基甲酸酯树脂、丙烯酸树脂、三聚氰胺树脂、聚苯乙烯、聚烯烃等。环氧树脂也可以包含用于赋予挠性的橡胶成分(羧基改性丁腈橡胶等)。Examples of the material of the adhesive bond layer include epoxy resin, polyester, polyimide, polyamideimide, polyamide, phenolic resin, polyurethane resin, acrylic resin, melamine resin, polyphenylene Ethylene, polyolefin, etc. The epoxy resin may contain a rubber component (carboxy-modified nitrile rubber, etc.) for imparting flexibility.

粘接剂层的厚度优选为1μm以上且100μm以下,更优选为1.5μm以上且60μm以下。The thickness of the adhesive bond layer is preferably 1 μm or more and 100 μm or less, and more preferably 1.5 μm or more and 60 μm or less.

形成在绝缘膜60上的通孔的开口部的形状没有特别限定。作为通孔的开口部的形状,例如,可列举圆形、椭圆形、四边形等。The shape of the opening of the through hole formed in the insulating film 60 is not particularly limited. As a shape of the opening part of a through-hole, a circle, an ellipse, a quadrangle, etc. are mentioned, for example.

<带有电磁波屏蔽膜的印刷线路板的制造方法><Manufacturing method of printed wiring board with electromagnetic wave shielding film>

本发明的第四方式的带有电磁波屏蔽膜的印刷线路板的制造方法具有下述工序:将在基板的至少单面设有印刷电路的印刷线路板和上述方式的电磁波屏蔽膜隔着绝缘膜进行压接,在压接时,使上述绝缘膜紧贴在上述印刷线路板的设有上述印刷电路一侧的面上,同时,也紧贴在上述电磁波屏蔽膜的上述导电性粘接剂层上。The method for producing a printed wiring board with an electromagnetic wave shielding film according to a fourth aspect of the present invention includes a step of connecting a printed wiring board with a printed circuit on at least one side of a substrate and the electromagnetic wave shielding film of the above aspect via an insulating film Crimp bonding is performed, and at the time of crimping, the insulating film is brought into close contact with the surface of the printed wiring board on the side where the printed circuit is provided, and at the same time, it is also closely adhered to the conductive adhesive layer of the electromagnetic wave shielding film. superior.

上述实施方式的带有电磁波屏蔽膜的印刷线路板2例如可以通过具有下述工序(a)~(d)的方法制造(参照图5)。The electromagnetic wave shielding film-equipped printed wiring board 2 of the above-described embodiment can be produced, for example, by a method including the following steps (a) to (d) (see FIG. 5 ).

工序(a):在柔性印刷线路板50的设有印刷电路54的一侧的表面上设置绝缘膜60,上述绝缘膜60在与印刷电路54相对应的位置处形成有通孔62,得到带有绝缘膜的印刷线路板3的工序。Step (a): Disposing an insulating film 60 on the surface of the flexible printed wiring board 50 on the side where the printed circuit 54 is provided, the insulating film 60 having through holes 62 formed at positions corresponding to the printed circuit 54, and obtaining a tape Process of the printed wiring board 3 with the insulating film.

工序(b):工序(a)之后,以各向异性导电性粘接剂层24与绝缘膜60的表面相接触的方式将带有绝缘膜的印刷线路板3和剥离脱模膜40后的电磁波屏蔽膜1重叠,并将它们压接的工序。Step (b): After the step (a), the printed wiring board 3 with the insulating film and the surface of the insulating film 40 are separated so that the anisotropic conductive adhesive layer 24 is in contact with the surface of the insulating film 60 . A process of overlapping the electromagnetic wave shielding films 1 and crimping them.

工序(c):工序(b)之后,在不需要载体膜30时,剥离载体膜30的工序。Step (c): After the step (b), when the carrier film 30 is unnecessary, the step of peeling off the carrier film 30 .

工序(d):根据需要,在工序(a)与工序(b)之间或工序(c)之后,使各向异性导电性粘接剂层24正式固化的工序。Step (d): If necessary, between the step (a) and the step (b) or after the step (c), a step of actually curing the anisotropic conductive adhesive layer 24 .

下面,参照图5对各工序进行详细说明。Next, each step will be described in detail with reference to FIG. 5 .

(工序(a))(Process (a))

工序(a)是在柔性印刷线路板50上层叠绝缘膜60,得到带有绝缘膜的印刷线路板3的工序。The step (a) is a step of laminating the insulating film 60 on the flexible printed wiring board 50 to obtain the printed wiring board 3 with the insulating film.

具体而言,首先,在柔性印刷线路板50上重叠在与印刷电路54相对应的位置处形成有通孔62的绝缘膜60。接着,在柔性印刷线路板50的表面上粘接绝缘膜60的粘接剂层(未图示)并使粘接剂层固化,由此得到带有绝缘膜的印刷线路板3。也可以在柔性印刷线路板50的表面上临时粘接绝缘膜60的粘接剂层,在工序(d)中对粘接剂层进行正式固化。Specifically, first, the insulating film 60 having the through holes 62 formed at the positions corresponding to the printed circuit 54 is superimposed on the flexible printed wiring board 50 . Next, an adhesive layer (not shown) of the insulating film 60 is adhered to the surface of the flexible printed wiring board 50 and the adhesive layer is cured, whereby the printed wiring board 3 with the insulating film is obtained. The adhesive layer of the insulating film 60 may be temporarily adhered to the surface of the flexible printed wiring board 50, and the adhesive layer may be mainly cured in the step (d).

