WO2010147082A1 - High-dielectric-constant resin composition, high-dielectric-constant resin sheet comprising same, and copper foil having high-dielectric-constant resin attached thereto - Google Patents
High-dielectric-constant resin composition, high-dielectric-constant resin sheet comprising same, and copper foil having high-dielectric-constant resin attached thereto Download PDFInfo
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- WO2010147082A1 WO2010147082A1 PCT/JP2010/060037 JP2010060037W WO2010147082A1 WO 2010147082 A1 WO2010147082 A1 WO 2010147082A1 JP 2010060037 W JP2010060037 W JP 2010060037W WO 2010147082 A1 WO2010147082 A1 WO 2010147082A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
Definitions
- the present invention relates to a high dielectric constant resin composition, a high dielectric constant resin sheet, and a high dielectric constant resin suitable for the production of substrate materials for electronic equipment, particularly electronic components and circuit boards used in equipment used in high frequency regions. Related to copper foil.
- oxide resin an organic resin
- the resin used for the laminated board has a high melt viscosity, and when used for the laminated insulating layer of a multilayer board, the gap between the circuits cannot be filled, resulting in a decrease in heat resistance. Application to applications was difficult.
- a press machine since it is necessary to raise the press temperature to the melting temperature of the thermoplastic resin, a press machine of 300 ° C. or higher is necessary, which is very problematic in terms of cost.
- JP 2007-123712 A JP-A-5-057852 JP-A-7-133359
- the present invention has a high dielectric constant, a low dielectric loss tangent, an excellent resin-filling characteristic of a circuit portion, and is suitable for an inter-circuit insulating layer, and can be molded by a general press machine of 200 ° C. or lower.
- An object of the present invention is to provide a resin composition, a high dielectric constant resin sheet using the resin composition, and a copper foil with a high dielectric constant resin.
- thermosetting polyphenylene ether having a number average molecular weight of 500 to 3000 having a terminal modified with styrene and a styrene elastomer, and a mixing ratio of the thermosetting polyphenylene ether and the styrene elastomer is 60:40 by mass ratio.
- a high dielectric constant inorganic insulating filler having an average particle diameter D50 of 0.7 ⁇ m or more and a maximum particle diameter of 10 ⁇ m or less is added to the mixed resin (A) blended so as to be ⁇ 80: 20, 100 parts by mass of the mixed resin (A)
- the high dielectric constant resin composition of the present invention has a specific composition as described above, it has a high dielectric constant and a low dielectric loss tangent, is excellent in resin filling characteristics of a circuit portion, and is a general press at 200 ° C. or lower. This is advantageous in terms of cost.
- the resin component comprises a thermosetting polyphenylene ether having a number average molecular weight of 500 to 3000 having a terminal modified with styrene and a styrene elastomer, and the mixing ratio of the thermosetting polyphenylene ether and the styrene elastomer is mass.
- the mixed resin (A) is blended so that the ratio is 60:40 to 80:20.
- styrene elastomer examples include styrene butadiene rubber (SBR), styrene thermoplastic elastomer (SBS), hydrogenated styrene thermoplastic elastomer (SEBS) that have high compatibility with the thermosetting polyphenylene ether and excellent dielectric properties. ) And modified products thereof.
- SBR styrene butadiene rubber
- SBS styrene thermoplastic elastomer
- SEBS hydrogenated styrene thermoplastic elastomer
- the mixing ratio of the thermosetting polyphenylene ether and the styrene elastomer is 60:40 to 80:20 (mass ratio of the thermosetting polyphenylene ether and the styrene elastomer). 100))).
- the mass ratio of the styrenic elastomer is less than 20, the fluidity of the resin composition becomes too high, and the resin easily flows from the edge of the laminated plate during press forming of the laminated plate, and the range of variation in the plate thickness is wide. Problem arises.
- the mass ratio of the styrene-based elastomer exceeds 40, the fluidity of the resin composition becomes too low, and the resin filling property between the circuits when laminated on the circuit becomes insufficient.
- thermosetting polyphenylene ether two or more of the thermosetting polyphenylene ether and the styrene elastomer may be used in combination.
- Examples of the high dielectric constant inorganic insulating filler used in the present invention include titanium dioxide, barium titanate, strontium titanate, calcium titanate, and lead titanate, and these can be used alone or in combination of two or more.
- the above-mentioned high dielectric constant inorganic insulating filler needs to have an average particle diameter D50 of 0.7 ⁇ m or more.
- the average particle diameter D50 is less than 0.7 ⁇ m, the thixotropy of the resin composition is increased and the resin fluidity is lowered, so that the resin filling property between the circuits when laminated on the circuit becomes insufficient.
- the high dielectric constant inorganic insulating filler needs to have a maximum particle size of 10 ⁇ m or less.
- a high dielectric constant resin composition is used as a capacitor, it is necessary to make the insulating layer thin in order to increase the capacity between two layers of a fixed area. In order not to penetrate, the thickness of the insulating layer needs to be larger than the maximum particle diameter of the high dielectric constant inorganic insulating filler.
- the maximum particle diameter of the high dielectric constant inorganic insulating filler exceeds 10 ⁇ m, the thickness of the insulating layer becomes too large, and when used as a capacitor, the capacity may be insufficient.
- the high dielectric constant inorganic insulating filler needs to be blended so as to be 250 to 900 parts by mass with respect to 100 parts by mass of the mixed resin (A).
- the content of the high dielectric constant inorganic insulating filler exceeds 900 parts by mass, it becomes difficult to mold the resin composition, and when it is less than 250 parts by mass, the dielectric constant decreases and the blending effect of the high dielectric constant inorganic insulating filler is observed. Absent.
- the dielectric constant at room temperature at a measurement frequency of 1 GHz of the cured resin composition can be 10 or more and the dielectric loss tangent can be less than 0.01.
- thermosetting polyphenylene ether constituting the mixed resin (A) and the styrene elastomer are dissolved in a solvent to form a solution.
- a resin composition in which a high dielectric constant inorganic insulating filler is dispersed in a mixed resin (A) by adding a high dielectric constant inorganic insulating filler, dispersing it, applying to a substrate, etc., and drying the solvent can be formed.
- Additives such as flame retardants and resin modifiers may be added to the high dielectric constant resin composition of the present invention as long as the effects of the present invention are not impaired.