粘接剂层的粘接和固化利用例如加压机(未图示)等通过热压来进行。The bonding and curing of the adhesive layer are performed by hot pressing using, for example, a press (not shown).

(工序(b))(Process (b))

工序(b)是在带有绝缘膜的印刷线路板3上压接电磁波屏蔽膜1的工序。The step (b) is a step of crimping the electromagnetic wave shielding film 1 on the printed wiring board 3 with an insulating film.

具体而言,在带有绝缘膜的印刷线路板3上重叠剥离脱模膜40后的电磁波屏蔽膜1,并通过热压等压接。由此,在绝缘膜60的表面上粘接各向异性导电性粘接剂层24,同时将各向异性导电性粘接剂层24压入通孔62内,填充通孔62内部,与印刷电路54电连接。由此,得到带有电磁波屏蔽膜的印刷线路板2。Specifically, the electromagnetic wave shielding film 1 after peeling the mold release film 40 is stacked on the printed wiring board 3 with an insulating film, and is crimped by thermocompression or the like. As a result, the anisotropic conductive adhesive layer 24 is adhered to the surface of the insulating film 60 , and the anisotropic conductive adhesive layer 24 is pressed into the through holes 62 to fill the interior of the through holes 62 . Circuit 54 is electrically connected. Thereby, the printed wiring board 2 with the electromagnetic wave shielding film was obtained.

各向异性导电性粘接剂层24的粘接和固化使用例如加压机(未图示)等通过热压来进行。The adhesion and curing of the anisotropic conductive adhesive layer 24 are performed by hot pressing using, for example, a press (not shown).

热压时间优选为20秒以上、60分钟以下,更优选为30秒以上、30分钟以下。如果热压时间为上述范围的下限值以上,则可以容易地在绝缘膜60的表面上粘接各向异性导电性粘接剂层24。如果热压时间为上述范围的上限值以下,则可以缩短带有电磁波屏蔽膜的印刷线路板2的制造时间。The hot pressing time is preferably 20 seconds or more and 60 minutes or less, and more preferably 30 seconds or more and 30 minutes or less. The anisotropic conductive adhesive layer 24 can be easily adhered to the surface of the insulating film 60 as long as the hot pressing time is equal to or more than the lower limit of the above-mentioned range. If the hot pressing time is equal to or less than the upper limit of the above range, the production time of the electromagnetic wave shielding film-attached printed wiring board 2 can be shortened.

热压温度(加压机的热板的温度)优选为140℃以上且190℃以下,更优选为150℃以上且175℃以下。如果热压的温度为上述范围的下限值以上,则可以容易地在绝缘膜60的表面上粘接各向异性导电性粘接剂层24。另外,可以缩短热压时间。如果热压温度为上述范围的上限值以下,则可以容易地抑制电磁波屏蔽膜1、柔性印刷线路板50等的劣化等。The hot pressing temperature (temperature of the hot plate of the press) is preferably 140°C or higher and 190°C or lower, and more preferably 150°C or higher and 175°C or lower. If the temperature of the hot pressing is equal to or higher than the lower limit value of the above range, the anisotropic conductive adhesive layer 24 can be easily adhered to the surface of the insulating film 60 . In addition, the hot pressing time can be shortened. If the hot pressing temperature is equal to or less than the upper limit value of the above-mentioned range, deterioration of the electromagnetic wave shielding film 1 , the flexible printed wiring board 50 , and the like can be easily suppressed.

热压的压力优选为0.5MPa以上且20MPa以下,更优选为1MPa以上且16MPa以下。如果热压的压力为上述范围的下限值以上,则能够在绝缘膜60的表面上粘接各向异性导电性粘接剂层24。另外,可以缩短热压时间。如果热压的压力为上述范围的上限值以下,则可以抑制电磁波屏蔽膜1、柔性印刷线路板50等的破损等。The pressure of the hot pressing is preferably 0.5 MPa or more and 20 MPa or less, and more preferably 1 MPa or more and 16 MPa or less. The anisotropic conductive adhesive layer 24 can be adhered to the surface of the insulating film 60 as long as the pressure of the hot pressing is equal to or more than the lower limit value of the above-mentioned range. In addition, the hot pressing time can be shortened. If the pressure of the hot pressing is equal to or less than the upper limit of the above-mentioned range, breakage and the like of the electromagnetic wave shielding film 1 , the flexible printed wiring board 50 , and the like can be suppressed.

(工序(c))(Process (c))

工序(c)是剥离载体膜30的工序。The step (c) is a step of peeling off the carrier film 30 .

具体而言,当不需要载体膜时,从绝缘树脂层10剥离载体膜30。Specifically, when the carrier film is not required, the carrier film 30 is peeled off from the insulating resin layer 10 .

(工序(d))(Process (d))

工序(d)是使各向异性导电性粘接剂层24正式固化的工序。Step (d) is a step of actually curing the anisotropic conductive adhesive layer 24 .

在工序(b)中的热压时间为20秒以上且10分钟以下的较短时间的情况下,优选在工序(b)和工序(c)之间、或在工序(c)之后进行各向异性导电性粘接剂层24的正式固化。When the hot pressing time in the step (b) is as short as 20 seconds or more and 10 minutes or less, it is preferable to perform each direction between the step (b) and the step (c), or after the step (c). The main curing of the anisotropic conductive adhesive layer 24 is completed.

各向异性导电性粘接剂层24的正式固化使用例如烘箱等加热装置来进行。The main curing of the anisotropic conductive adhesive layer 24 is performed using, for example, a heating device such as an oven.

加热时间优选为15分钟以上且120分钟以下,更优选为30分钟以上且60分钟以下。如果加热时间为上述范围的下限值以上,则可以使各向异性导电性粘接剂层24充分固化。如果加热时间为上述范围的上限值以下,则可以缩短带有电磁波屏蔽膜的印刷线路板2的制造时间。The heating time is preferably 15 minutes or more and 120 minutes or less, and more preferably 30 minutes or more and 60 minutes or less. When the heating time is equal to or more than the lower limit of the above range, the anisotropic conductive adhesive layer 24 can be sufficiently cured. If the heating time is equal to or less than the upper limit value of the above range, the production time of the electromagnetic wave shielding film-attached printed wiring board 2 can be shortened.

加热温度(烘箱中的气氛温度)优选为120℃以上且180℃以下,更优选为120℃以上且150℃以下。如果加热温度为上述范围的下限值以上,则可以缩短加热时间。如果加热温度为上述范围的上限值以下,则可以抑制电磁波屏蔽膜1、柔性印刷线路板50等的劣化等。The heating temperature (atmosphere temperature in the oven) is preferably 120°C or higher and 180°C or lower, and more preferably 120°C or higher and 150°C or lower. If the heating temperature is equal to or higher than the lower limit value of the above-mentioned range, the heating time can be shortened. If the heating temperature is equal to or less than the upper limit of the above-mentioned range, deterioration of the electromagnetic wave shielding film 1 , the flexible printed wiring board 50 , and the like can be suppressed.

(作用效果)(Effect)

本方式的带有电磁波屏蔽膜的印刷线路板由于使用了上述电磁波屏蔽膜1,因此绝缘树脂层10与包含金属的导电层20的粘接力足够高。因此,可以防止绝缘树脂层10与导电层20之间的层间剥离。Since the electromagnetic wave shielding film 1 described above is used in the printed wiring board with the electromagnetic wave shielding film of the present embodiment, the adhesive force between the insulating resin layer 10 and the conductive layer 20 made of metal is sufficiently high. Therefore, interlayer peeling between the insulating resin layer 10 and the conductive layer 20 can be prevented.

(其它实施方式)(Other Embodiments)

本方式的带有电磁波屏蔽膜的印刷线路板不限定于上述实施方式。The printed wiring board with the electromagnetic wave shielding film of this embodiment is not limited to the above-mentioned embodiment.

例如,柔性印刷线路板50可以在背面侧具有地线层。另外,柔性印刷线路板50可以在双面具有印刷电路54,并在双面粘贴有绝缘膜60和电磁波屏蔽膜1。For example, the flexible printed wiring board 50 may have a ground layer on the back side. In addition, the flexible printed wiring board 50 may have the printed circuit 54 on both sides, and the insulating film 60 and the electromagnetic wave shielding film 1 may be pasted on both sides.

也可以使用无柔软性的刚性印刷基板来代替柔性印刷线路板50。In place of the flexible printed wiring board 50, a rigid printed circuit board having no flexibility may be used.

也可以使用第二实施方式的电磁波屏蔽膜1或第三实施方式的电磁波屏蔽膜1来代替第一实施方式的电磁波屏蔽膜1。Instead of the electromagnetic wave shielding film 1 of the first embodiment, the electromagnetic wave shielding film 1 of the second embodiment or the electromagnetic wave shielding film 1 of the third embodiment may be used.

实施例Example

[实施例1][Example 1]

(混合树脂的制备和膜成型)(Preparation of Hybrid Resin and Film Formation)

首先将PEEK〔Solvay Specialty Polymers公司制制品名:KetaSpire聚醚醚酮品类名:KT-851NL SP〕和PEI〔SABIC公司制制品名:ULTEM、9011-1000-NB、玻璃化转变温度:210℃〕以组成质量比率为PEEK:90质量%、PEI:10质量%的方式投入转鼓式混合机,将该转鼓式混合机在23℃搅拌混合1小时,从而制备搅拌混合物。First, PEEK [Product name from Solvay Specialty Polymers: KetaSpire Polyetheretherketone Product name: KT-851NL SP] and PEI [Product name from SABIC: ULTEM, 9011-1000-NB, glass transition temperature: 210°C] The composition mass ratio was put into a drum mixer so that PEEK: 90 mass % and PEI: 10 mass %, and the drum mixer was stirred and mixed at 23° C. for 1 hour to prepare a stirred mixture.

将对PEEK和PEI进行搅拌混合而得的搅拌混合物供给到带真空泵的双螺杆挤出成型机,在减压下熔融混炼,从双螺杆挤出成型机的前端部的模头挤出成棒状,水冷后切断,从而制备颗粒形的作为中间体的成型材料。在料筒温度360~380℃、模具温度380℃、连接双螺杆挤出成型机和模具的连接管的温度380℃的条件下对搅拌混合物进行熔融混炼。The stirred mixture obtained by stirring and mixing PEEK and PEI is supplied to a twin-screw extruder with a vacuum pump, melt-kneaded under reduced pressure, and extruded into a rod shape from a die at the front end of the twin-screw extruder. , water-cooled and then cut to prepare a pellet-shaped molding material as an intermediate. The stirred mixture was melt-kneaded under the conditions of a barrel temperature of 360 to 380°C, a die temperature of 380°C, and a temperature of 380°C of a connecting pipe connecting the twin-screw extruder and the die.