- the high dielectric constant resin composition of the present invention forms a B-stage high dielectric constant resin sheet by forming a resin layer having a thickness of 10 to 100 ⁇ m comprising the high dielectric constant resin composition of the present invention on the surface of a substrate.
- a resin layer having a thickness of 10 to 100 ⁇ m comprising the high dielectric constant resin composition of the present invention on the surface of a substrate.
- a polyethylene terephthalate film or the like can be used as the substrate.
- the high dielectric constant resin composition of the present invention is formed in a B-stage shape by forming a resin layer having a thickness of 10 to 100 ⁇ m made of the high dielectric constant resin composition of the present invention on the surface of a copper foil for printed wiring boards.
- the copper foil with a high dielectric constant resin can be formed.
- the copper foil with a high dielectric constant resin can fill the space between the circuits by arranging the resin layer surface on the circuit and performing hot pressing or the like. Since the high dielectric constant resin composition of the present invention has the above-described configuration, it can be molded with a general press at 200 ° C. or lower while having good dielectric properties.
- the method for forming the resin layer in the high dielectric constant resin sheet and the copper foil with high dielectric constant resin after adding and dispersing the high dielectric constant inorganic insulating filler to the mixed resin (A) solution, It can apply
- the high dielectric constant resin sheet and the high dielectric constant resin-attached copper foil may have a multilayer structure having a plurality of resin layers or other layers within a range not impeding the action of the present invention.
- a mixed resin (A) component 60 parts by mass of a thermosetting polyphenylene ether having a number average molecular weight of 1200 having a terminal modified with styrene and a hydrogenated styrene-based thermoplastic elastomer (SEBS: Tuftec H1041, manufactured by Asahi Kasei Chemicals Corporation) are 40 masses. Part is dissolved in toluene at room temperature to obtain a solution having a resin solid content concentration of 35% by weight, and then a barium titanate powder having an average particle diameter D50 of 0.8 ⁇ m is mixed resin (A) component 100 as a high dielectric constant inorganic insulating filler.
- SEBS hydrogenated styrene-based thermoplastic elastomer
- a varnish containing the high dielectric constant resin composition of the present invention was prepared by adding 400 parts by mass with respect to parts by mass and stirring until completely dispersed.
- the varnish is applied on one surface of a 50 ⁇ m thick polyethylene terephthalate (PET) film as a base material and dried at 80 ° C. for 5 minutes to form a resin layer made of a high dielectric constant resin composition having a thickness of 50 ⁇ m.
- a resin sheet was obtained.
- the above varnish was applied on a copper foil of a 35 ⁇ m thick electrolytic copper foil (copper foil for printed wiring board: JTC, manufactured by Nikko Metal Co., Ltd.) and dried at 80 ° C. for 5 minutes to obtain a high thickness of 50 ⁇ m.
- a copper foil with resin having a resin layer made of a dielectric constant resin composition was obtained.
- Ten sheets of the above-mentioned resin sheets were laminated and press-molded at a temperature of 180 ° C. and a pressure of 40 kg / cm 2 to obtain a 0.5 mm-thick plate, and the dielectric constant and dielectric loss tangent at 1 GHz were measured by the RF IV method. did.
- the mixed resin (A) component is composed of 70 parts by mass of a thermosetting polyphenylene ether having a number-average molecular weight of 1200 having a terminal modified with styrene and a hydrogenated styrene-based thermoplastic elastomer (SEBS: Tuftec H1041, manufactured by Asahi Kasei Chemicals Corporation).
- SEBS hydrogenated styrene-based thermoplastic elastomer
- thermosetting resin of the mixed resin (A) component was changed to 60 parts by mass of thermosetting polyphenylene ether having a number average molecular weight of 2200 having a terminal modified with styrene. Thereafter, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
- Comparative Example 1 Resin sheet and copper foil with resin in the same manner as in Example 1 except that the thermosetting resin of the mixed resin (A) component was changed to 60 parts by mass of thermosetting polyphenylene ether having a number average molecular weight of 16000 whose terminal was modified with styrene. Thereafter, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
- Comparative Example 2 As a mixed resin component, 50 parts by mass of a thermosetting polyphenylene ether having a number average molecular weight of 1200 having a terminal modified with styrene and a hydrogenated styrene-based thermoplastic elastomer (SEBS: Tuftec H1041, manufactured by Asahi Kasei Chemicals Corporation) were used. The resin sheet and the resin-attached copper foil were obtained in the same manner as in Example 1 except that the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
- SEBS hydrogenated styrene-based thermoplastic elastomer
- Comparative Example 3 Resin as in Example 1 except that 950 parts by mass of barium titanate powder having an average particle diameter D50 of 0.8 ⁇ m as a high dielectric constant inorganic insulating filler was added to 100 parts by mass of the mixed resin (A) component. An attempt was made to obtain a sheet and a copper foil with resin, but molding was impossible.
- Comparative Example 4 Instead of the hydrogenated styrene-based thermoplastic elastomer of Example 1 (SEBS: Tuftec H1041, manufactured by Asahi Kasei Chemicals Corporation), 40 parts by mass of nitrile butadiene rubber (NBR: Nipol 1001, manufactured by Nippon Zeon Co., Ltd.) is used. A resin sheet and a resin-attached copper foil were obtained in the same manner as in Example 1 except that the dielectric constant, dielectric loss tangent, and resin fillability of the circuit portion were confirmed in the same manner as in Example 1.
- SEBS Tuftec H1041, manufactured by Asahi Kasei Chemicals Corporation
- NBR Nipol 1001, manufactured by Nippon Zeon Co., Ltd.
- Comparative Example 5 Resin in the same manner as in Example 3 except that 400 parts by mass of strontium titanate having an average particle diameter D50 of 0.3 ⁇ m as a high dielectric constant inorganic insulating filler was added to 100 parts by mass of the mixed resin (A) component. After obtaining the sheet and the copper foil with resin, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
- Comparative Example 6 Resin in the same manner as in Example 1 except that 200 parts by mass of barium titanate powder having an average particle diameter D50 of 0.8 ⁇ m as a high dielectric constant inorganic insulating filler was added to 100 parts by mass of the mixed resin (A) component. After obtaining the sheet and the copper foil with resin, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
- Table 1 shows the blending ratios of the resin compositions of the above examples and comparative examples, and the results of the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion.