然后将该成型材料在加热到150℃的除湿干燥机中干燥12小时,将该干燥后的成型材料置于具有宽度900mm的T模、螺杆直径为40mm的单螺杆挤出成型机中,进行熔融混炼。将该熔融混炼后的成型材料从单螺杆挤出成型机的T模连续挤出,从而以带状挤出成型出绝缘树脂层用膜(厚度5μm)。The molding material was then dried in a dehumidifying dryer heated to 150°C for 12 hours, and the dried molding material was placed in a single-screw extruder with a T-die with a width of 900 mm and a screw diameter of 40 mm, and melted. kneading. The melt-kneaded molding material was continuously extruded from the T-die of the single-screw extruder to extrude a film for an insulating resin layer (thickness 5 μm) in a strip shape.

使用差示扫描量热计〔SII Nano Technology公司制:制品名高灵敏度差示扫描量热计X-DSC7000〕,基于JIS K7121以升温速度10℃/分钟的条件测定绝缘树脂层用膜的玻璃化转变温度。以下的实施例、比较例中的该玻璃化转变温度的测定也同样。绝缘树脂层用膜的玻璃化转变温度为148℃。The vitrification of the film for insulating resin layers was measured using a differential scanning calorimeter [manufactured by SII Nano Technology Co., Ltd.: product name high-sensitivity differential scanning calorimeter X-DSC7000] based on JIS K7121 at a temperature increase rate of 10°C/min. transition temperature. The same applies to the measurement of the glass transition temperature in the following Examples and Comparative Examples. The glass transition temperature of the film for insulating resin layers was 148°C.

如下所述地对于膜的挤出方向和宽度方向(垂直于挤出方向的方向)测定绝缘树脂层用膜的160℃下的拉伸模量。按照JIS K7160 3型切出试验片,将该试验片安装于带有已预先加热到160℃的恒温槽的拉伸试验机的夹具上,关闭恒温槽的门,在恒温槽的温度达到160℃±2℃后放置3分钟,然后基于JIS K7127以拉伸速度50mm/分钟进行测定。测定的结果如下所示。The tensile modulus at 160° C. of the film for an insulating resin layer was measured with respect to the extrusion direction and the width direction (direction perpendicular to the extrusion direction) of the film as described below. A test piece was cut out according to JIS K7160 type 3, and the test piece was mounted on a jig of a tensile testing machine with a thermostatic bath preheated to 160°C. The door of the thermostatic bath was closed, and the temperature of the thermostatic bath reached 160°C. After standing at ±2°C for 3 minutes, it was measured at a tensile speed of 50 mm/min based on JIS K7127. The results of the measurement are shown below.

膜的挤出方向的拉伸模量:1100N/mm2 Tensile modulus of film in extrusion direction: 1100 N/mm 2

膜的宽度方向的拉伸模量:1046N/mm2 Tensile modulus in the width direction of the film: 1046N/mm 2

(电磁波屏蔽膜的制造)(Manufacture of electromagnetic wave shielding film)

准备载体膜,该载体膜在PET膜(载体膜主体)的单面上设有包含丙烯酸系粘合剂的粘合剂层。在载体膜的粘合剂层的表面上贴合包含上述的绝缘树脂层用膜的绝缘树脂层。A carrier film provided with an adhesive layer containing an acrylic adhesive on one side of a PET film (carrier film main body) was prepared. The insulating resin layer containing the film for insulating resin layers described above is bonded to the surface of the adhesive layer of the carrier film.

接着,通过电子束蒸镀法,在上述绝缘树脂层的与载体膜相反侧的面上物理蒸镀铜,形成金属薄膜层(铜蒸镀膜、厚度0.07μm、表面电阻0.3Ω)。Next, copper was physically vapor-deposited on the surface of the insulating resin layer opposite to the carrier film by electron beam vapor deposition to form a metal thin film layer (copper vapor-deposited film, thickness 0.07 μm, surface resistance 0.3Ω).

将包含环氧树脂的热固性粘接剂(DIC公司制造、EXA-4816)100质量份、固化剂(AjinomotoFine-TechnoCo.,Inc.制造、PN-23)20质量份混合,得到潜在固化性环氧树脂组合物。100 parts by mass of a thermosetting adhesive containing an epoxy resin (manufactured by DIC Corporation, EXA-4816) and 20 parts by mass of a curing agent (manufactured by Ajinomoto Fine-Techno Co., Inc., PN-23) were mixed to obtain a latent curable epoxy resin resin composition.

使上述潜在固化性环氧树脂组合物和包含铜粒子的导电性粒子(平均粒径7.5μm)40质量份溶解或分散在包含甲基乙基酮的溶剂200质量份中,得到导电性粘接剂涂料。The above-mentioned latent curable epoxy resin composition and 40 parts by mass of conductive particles (average particle diameter: 7.5 μm) containing copper particles were dissolved or dispersed in 200 parts by mass of a solvent containing methyl ethyl ketone to obtain conductive adhesion agent paint.

接着,使用模涂机,将上述导电性粘接剂涂料涂布在上述金属薄膜层的与绝缘树脂层相反一侧的表面上,使溶剂挥发而进行B阶化,由此,形成各向异性导电性粘接剂层(厚度7μm、铜粒子4.5体积%)。Next, using a die coater, the conductive adhesive paint is applied on the surface of the metal thin film layer opposite to the insulating resin layer, and the solvent is volatilized to B-stage, thereby forming anisotropy. Conductive adhesive layer (thickness 7 μm, copper particle 4.5 volume %).

准备脱模膜(lintec公司制造,T157),该脱模膜中,在PET膜(厚度50μm)的单面上设有包含非有机硅系脱模剂的脱模剂层(厚度0.1μm)。A release film (manufactured by Lintec, T157) in which a release agent layer (thickness 0.1 μm) containing a non-silicone-based release agent was provided on one side of a PET film (thickness 50 μm) was prepared.

以使上述脱模剂层与上述各向异性导电性粘接剂层接触的方式,在上述各向异性导电性粘接剂层的与金属薄膜层相反侧的面粘贴上述脱模膜,得到实施例1的电磁波屏蔽膜。The above-mentioned release film was attached to the surface opposite to the metal thin film layer of the above-mentioned anisotropic conductive adhesive layer so that the above-mentioned release agent layer was brought into contact with the above-mentioned anisotropic conductive adhesive layer, and the implementation was carried out. The electromagnetic wave shielding film of Example 1.

[实施例2][Example 2]

将PEEK〔Daicel Evonik公司制、制品名:VESTAKEEP、品类名:3300G〕和PEI〔SABIC公司制制品名:ULTEM:1010-1000-NB、玻璃化转变温度:211℃〕以组成质量比率为PEEK:70质量%、PEI:30质量%的方式投入转鼓式混合机,此后按照与实施例1同样的方法制备搅拌混合物、制造电磁波屏蔽膜。绝缘树脂层用膜的玻璃化转变温度为160℃。绝缘树脂层用膜的160℃下的拉伸模量如下所示。PEEK [manufactured by Daicel Evonik, product name: VESTAKEEP, product name: 3300G] and PEI [manufactured by SABIC, product name: ULTEM: 1010-1000-NB, glass transition temperature: 211°C], and the composition mass ratio is PEEK: 70 mass % and PEI: 30 mass % were put into a drum mixer, and thereafter, a stirring mixture was prepared in the same manner as in Example 1, and an electromagnetic wave shielding film was produced. The glass transition temperature of the film for insulating resin layers was 160°C. The tensile modulus in 160 degreeC of the film for insulating resin layers is as follows.

膜的挤出方向的拉伸模量:2239N/mm2 Tensile modulus of film in extrusion direction: 2239N/mm 2

膜的宽度方向的拉伸模量:1661N/mm2 Tensile modulus in the width direction of the film: 1661 N/mm 2

[实施例3][Example 3]

将PEEK〔Solvay Specialty Polymers公司制品名:KetaSpire聚醚醚酮品类名:KT-820NT〕和实施例2中使用的PEI以组成质量比率为PEEK:50质量%、PEI:50质量%的方式投入转鼓式混合机,此后按照与实施例1同样的方法制备搅拌混合物、制造电磁波屏蔽膜。绝缘树脂层用膜的玻璃化转变温度为174℃。绝缘树脂层用膜的160℃下的拉伸模量如下所示。PEEK [Solvay Specialty Polymers company product name: KetaSpire polyether ether ketone product name: KT-820NT] and the PEI used in Example 2 were put into the rotary A drum mixer was used, and thereafter, in the same manner as in Example 1, a stirring mixture was prepared, and an electromagnetic wave shielding film was produced. The glass transition temperature of the film for insulating resin layers was 174°C. The tensile modulus in 160 degreeC of the film for insulating resin layers is as follows.

膜的挤出方向的拉伸模量:2331N/mm2 Tensile modulus of film in extrusion direction: 2331N/mm 2

膜的宽度方向的拉伸模量:2013N/mm2 Tensile modulus in the width direction of the film: 2013N/mm 2

[实施例4][Example 4]

将PEEK〔Victrex公司制制品名:VictrexPEEK381G〕和实施例2中使用的PEI以组成质量比率为PEEK:20质量%、PEI:80质量%的方式投入转鼓式混合机,此后按照与实施例1同样的方法制备搅拌混合物、制造电磁波屏蔽膜。绝缘树脂层用膜的玻璃化转变温度为198℃。绝缘树脂层用膜的160℃下的拉伸模量如下所示。PEEK (product name: Victrex PEEK381G, manufactured by Victrex) and PEI used in Example 2 were put into a drum mixer so that the composition mass ratios were PEEK: 20 mass % and PEI: 80 mass %. The same method was used to prepare the stirring mixture and manufacture the electromagnetic wave shielding film. The glass transition temperature of the film for insulating resin layers was 198°C. The tensile modulus in 160 degreeC of the film for insulating resin layers is as follows.

膜的挤出方向的拉伸模量:2720N/mm2 Tensile modulus of film in extrusion direction: 2720N/mm 2

膜的宽度方向的拉伸模量:2568N/mm2 Tensile modulus in the width direction of the film: 2568 N/mm 2

[实施例5][Example 5]

将实施例1中使用的PEEK和PEI以组成质量比率为PEEK:10质量%、PEI:90质量%的方式投入转鼓式混合机,此后按照与实施例1同样的方法制备搅拌混合物、制造电磁波屏蔽膜。绝缘树脂层用膜的玻璃化转变温度为202℃。绝缘树脂层用膜的160℃下的拉伸模量如下所示。The PEEK and PEI used in Example 1 were put into a tumbler mixer so that the composition mass ratios were PEEK: 10 mass % and PEI: 90 mass %, and then a stirring mixture was prepared and electromagnetic waves were produced in the same manner as in Example 1. shielding film. The glass transition temperature of the film for insulating resin layers was 202°C. The tensile modulus in 160 degreeC of the film for insulating resin layers is as follows.