- each mixed resin component is as follows.
- PPE resin Thermosetting polyphenylene ether with styrene-modified terminal
- A Number average molecular weight 1200
- B Number average molecular weight 2200
- C Number average molecular weight 16000
- SEBS B NBR Inorganic filler (high dielectric constant inorganic insulating filler)
- Maximum particle size 5 ⁇ m B: Strontium titanate average particle diameter D50 0.9 ⁇ m
- Maximum particle size 5 ⁇ m C Strontium titanate average particle diameter D50 0.3 ⁇ m
- the high dielectric constant resin composition of the present invention has a high dielectric constant and a low dielectric loss tangent, and is excellent in resin filling characteristics of a circuit portion. Therefore, the high dielectric constant resin composition of the present invention is suitable for use in an insulating layer between circuits.
- a material By using a material, a high dielectric constant resin sheet and a copper foil with a high dielectric constant resin are formed, so that it is suitable as a substrate material for electronic equipment, particularly for electronic components and circuit boards used in equipment used in a high frequency region. Used for.
Abstract
Disclosed is a high-dielectric-constant resin composition which has a high dielectric constant and a low dielectric tangent, can achieve excellent resin embedding in circuits, and can be used suitably in a layer for insulating between circuits. For producing the resin composition, 250 to 900 parts by mass of a high-dielectric-constant inorganic insulation filler having an average particle diameter (D50) of 0.7 μm or more and a maximum particle diameter of 10 μm or less is blended into 100 parts by mass of a mixed resin (A) which is prepared by mixing a heat-curable polyphenylene ether having a styrene-modified terminal and having a number average molecular weight of 500 to 3000 with a styrene elastomer at a mixing ratio of the heat-curable polyphenylene ether to the styrene elastomer of 60:40 to 80:20 by mass.
Description
本発明は、電子機器用の基板材料、特に高周波領域で用いられる機器に使用される電子部品および回路基板の製造に好適な高誘電率樹脂組成物、高誘電率樹脂シートおよび高誘電率樹脂付銅箔に関する。
The present invention relates to a high dielectric constant resin composition, a high dielectric constant resin sheet, and a high dielectric constant resin suitable for the production of substrate materials for electronic equipment, particularly electronic components and circuit boards used in equipment used in high frequency regions. Related to copper foil.
現在、電子工業，通信工業の各分野で使用される周波数は，高周波領域での利用が増えてきている。このような高周波領域で用いられる機器に使用されるプリント配線板としては、誘電正接が低いものが必要となり、又回路の小型化には誘電率の高い物が必要となってきている。
Currently, the frequencies used in the fields of the electronics industry and the telecommunications industry are increasing in the high frequency region. As a printed wiring board used for such a device used in a high frequency region, one having a low dielectric loss tangent is required, and one having a high dielectric constant is required for downsizing a circuit.
これらを満足するものとしてガラス布基材に高誘電率フィラーを配したフッ素樹脂を含浸し、それらを積層した積層板や，ガラス布基材に高誘電率フィラーを配したポリフェニレンエーテル樹脂（＝ポリフェニレンオキサイド樹脂）を含浸した積層板などがある（下記特許文献１、２参照）。しかしながら上記積層板に使用される樹脂は溶融粘度が高く、多層板の積載絶縁層に用いた場合、回路間を埋めきれずボイドが生じ、耐熱性の低下の原因となる為、回路間絶縁層用途への適用は困難であった。また，フッ素樹脂の場合は、熱可塑性樹脂の溶融温度までプレス温度を上げる必要があるため、３００℃以上のプレス機が必要となり、コスト的に非常に問題となっている。
In order to satisfy these requirements, a glass cloth substrate is impregnated with a fluororesin with a high dielectric constant filler and laminated, or a polyphenylene ether resin with a high dielectric constant filler on a glass cloth base (= polyphenylene) There are laminates impregnated with (oxide resin) (see Patent Documents 1 and 2 below). However, the resin used for the laminated board has a high melt viscosity, and when used for the laminated insulating layer of a multilayer board, the gap between the circuits cannot be filled, resulting in a decrease in heat resistance. Application to applications was difficult. In the case of a fluororesin, since it is necessary to raise the press temperature to the melting temperature of the thermoplastic resin, a press machine of 300 ° C. or higher is necessary, which is very problematic in terms of cost.
樹脂の溶融粘度を下げる目的で、樹脂にエポキシ樹脂を用いた高誘電率フィラー配合プリプレグの開示もあるが（下記特許文献３参照）、樹脂自体の誘電正接がフッ素樹脂、ポリフェニレンエーテル樹脂に比べ高くなる為、低誘電正接を目的にするには不十分なものになるという問題がある。
There is also a disclosure of a prepreg with a high dielectric constant filler using an epoxy resin for the purpose of lowering the melt viscosity of the resin (see Patent Document 3 below), but the dielectric loss tangent of the resin itself is higher than that of fluororesin and polyphenylene ether resin. Therefore, there is a problem that it is insufficient for the purpose of low dielectric loss tangent.
本発明は、高誘電率、低誘電正接で、回路部分の樹脂埋め特性に優れて回路間絶縁層用途に好適であり、一般的な２００℃以下のプレス機での成型が可能な高誘電率樹脂組成物、さらにそれを用いた高誘電率樹脂シートおよび高誘電率樹脂付銅箔の提供を目的とする。
The present invention has a high dielectric constant, a low dielectric loss tangent, an excellent resin-filling characteristic of a circuit portion, and is suitable for an inter-circuit insulating layer, and can be molded by a general press machine of 200 ° C. or lower. An object of the present invention is to provide a resin composition, a high dielectric constant resin sheet using the resin composition, and a copper foil with a high dielectric constant resin.
上記課題を解決するために、本発明は下記の構成を有する。
（１）末端をスチレン変性した数平均分子量５００～３０００の熱硬化性ポリフェニレンエーテルと、スチレン系エラストマーとを、前記熱硬化性ポリフェニレンエーテルと前記スチレン系エラストマーとの混合比が質量比で６０：４０～８０：２０となるよう配合した混合樹脂（Ａ）に、、平均粒径Ｄ５０が０．７μｍ以上で最大粒子径１０μｍ以下の高誘電率無機絶縁フィラーを、前記混合樹脂（Ａ）１００質量部に対して２５０～９００質量部となるよう配合した、測定周波数１ＧＨｚでの室温における誘電率が１０以上、誘電正接が０．０１未満であることを特長とする高誘電率樹脂組成物。 In order to solve the above problems, the present invention has the following configuration.
(1) A thermosetting polyphenylene ether having a number average molecular weight of 500 to 3000 having a terminal modified with styrene and a styrene elastomer, and a mixing ratio of the thermosetting polyphenylene ether and the styrene elastomer is 60:40 by mass ratio. A high dielectric constant inorganic insulating filler having an average particle diameter D50 of 0.7 μm or more and a maximum particle diameter of 10 μm or less is added to the mixed resin (A) blended so as to be ˜80: 20, 100 parts by mass of the mixed resin (A) A high dielectric constant resin composition characterized by having a dielectric constant of 10 or more and a dielectric loss tangent of less than 0.01 at room temperature at a measurement frequency of 1 GHz, blended so as to be 250 to 900 parts by mass based on
（１）末端をスチレン変性した数平均分子量５００～３０００の熱硬化性ポリフェニレンエーテルと、スチレン系エラストマーとを、前記熱硬化性ポリフェニレンエーテルと前記スチレン系エラストマーとの混合比が質量比で６０：４０～８０：２０となるよう配合した混合樹脂（Ａ）に、、平均粒径Ｄ５０が０．７μｍ以上で最大粒子径１０μｍ以下の高誘電率無機絶縁フィラーを、前記混合樹脂（Ａ）１００質量部に対して２５０～９００質量部となるよう配合した、測定周波数１ＧＨｚでの室温における誘電率が１０以上、誘電正接が０．０１未満であることを特長とする高誘電率樹脂組成物。 In order to solve the above problems, the present invention has the following configuration.
(1) A thermosetting polyphenylene ether having a number average molecular weight of 500 to 3000 having a terminal modified with styrene and a styrene elastomer, and a mixing ratio of the thermosetting polyphenylene ether and the styrene elastomer is 60:40 by mass ratio. A high dielectric constant inorganic insulating filler having an average particle diameter D50 of 0.7 μm or more and a maximum particle diameter of 10 μm or less is added to the mixed resin (A) blended so as to be ˜80: 20, 100 parts by mass of the mixed resin (A) A high dielectric constant resin composition characterized by having a dielectric constant of 10 or more and a dielectric loss tangent of less than 0.01 at room temperature at a measurement frequency of 1 GHz, blended so as to be 250 to 900 parts by mass based on
（２）基材表面に、前記（１）記載の高誘電率樹脂組成物からなる１０～１００μｍ厚さの樹脂層を有するＢステージ状の高誘電率樹脂シート。
(2) A B-stage high dielectric constant resin sheet having a resin layer having a thickness of 10 to 100 μm made of the high dielectric constant resin composition described in (1) above on the substrate surface.
（３）プリント配線板用銅箔の表面に、前記（１）記載の高誘電率樹脂組成物からなる１０～１００μｍ厚さの樹脂層を有するＢステージ状の高誘電率樹脂付銅箔。
(3) A copper foil with a B-stage high dielectric constant resin having a resin layer having a thickness of 10 to 100 μm made of the high dielectric constant resin composition described in (1) above on the surface of the copper foil for printed wiring board.
本発明の高誘電率樹脂組成物は、上記のように特定の組成を有するため、高誘電率、低誘電正接であり、回路部分の樹脂埋め特性に優れ、一般的な２００℃以下のプレス機での成型が可能であってコストの点からも有利である。
Since the high dielectric constant resin composition of the present invention has a specific composition as described above, it has a high dielectric constant and a low dielectric loss tangent, is excellent in resin filling characteristics of a circuit portion, and is a general press at 200 ° C. or lower. This is advantageous in terms of cost.
以下に本発明を更に詳細に説明する。
本発明において、樹脂成分は、末端をスチレン変性した数平均分子量５００～３０００の熱硬化性ポリフェニレンエーテルと、スチレン系エラストマーとを、前記熱硬化性ポリフェニレンエーテルと前記スチレン系エラストマーとの混合比が質量比で６０：４０～８０：２０となるよう配合した混合樹脂（Ａ）からなる。 The present invention is described in further detail below.
In the present invention, the resin component comprises a thermosetting polyphenylene ether having a number average molecular weight of 500 to 3000 having a terminal modified with styrene and a styrene elastomer, and the mixing ratio of the thermosetting polyphenylene ether and the styrene elastomer is mass. The mixed resin (A) is blended so that the ratio is 60:40 to 80:20.
本発明において、樹脂成分は、末端をスチレン変性した数平均分子量５００～３０００の熱硬化性ポリフェニレンエーテルと、スチレン系エラストマーとを、前記熱硬化性ポリフェニレンエーテルと前記スチレン系エラストマーとの混合比が質量比で６０：４０～８０：２０となるよう配合した混合樹脂（Ａ）からなる。 The present invention is described in further detail below.
In the present invention, the resin component comprises a thermosetting polyphenylene ether having a number average molecular weight of 500 to 3000 having a terminal modified with styrene and a styrene elastomer, and the mixing ratio of the thermosetting polyphenylene ether and the styrene elastomer is mass. The mixed resin (A) is blended so that the ratio is 60:40 to 80:20.
上記スチレン系エラストマーとしては、上記熱硬化性ポリフェニレンエーテルとの相溶性が高く、誘電特性に優れるスチレンブタジエンゴム（ＳＢＲ）、スチレン系熱可塑性エラストマー（ＳＢＳ）、水添型スチレン系熱可塑性エラストマー（ＳＥＢＳ）およびその変性体が挙げられる。
Examples of the styrene elastomer include styrene butadiene rubber (SBR), styrene thermoplastic elastomer (SBS), hydrogenated styrene thermoplastic elastomer (SEBS) that have high compatibility with the thermosetting polyphenylene ether and excellent dielectric properties. ) And modified products thereof.