膜的挤出方向的拉伸模量:2830N/mm2 Tensile modulus of film in extrusion direction: 2830N/mm 2

膜的宽度方向的拉伸模量:2660N/mm2 Tensile modulus in the width direction of the film: 2660 N/mm 2

[实施例6][Example 6]

使用PEKK(ARKEMA公司制制品名:KEPSTAN 8002)代替PEEK,除此以外与实施例2同样进行制造,得到实施例6的电磁波屏蔽膜。绝缘树脂层用膜的玻璃化转变温度为204℃。绝缘树脂层用膜的160℃下的拉伸模量如下所示。The electromagnetic wave shielding film of Example 6 was obtained in the same manner as in Example 2, except that PEKK (product name: KEPSTAN 8002, manufactured by ARKEMA) was used instead of PEEK. The glass transition temperature of the film for insulating resin layers was 204°C. The tensile modulus in 160 degreeC of the film for insulating resin layers is as follows.

膜的挤出方向的拉伸模量:2530N/mm2 Tensile modulus of film in extrusion direction: 2530N/mm 2

膜的宽度方向的拉伸模量:2439N/mm2 Tensile modulus in the width direction of the film: 2439 N/mm 2

(比较例1)(Comparative Example 1)

作为用于形成绝缘树脂层的涂料,将双酚A型环氧树脂(DIC公司制造,epichlone 840-S)100质量份、固化剂(三菱化学公司制造、JER Cure 113)20质量份、2-乙基-4-甲基咪唑2质量份和炭黑2质量份溶解在甲基乙基酮200质量份中,制备涂料。As a coating material for forming the insulating resin layer, 100 parts by mass of a bisphenol A epoxy resin (manufactured by DIC, epichlone 840-S), 20 parts by mass of a curing agent (manufactured by Mitsubishi Chemical Corporation, JER Cure 113), 2- 2 parts by mass of ethyl-4-methylimidazole and 2 parts by mass of carbon black were dissolved in 200 parts by mass of methyl ethyl ketone to prepare a coating material.

将上述用于形成绝缘树脂层的涂料涂布在与实施例1中使用的载体膜相同的载体膜的粘合剂层表面上,60℃下加热2分钟使其干燥,并半固化,形成厚度5μm的绝缘树脂层。在该绝缘树脂层上观察到1个/m2以上且3个/m2以下的针孔。The above-mentioned coating material for forming the insulating resin layer was applied on the surface of the adhesive layer of the same carrier film as the carrier film used in Example 1, heated at 60° C. for 2 minutes, dried, and semi-cured to form a thickness of 5μm insulating resin layer. In this insulating resin layer, 1 pinhole/m 2 or more and 3 pinholes/m 2 or less were observed.

选择没有针孔的区域,并通过电子束蒸镀法在所选择的区域中的绝缘树脂层的表面上物理蒸镀铜,形成金属薄膜层(铜蒸镀膜、厚度0.07μm、表面电阻0.3Ω)。A region without pinholes is selected, and copper is physically evaporated on the surface of the insulating resin layer in the selected region by electron beam evaporation to form a metal thin film layer (copper evaporation film, thickness 0.07 μm, surface resistance 0.3Ω) .

与实施例1同样地,在金属薄膜层的与绝缘树脂层相反侧的面上形成各向异性导电性粘接剂层,并在各向异性导电性粘接剂层上粘贴脱模膜,得到比较例1的电磁波屏蔽膜。In the same manner as in Example 1, an anisotropic conductive adhesive layer was formed on the surface opposite to the insulating resin layer of the metal thin film layer, and a release film was pasted on the anisotropic conductive adhesive layer to obtain The electromagnetic wave shielding film of Comparative Example 1.

[评价][Evaluation]

通过下述方法,对各例的电磁波屏蔽膜的绝缘树脂层与导电层的粘接性进行评价。The adhesiveness of the insulating resin layer and the conductive layer of the electromagnetic wave shielding film of each example was evaluated by the following method.

在厚度25μm的聚酰亚胺膜上重叠剥离脱模膜后的电磁波屏蔽膜,使用热压装置(折原制作所公司制造,G-12),在热板温度:180℃、载荷:2MPa下热压120秒。接着,剥离载体膜。由此,在绝缘膜的表面上暂时粘接各向异性导电性粘接剂层,得到带有电磁波屏蔽膜的聚酰亚胺。The electromagnetic wave shielding film after peeling the release film was superimposed on a polyimide film with a thickness of 25 μm, and heated at a hot plate temperature: 180° C. and a load: 2 MPa using a hot pressing apparatus (manufactured by Orihara, Ltd., G-12). Press for 120 seconds. Next, the carrier film is peeled off. Thereby, the anisotropic conductive adhesive layer was temporarily adhered to the surface of the insulating film, and the polyimide with the electromagnetic wave shielding film was obtained.

使用高温槽(楠本化成公司制造,HT210),在温度160℃下加热上述带有电磁波屏蔽膜的聚酰亚胺膜1小时,由此,使各向异性导电性粘接剂层正式固化。The anisotropic conductive adhesive layer was fully cured by heating the above-mentioned polyimide film with an electromagnetic wave shielding film at a temperature of 160° C. for 1 hour using a high-temperature bath (manufactured by Kusumoto Chemical Co., Ltd., HT210).

接着,通过粘结片(Dexerials公司制造,D3410),在电磁波屏蔽膜的绝缘树脂层的表面上热压接厚度25μm的聚酰亚胺增强板,由此制作用于拉伸试验的试验片。Next, a polyimide reinforcing plate having a thickness of 25 μm was thermocompression-bonded on the surface of the insulating resin layer of the electromagnetic wave shielding film with an adhesive sheet (manufactured by Dexerias, D3410), thereby producing a test piece for a tensile test.