上記混合樹脂（Ａ）において、上記熱硬化性ポリフェニレンエーテルと上記スチレン系エラストマーとの混合比は、質量比で６０：４０～８０：２０（上記熱硬化性ポリフェニレンエーテルと上記スチレン系エラストマーの合計を１００とする。）となるよう配合する必要がある。上記スチレン系エラストマーの質量比が２０未満であると、樹脂組成物の流動性が高くなり過ぎて積層板作成のプレス成形時に樹脂が積層板端部から流れ易くなり、板厚のバラツキ範囲が広くなるという問題が生じる。また、上記スチレン系エラストマーの質量比が４０を超えると、樹脂組成物の流動性が低くなり過ぎて、回路上に積層した際の回路間の樹脂埋め性が不十分になる。
In the mixed resin (A), the mixing ratio of the thermosetting polyphenylene ether and the styrene elastomer is 60:40 to 80:20 (mass ratio of the thermosetting polyphenylene ether and the styrene elastomer). 100))). When the mass ratio of the styrenic elastomer is less than 20, the fluidity of the resin composition becomes too high, and the resin easily flows from the edge of the laminated plate during press forming of the laminated plate, and the range of variation in the plate thickness is wide. Problem arises. On the other hand, when the mass ratio of the styrene-based elastomer exceeds 40, the fluidity of the resin composition becomes too low, and the resin filling property between the circuits when laminated on the circuit becomes insufficient.
なお、上記混合樹脂（Ａ）において、上記熱硬化性ポリフェニレンエーテル、上記スチレン系エラストマーのそれぞれは２種以上を混合して使用しても良い。
In the mixed resin (A), two or more of the thermosetting polyphenylene ether and the styrene elastomer may be used in combination.
本発明に使用する高誘電率無機絶縁フィラーとしては、二酸化チタン、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルウシム、チタン酸鉛が挙げられ、これらは単独もしくは２種以上を混合して使用できる。
Examples of the high dielectric constant inorganic insulating filler used in the present invention include titanium dioxide, barium titanate, strontium titanate, calcium titanate, and lead titanate, and these can be used alone or in combination of two or more.
上記高誘電率無機絶縁フィラーは、平均粒径Ｄ５０が０．７μｍ以上である必要がある。平均粒径Ｄ５０が０．７μｍ未満であると、樹脂組成物のチキソ性が大きくなり樹脂流動性が低下するため、回路上に積層した際の回路間の樹脂埋め性が不十分になる。
The above-mentioned high dielectric constant inorganic insulating filler needs to have an average particle diameter D50 of 0.7 μm or more. When the average particle diameter D50 is less than 0.7 μm, the thixotropy of the resin composition is increased and the resin fluidity is lowered, so that the resin filling property between the circuits when laminated on the circuit becomes insufficient.
また、本発明において、上記高誘電率無機絶縁フィラーは、最大粒径が１０μｍ以下である必要がある。高誘電率樹脂組成物をキャパシタとして使用する場合，一定面積の２層回路間で容量を上げるには絶縁層を薄くする必要があるが、高誘電率無機絶縁フィラーが２層回路間で上下に突き抜けないように絶縁層の厚みを高誘電率無機絶縁フィラーの最大粒径以上にする必要がある。高誘電率無機絶縁フィラーの最大粒径が１０μｍを超えると、絶縁層の厚みが大きくなりすぎ、キャパシタとして使用する場合、容量不足となる可能性がある。
In the present invention, the high dielectric constant inorganic insulating filler needs to have a maximum particle size of 10 μm or less. When a high dielectric constant resin composition is used as a capacitor, it is necessary to make the insulating layer thin in order to increase the capacity between two layers of a fixed area. In order not to penetrate, the thickness of the insulating layer needs to be larger than the maximum particle diameter of the high dielectric constant inorganic insulating filler. When the maximum particle diameter of the high dielectric constant inorganic insulating filler exceeds 10 μm, the thickness of the insulating layer becomes too large, and when used as a capacitor, the capacity may be insufficient.
上記高誘電率無機絶縁フィラーは、前記混合樹脂（Ａ）１００質量部に対して２５０～９００質量部となるよう配合する必要がある。高誘電率無機絶縁フィラーの含有量が９００質量部を超えると樹脂組成物の成形が困難となり、２５０質量部未満であると誘電率が低くなり、高誘電率無機絶縁フィラーの配合効果が見られない。
The high dielectric constant inorganic insulating filler needs to be blended so as to be 250 to 900 parts by mass with respect to 100 parts by mass of the mixed resin (A). When the content of the high dielectric constant inorganic insulating filler exceeds 900 parts by mass, it becomes difficult to mold the resin composition, and when it is less than 250 parts by mass, the dielectric constant decreases and the blending effect of the high dielectric constant inorganic insulating filler is observed. Absent.
本発明の高誘電率樹脂組成物は、上記の構成を有することにより、樹脂組成物硬化物の測定周波数１ＧＨｚでの室温における誘電率が１０以上、誘電正接が０．０１未満とすることができ、かつ回路上に積層した際の良好な回路間の樹脂埋め性を得ることができる。
Since the high dielectric constant resin composition of the present invention has the above-described configuration, the dielectric constant at room temperature at a measurement frequency of 1 GHz of the cured resin composition can be 10 or more and the dielectric loss tangent can be less than 0.01. In addition, it is possible to obtain a good resin embedding property between circuits when stacked on the circuit.
本発明の高誘電率樹脂組成物の製造方法としては、例えば、混合樹脂（Ａ）を構成する上記熱硬化性ポリフェニレンエーテルと、上記スチレン系エラストマーとを溶媒に溶解して溶液とし、該溶液に高誘電率無機絶縁フィラーを添加して分散させたのち、基材等に塗布するなどし、溶媒を乾燥させることで混合樹脂（Ａ）中に高誘電率無機絶縁フィラーが分散された樹脂組成物を形成できる。
As a method for producing the high dielectric constant resin composition of the present invention, for example, the thermosetting polyphenylene ether constituting the mixed resin (A) and the styrene elastomer are dissolved in a solvent to form a solution. A resin composition in which a high dielectric constant inorganic insulating filler is dispersed in a mixed resin (A) by adding a high dielectric constant inorganic insulating filler, dispersing it, applying to a substrate, etc., and drying the solvent Can be formed.
本発明の高誘電率樹脂組成物には、本発明の作用を阻害しない範囲で難燃剤、樹脂改質剤等の添加剤を添加しても良い。
Additives such as flame retardants and resin modifiers may be added to the high dielectric constant resin composition of the present invention as long as the effects of the present invention are not impaired.
本発明の高誘電率樹脂組成物は、基材表面に、本発明の高誘電率樹脂組成物からなる１０～１００μｍ厚さの樹脂層を形成することでＢステージ状の高誘電率樹脂シートを形成できる。基材としては、ポリエチレンテレフタレートフィルム等が使用できる。
The high dielectric constant resin composition of the present invention forms a B-stage high dielectric constant resin sheet by forming a resin layer having a thickness of 10 to 100 μm comprising the high dielectric constant resin composition of the present invention on the surface of a substrate. Can be formed. As the substrate, a polyethylene terephthalate film or the like can be used.
また、本発明の高誘電率樹脂組成物は、プリント配線板用銅箔の表面に、本発明の高誘電率樹脂組成物からなる１０～１００μｍ厚さの樹脂層を形成することでＢステージ状の高誘電率樹脂付銅箔を形成できる。高誘電率樹脂付銅箔は樹脂層面を回路上に配置して、熱プレス等を行うことにより、回路間を樹脂で埋めることが出来る。本発明の高誘電率樹脂組成物は、上記構成を有することにより、良好な誘電特性を有しながら、一般的な２００℃以下のプレス機での成型が可能である。
In addition, the high dielectric constant resin composition of the present invention is formed in a B-stage shape by forming a resin layer having a thickness of 10 to 100 μm made of the high dielectric constant resin composition of the present invention on the surface of a copper foil for printed wiring boards. The copper foil with a high dielectric constant resin can be formed. The copper foil with a high dielectric constant resin can fill the space between the circuits by arranging the resin layer surface on the circuit and performing hot pressing or the like. Since the high dielectric constant resin composition of the present invention has the above-described configuration, it can be molded with a general press at 200 ° C. or lower while having good dielectric properties.
上記高誘電率樹脂シートおよび高誘電率樹脂付銅箔における樹脂層の形成方法は、上述したように、混合樹脂（Ａ）の溶液に高誘電率無機絶縁フィラーを添加して分散させたのち、基材あるいは銅箔表面に塗布し、溶媒を乾燥させて形成できる。上記高誘電率樹脂シートおよび高誘電率樹脂付銅箔には、本発明の作用を阻害しない範囲で、複数の樹脂層を有する多層構成としたり、他層を有していても良い。
The method for forming the resin layer in the high dielectric constant resin sheet and the copper foil with high dielectric constant resin, as described above, after adding and dispersing the high dielectric constant inorganic insulating filler to the mixed resin (A) solution, It can apply | coat to a base material or the surface of copper foil, and can form by drying a solvent. The high dielectric constant resin sheet and the high dielectric constant resin-attached copper foil may have a multilayer structure having a plurality of resin layers or other layers within a range not impeding the action of the present invention.
以下に実施例により本発明を具体的に説明するが，本発明はこれらの実施例に限定されるものではない。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
混合樹脂（Ａ）成分として、末端をスチレン変性した数平均分子量１２００の熱硬化性ポリフェニレンエーテル６０質量部と水添型スチレン系熱可塑性エラストマー（ＳＥＢＳ：タフテックＨ１０４１，旭化成ケミカルズ（株）製）４０質量部を、室温のトルエンに溶解させ、樹脂固形分濃度３５重量％の溶液とし、その後高誘電率無機絶縁フィラーとして平均粒径Ｄ５０が０．８μｍのチタン酸バリウム粉末を混合樹脂（Ａ）成分１００質量部に対して４００質量部添加し、完全に分散するまで攪拌して本発明の高誘電率樹脂組成物を含むワニスを作製した。このワニスを、基材である厚さ５０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムの一方の表面上に塗布し、８０℃で５分乾燥させて厚さ５０μｍの高誘電率樹脂組成物からなる樹脂層を有する樹脂シートを得た。別途、上記ワニスを厚さ３５μｍの電解銅箔（プリント配線板用銅箔：ＪＴＣ，日鉱金属（株）製）の銅箔上に塗布し、８０℃で５分乾燥させて厚さ５０μｍの高誘電率樹脂組成物からなる樹脂層を有する樹脂付銅箔を得た。
作成した上記樹脂シートを１０枚積層し，温度１８０℃，圧力４０ｋｇ／ｃｍ２でプレス成型して厚さ０．５ｍｍの板を得、ＲＦ Ｉ－Ｖ法により１ＧＨｚにおける誘電率および誘電正接を測定した。
また，樹脂付銅箔の樹脂層面を、導体厚さ３５μｍ、Ｌ／Ｎ ＝７５μｍの回路上に重ね、温度１８０℃，圧力４０ｋｇ／ｃｍ２でプレス成型して張り合わせ、その断面を４５０倍の顕微鏡で隙間の存在を観察して、回路部分の樹脂埋め性を確認した。 As a mixed resin (A) component, 60 parts by mass of a thermosetting polyphenylene ether having a number average molecular weight of 1200 having a terminal modified with styrene and a hydrogenated styrene-based thermoplastic elastomer (SEBS: Tuftec H1041, manufactured by Asahi Kasei Chemicals Corporation) are 40 masses. Part is dissolved in toluene at room temperature to obtain a solution having a resin solid content concentration of 35% by weight, and then a barium titanate powder having an average particle diameter D50 of 0.8 μm is mixed resin (A) component 100 as a high dielectric constant inorganic insulating filler. A varnish containing the high dielectric constant resin composition of the present invention was prepared by adding 400 parts by mass with respect to parts by mass and stirring until completely dispersed. The varnish is applied on one surface of a 50 μm thick polyethylene terephthalate (PET) film as a base material and dried at 80 ° C. for 5 minutes to form a resin layer made of a high dielectric constant resin composition having a thickness of 50 μm. A resin sheet was obtained. Separately, the above varnish was applied on a copper foil of a 35 μm thick electrolytic copper foil (copper foil for printed wiring board: JTC, manufactured by Nikko Metal Co., Ltd.) and dried at 80 ° C. for 5 minutes to obtain a high thickness of 50 μm. A copper foil with resin having a resin layer made of a dielectric constant resin composition was obtained.
Ten sheets of the above-mentioned resin sheets were laminated and press-molded at a temperature of 180 ° C. and a pressure of 40 kg / cm 2 to obtain a 0.5 mm-thick plate, and the dielectric constant and dielectric loss tangent at 1 GHz were measured by the RF IV method. did.