在上述试验片的聚酰亚胺膜与聚酰亚胺增强板上安装拉伸试验机的夹具,根据JISZ0237,在180°剥离方向、拉伸速度50mm/分钟的条件下进行剥离试验。A jig of a tensile tester was attached to the polyimide film and the polyimide reinforcing plate of the test piece, and a peel test was performed under the conditions of a 180° peeling direction and a tensile speed of 50 mm/min according to JISZ0237.

[结果][result]

在使用实施例1的电磁波屏蔽膜的试验片中,剥离强度为7.5N/cm,在绝缘树脂层与金属薄膜层的界面发生剥离。In the test piece using the electromagnetic wave shielding film of Example 1, the peeling strength was 7.5 N/cm, and peeling occurred at the interface between the insulating resin layer and the metal thin film layer.

在使用实施例2的电磁波屏蔽膜的试验片中,剥离强度为7.2N/cm,在绝缘树脂层与金属薄膜层的界面发生剥离。In the test piece using the electromagnetic wave shielding film of Example 2, the peeling strength was 7.2 N/cm, and peeling occurred at the interface between the insulating resin layer and the metal thin film layer.

在使用实施例3的电磁波屏蔽膜的试验片中,剥离强度为7.8N/cm,在绝缘树脂层与金属薄膜层的界面发生剥离。In the test piece using the electromagnetic wave shielding film of Example 3, the peeling strength was 7.8 N/cm, and peeling occurred at the interface between the insulating resin layer and the metal thin film layer.

在使用实施例4的电磁波屏蔽膜的试验片中,剥离强度为7.3N/cm,在绝缘树脂层与金属薄膜层的界面发生剥离。In the test piece using the electromagnetic wave shielding film of Example 4, the peeling strength was 7.3 N/cm, and peeling occurred at the interface between the insulating resin layer and the metal thin film layer.

在使用实施例5的电磁波屏蔽膜的试验片中,剥离强度为7.5N/cm,在绝缘树脂层与金属薄膜层的界面发生剥离。In the test piece using the electromagnetic wave shielding film of Example 5, the peeling strength was 7.5 N/cm, and peeling occurred at the interface between the insulating resin layer and the metal thin film layer.

在使用实施例6的电磁波屏蔽膜的试验片中,剥离强度为5.3N/cm,在绝缘树脂层与金属薄膜层的界面发生剥离。In the test piece using the electromagnetic wave shielding film of Example 6, the peeling strength was 5.3 N/cm, and peeling occurred at the interface between the insulating resin layer and the metal thin film layer.

在使用比较例1的电磁波屏蔽膜的试验片中,剥离强度3.5N/cm,在绝缘树脂层与金属薄膜层之间发生层间剥离。In the test piece using the electromagnetic wave shielding film of Comparative Example 1, the peel strength was 3.5 N/cm, and interlayer peeling occurred between the insulating resin layer and the metal thin film layer.

由这些结果可知,由作为芳香族聚醚酮的一种的PEEK或PEKK与PEI构成的绝缘树脂层与由以往使用的热固性树脂构成的绝缘树脂层相比,与金属薄膜层的粘接力更强。From these results, it was found that the insulating resin layer composed of PEEK, PEKK, and PEI, which is a kind of aromatic polyether ketone, had better adhesion to the metal thin film layer than the insulating resin layer composed of the conventionally used thermosetting resin. powerful.

在实施例1~6的绝缘树脂层中,随着PEI的含量相对于PEEK增加,绝缘树脂层的玻璃化转变温度升高。正如反映该结果所示出那样,制作的电磁波屏蔽膜的绝缘树脂层的外观随着玻璃化转变温度升高而更平滑、良好。另外,玻璃化转变温度为160℃以下的实施例1、2的绝缘树脂层中,表面存在通过目视可勉强识别的程度的波纹。其是由于用来进行各向异性导电性片的正式固化的加热处理(160℃)而产生的。此种波纹虽然并未影响剥离强度,但可能损害外观。In the insulating resin layers of Examples 1 to 6, as the content of PEI increased with respect to PEEK, the glass transition temperature of the insulating resin layers increased. As reflected in this result, the appearance of the insulating resin layer of the produced electromagnetic wave shielding film became smoother and more favorable as the glass transition temperature increased. In addition, in the insulating resin layers of Examples 1 and 2 having a glass transition temperature of 160° C. or lower, there were waves on the surface of such an extent that they were barely recognizable by visual observation. This is caused by heat treatment (160° C.) for main curing of the anisotropic conductive sheet. This waviness, while not affecting peel strength, may impair appearance.

构成实施例1~6的绝缘树脂层的膜的、160℃下的拉伸模量均良好,不易受到制造时的加热处理的影响、使用时的高温环境的影响。特别是实施例1~6中的实施例3~5,拉伸模量优异且剥离强度也优异。The films constituting the insulating resin layers of Examples 1 to 6 all had good tensile modulus at 160° C., and were hardly affected by the heat treatment during production and the high temperature environment during use. In particular, Examples 3 to 5 among Examples 1 to 6 were excellent in tensile modulus and excellent in peel strength.