In addition, the resin layer surface of the copper foil with resin is superimposed on a circuit having a conductor thickness of 35 μm and L / N = 75 μm, and press-molded and bonded at a temperature of 180 ° C. and a pressure of 40 kg / cm 2. Then, the presence of a gap was observed, and the resin filling property of the circuit portion was confirmed.
作成した上記樹脂シートを１０枚積層し，温度１８０℃，圧力４０ｋｇ／ｃｍ２でプレス成型して厚さ０．５ｍｍの板を得、ＲＦ Ｉ－Ｖ法により１ＧＨｚにおける誘電率および誘電正接を測定した。
また，樹脂付銅箔の樹脂層面を、導体厚さ３５μｍ、Ｌ／Ｎ ＝７５μｍの回路上に重ね、温度１８０℃，圧力４０ｋｇ／ｃｍ２でプレス成型して張り合わせ、その断面を４５０倍の顕微鏡で隙間の存在を観察して、回路部分の樹脂埋め性を確認した。 As a mixed resin (A) component, 60 parts by mass of a thermosetting polyphenylene ether having a number average molecular weight of 1200 having a terminal modified with styrene and a hydrogenated styrene-based thermoplastic elastomer (SEBS: Tuftec H1041, manufactured by Asahi Kasei Chemicals Corporation) are 40 masses. Part is dissolved in toluene at room temperature to obtain a solution having a resin solid content concentration of 35% by weight, and then a barium titanate powder having an average particle diameter D50 of 0.8 μm is mixed resin (A) component 100 as a high dielectric constant inorganic insulating filler. A varnish containing the high dielectric constant resin composition of the present invention was prepared by adding 400 parts by mass with respect to parts by mass and stirring until completely dispersed. The varnish is applied on one surface of a 50 μm thick polyethylene terephthalate (PET) film as a base material and dried at 80 ° C. for 5 minutes to form a resin layer made of a high dielectric constant resin composition having a thickness of 50 μm. A resin sheet was obtained. Separately, the above varnish was applied on a copper foil of a 35 μm thick electrolytic copper foil (copper foil for printed wiring board: JTC, manufactured by Nikko Metal Co., Ltd.) and dried at 80 ° C. for 5 minutes to obtain a high thickness of 50 μm. A copper foil with resin having a resin layer made of a dielectric constant resin composition was obtained.
Ten sheets of the above-mentioned resin sheets were laminated and press-molded at a temperature of 180 ° C. and a pressure of 40 kg / cm 2 to obtain a 0.5 mm-thick plate, and the dielectric constant and dielectric loss tangent at 1 GHz were measured by the RF IV method. did.
In addition, the resin layer surface of the copper foil with resin is superimposed on a circuit having a conductor thickness of 35 μm and L / N = 75 μm, and press-molded and bonded at a temperature of 180 ° C. and a pressure of 40 kg / cm 2. Then, the presence of a gap was observed, and the resin filling property of the circuit portion was confirmed.
高誘電率無機絶縁フィラーとして、チタン酸バリウム粉末の代わりに、平均粒径Ｄ５０が０．９μｍのチタン酸ストロンチウム粉末を混合樹脂（Ａ）成分１００質量部に対して４００質量部添加した以外は実施例１と同様にして、樹脂シートおよび樹脂付銅箔を得た後，実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。
Implemented except that 400 parts by mass of strontium titanate powder having an average particle diameter D50 of 0.9 μm was added as a high dielectric constant inorganic insulating filler to 100 parts by mass of the mixed resin (A) component instead of barium titanate powder. After obtaining a resin sheet and a resin-attached copper foil in the same manner as in Example 1, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
混合樹脂（Ａ）成分を、末端をスチレン変性した数平均分子量１２００の熱硬化性ポリフェニレンエーテル７０質量部と水添型スチレン系熱可塑性エラストマー（ＳＥＢＳ：タフテックＨ１０４１，旭化成ケミカルズ（株）製）３０質量部とした以外は、実施例２と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。
The mixed resin (A) component is composed of 70 parts by mass of a thermosetting polyphenylene ether having a number-average molecular weight of 1200 having a terminal modified with styrene and a hydrogenated styrene-based thermoplastic elastomer (SEBS: Tuftec H1041, manufactured by Asahi Kasei Chemicals Corporation). The resin sheet and the resin-attached copper foil were obtained in the same manner as in Example 2 except that the part was made a part, and the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
高誘電率無機絶縁フィラーとして、平均粒径Ｄ５０が０．８μｍのチタン酸バリウム粉末を混合樹脂（Ａ）成分１００質量部に対して３００質量部添加した以外は、実施例１と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。
Resin in the same manner as in Example 1 except that 300 parts by mass of barium titanate powder having an average particle diameter D50 of 0.8 μm as a high dielectric constant inorganic insulating filler was added to 100 parts by mass of the mixed resin (A) component. After obtaining the sheet and the copper foil with resin, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
混合樹脂（Ａ）成分の熱硬化性樹脂を、末端をスチレン変性した数平均分子量２２００の熱硬化性ポリフェニレンエーテル６０質量部とした以外は、実施例１と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。
Resin sheet and copper foil with resin in the same manner as in Example 1 except that the thermosetting resin of the mixed resin (A) component was changed to 60 parts by mass of thermosetting polyphenylene ether having a number average molecular weight of 2200 having a terminal modified with styrene. Thereafter, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
比較例１
混合樹脂（Ａ）成分の熱硬化性樹脂を、末端をスチレン変性した数平均分子量１６０００の熱硬化性ポリフェニレンエーテル６０質量部とした以外は、実施例１と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。 Comparative Example 1
Resin sheet and copper foil with resin in the same manner as in Example 1 except that the thermosetting resin of the mixed resin (A) component was changed to 60 parts by mass of thermosetting polyphenylene ether having a number average molecular weight of 16000 whose terminal was modified with styrene. Thereafter, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
混合樹脂（Ａ）成分の熱硬化性樹脂を、末端をスチレン変性した数平均分子量１６０００の熱硬化性ポリフェニレンエーテル６０質量部とした以外は、実施例１と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。 Comparative Example 1