符号说明Symbol Description

1 电磁波屏蔽膜,1 Electromagnetic wave shielding film,

2 带有电磁波屏蔽膜的柔性印刷线路板,2 Flexible printed circuit board with electromagnetic wave shielding film,

3 带有绝缘膜的柔性印刷线路板,3 Flexible printed circuit boards with insulating films,

10 绝缘树脂层,10 insulating resin layer,

22 金属薄膜层,22 metal film layer,

20 导电层,20 conductive layers,

24 各向异性导电性粘接剂层,24 Anisotropic conductive adhesive layer,

24a 热固性粘接剂,24a Thermosetting adhesives,

24b 导电性粒子,24b Conductive particles,

26 各向同性导电性粘接剂层,26 isotropic conductive adhesive layer,

26a 热固性粘接剂,26a Thermosetting adhesives,

26b 导电性粒子,26b Conductive particles,

30 载体膜,30 carrier film,

32 载体膜主体,32 carrier film body,

34 粘着剂层,34 Adhesive layer,

40 脱模膜,40 release film,

42 脱模膜主体,42 Release film body,

44 脱模剂层,44 release agent layer,

50 柔性印刷线路板,50 flexible printed circuit boards,

52 基膜,52 basement membrane,

54 印刷电路,54 printed circuits,

60 绝缘膜,60 insulating film,

62 通孔。62 through holes.

Claims (11)

1.一种电磁波屏蔽膜,其具有绝缘树脂层、和与所述绝缘树脂层邻接的包含金属的导电层,1. An electromagnetic wave shielding film comprising an insulating resin layer and a conductive layer containing a metal adjacent to the insulating resin layer, 所述绝缘树脂层含有芳香族聚醚酮和聚醚酰亚胺。The insulating resin layer contains aromatic polyetherketone and polyetherimide. 2.根据权利要求1所述的电磁波屏蔽膜,其中,所述芳香族聚醚酮为聚醚醚酮或聚醚酮酮。2 . The electromagnetic wave shielding film according to claim 1 , wherein the aromatic polyetherketone is polyetheretherketone or polyetherketoneketone. 3 . 3.根据权利要求1或2所述的电磁波屏蔽膜,其中,所述聚醚酰亚胺的玻璃化转变温度为200℃以上,具有下述化学式(A)所示的重复单元;3. The electromagnetic wave shielding film according to claim 1 or 2, wherein the polyetherimide has a glass transition temperature of 200° C. or higher, and has a repeating unit represented by the following chemical formula (A);
Figure FDA0002126515500000011
Figure FDA0002126515500000011
4.根据权利要求1~3中任一项所述的电磁波屏蔽膜,其中,相对于所述绝缘树脂层的总质量,所述芳香族聚醚酮的含量为5质量%以上且95质量%以下,所述聚醚酰亚胺的含量为5质量%以上且95质量%以下。4 . The electromagnetic wave shielding film according to claim 1 , wherein the content of the aromatic polyether ketone is 5% by mass or more and 95% by mass relative to the total mass of the insulating resin layer. 5 . Below, content of the said polyetherimide is 5 mass % or more and 95 mass % or less. 5.根据权利要求1~4中任一项所述的电磁波屏蔽膜,其中,所述绝缘树脂层的厚度为2μm以上且30μm以下。5 . The electromagnetic wave shielding film according to claim 1 , wherein the insulating resin layer has a thickness of 2 μm or more and 30 μm or less. 6 . 6.根据权利要求1~5中任一项所述的电磁波屏蔽膜,其中,所述导电层为金属蒸镀层。6 . The electromagnetic wave shielding film according to claim 1 , wherein the conductive layer is a metal vapor deposition layer. 7 . 7.根据权利要求6所述的电磁波屏蔽膜,其中,所述金属蒸镀层为银蒸镀层或铜蒸镀层。7. The electromagnetic wave shielding film according to claim 6, wherein the metal vapor deposition layer is a silver vapor deposition layer or a copper vapor deposition layer. 8.根据权利要求1~7中任一项所述的电磁波屏蔽膜,其中,在所述绝缘树脂层的与所述导电层的相反侧的面上还具有载体膜。8 . The electromagnetic wave shielding film according to claim 1 , further comprising a carrier film on the surface of the insulating resin layer opposite to the conductive layer. 9 . 9.一种带有电磁波屏蔽膜的印刷线路板,其具有:9. A printed circuit board with an electromagnetic wave shielding film, comprising: 印刷线路板,其在基板的至少单面设有印刷电路;A printed circuit board, which is provided with a printed circuit on at least one side of a substrate; 绝缘膜,其与所述印刷线路板的设有所述印刷电路的一侧的面邻接;和,an insulating film adjacent to the face of the printed wiring board on the side where the printed circuit is provided; and, 权利要求1~8中任一项所述的电磁波屏蔽膜,其以使所述导电层与所述绝缘膜邻接的方式设置。The electromagnetic wave shielding film of any one of Claims 1-8 provided so that the said conductive layer and the said insulating film may adjoin. 10.一种电磁波屏蔽膜的制造方法,其包含下述步骤:将芳香族聚醚酮与聚醚酰亚胺的混合树脂成型为膜状,形成绝缘树脂层,在所述绝缘树脂层的一面侧形成导电层。10. A method for producing an electromagnetic wave shielding film, comprising the steps of: molding a mixed resin of aromatic polyetherketone and polyetherimide into a film shape, forming an insulating resin layer, and forming an insulating resin layer on one side of the insulating resin layer. A conductive layer is formed on the side. 11.一种带有电磁波屏蔽膜的印刷线路板的制造方法,其包含下述步骤:将在基板的至少单面设有印刷电路的印刷线路板和权利要求1~8中任一项所述的电磁波屏蔽膜隔着绝缘膜进行压接。11. A method of manufacturing a printed wiring board with an electromagnetic wave shielding film, comprising the step of: combining a printed wiring board with a printed circuit on at least one side of a substrate and the method according to any one of claims 1 to 8. The electromagnetic wave shielding film is crimped through the insulating film.
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