Resin sheet and copper foil with resin in the same manner as in Example 1 except that the thermosetting resin of the mixed resin (A) component was changed to 60 parts by mass of thermosetting polyphenylene ether having a number average molecular weight of 16000 whose terminal was modified with styrene. Thereafter, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
比較例２
混合樹脂成分として、末端をスチレン変性した数平均分子量１２００の熱硬化性ポリフェニレンエーテル５０質量部と水添型スチレン系熱可塑性エラストマー（ＳＥＢＳ：タフテックＨ１０４１，旭化成ケミカルズ（株）製）５０質量部とした以外は実施例１と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。 Comparative Example 2
As a mixed resin component, 50 parts by mass of a thermosetting polyphenylene ether having a number average molecular weight of 1200 having a terminal modified with styrene and a hydrogenated styrene-based thermoplastic elastomer (SEBS: Tuftec H1041, manufactured by Asahi Kasei Chemicals Corporation) were used. The resin sheet and the resin-attached copper foil were obtained in the same manner as in Example 1 except that the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
混合樹脂成分として、末端をスチレン変性した数平均分子量１２００の熱硬化性ポリフェニレンエーテル５０質量部と水添型スチレン系熱可塑性エラストマー（ＳＥＢＳ：タフテックＨ１０４１，旭化成ケミカルズ（株）製）５０質量部とした以外は実施例１と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。 Comparative Example 2
As a mixed resin component, 50 parts by mass of a thermosetting polyphenylene ether having a number average molecular weight of 1200 having a terminal modified with styrene and a hydrogenated styrene-based thermoplastic elastomer (SEBS: Tuftec H1041, manufactured by Asahi Kasei Chemicals Corporation) were used. The resin sheet and the resin-attached copper foil were obtained in the same manner as in Example 1 except that the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
比較例３
高誘電率無機絶縁フィラーとして平均粒径Ｄ５０が０．８μｍのチタン酸バリウム粉末を、混合樹脂（Ａ）成分１００質量部に対して９５０質量部を添加した以外は実施例１と同様にして樹脂シートおよび樹脂付銅箔を得ようとしたが、成形不能であった。 Comparative Example 3
Resin as in Example 1 except that 950 parts by mass of barium titanate powder having an average particle diameter D50 of 0.8 μm as a high dielectric constant inorganic insulating filler was added to 100 parts by mass of the mixed resin (A) component. An attempt was made to obtain a sheet and a copper foil with resin, but molding was impossible.
高誘電率無機絶縁フィラーとして平均粒径Ｄ５０が０．８μｍのチタン酸バリウム粉末を、混合樹脂（Ａ）成分１００質量部に対して９５０質量部を添加した以外は実施例１と同様にして樹脂シートおよび樹脂付銅箔を得ようとしたが、成形不能であった。 Comparative Example 3
Resin as in Example 1 except that 950 parts by mass of barium titanate powder having an average particle diameter D50 of 0.8 μm as a high dielectric constant inorganic insulating filler was added to 100 parts by mass of the mixed resin (A) component. An attempt was made to obtain a sheet and a copper foil with resin, but molding was impossible.
比較例４
実施例１の水添型スチレン系熱可塑性エラストマー（ＳＥＢＳ：タフテックＨ１０４１，旭化成ケミカルズ（株）製）の代わりに、ニトリルブタジエンゴム（ＮＢＲ：Ｎｉｐｏｌ １００１、日本ゼオン（株）製）４０質量部を用いた以外は実施例１と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。 Comparative Example 4
Instead of the hydrogenated styrene-based thermoplastic elastomer of Example 1 (SEBS: Tuftec H1041, manufactured by Asahi Kasei Chemicals Corporation), 40 parts by mass of nitrile butadiene rubber (NBR: Nipol 1001, manufactured by Nippon Zeon Co., Ltd.) is used. A resin sheet and a resin-attached copper foil were obtained in the same manner as in Example 1 except that the dielectric constant, dielectric loss tangent, and resin fillability of the circuit portion were confirmed in the same manner as in Example 1.
実施例１の水添型スチレン系熱可塑性エラストマー（ＳＥＢＳ：タフテックＨ１０４１，旭化成ケミカルズ（株）製）の代わりに、ニトリルブタジエンゴム（ＮＢＲ：Ｎｉｐｏｌ １００１、日本ゼオン（株）製）４０質量部を用いた以外は実施例１と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。 Comparative Example 4
Instead of the hydrogenated styrene-based thermoplastic elastomer of Example 1 (SEBS: Tuftec H1041, manufactured by Asahi Kasei Chemicals Corporation), 40 parts by mass of nitrile butadiene rubber (NBR: Nipol 1001, manufactured by Nippon Zeon Co., Ltd.) is used. A resin sheet and a resin-attached copper foil were obtained in the same manner as in Example 1 except that the dielectric constant, dielectric loss tangent, and resin fillability of the circuit portion were confirmed in the same manner as in Example 1.
比較例５
高誘電率無機絶縁フィラーとして、平均粒径Ｄ５０が０．３μｍのチタン酸ストロンチウムを、混合樹脂（Ａ）成分１００質量部に対して４００質量部を添加した以外は実施例３と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。 Comparative Example 5
Resin in the same manner as in Example 3 except that 400 parts by mass of strontium titanate having an average particle diameter D50 of 0.3 μm as a high dielectric constant inorganic insulating filler was added to 100 parts by mass of the mixed resin (A) component. After obtaining the sheet and the copper foil with resin, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
高誘電率無機絶縁フィラーとして、平均粒径Ｄ５０が０．３μｍのチタン酸ストロンチウムを、混合樹脂（Ａ）成分１００質量部に対して４００質量部を添加した以外は実施例３と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。 Comparative Example 5
Resin in the same manner as in Example 3 except that 400 parts by mass of strontium titanate having an average particle diameter D50 of 0.3 μm as a high dielectric constant inorganic insulating filler was added to 100 parts by mass of the mixed resin (A) component. After obtaining the sheet and the copper foil with resin, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
比較例６
高誘電率無機絶縁フィラーとして平均粒径Ｄ５０が０．８μｍのチタン酸バリウム粉末を、混合樹脂（Ａ）成分１００質量部に対して２００質量部を添加した以外は実施例１と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。 Comparative Example 6
Resin in the same manner as in Example 1 except that 200 parts by mass of barium titanate powder having an average particle diameter D50 of 0.8 μm as a high dielectric constant inorganic insulating filler was added to 100 parts by mass of the mixed resin (A) component. After obtaining the sheet and the copper foil with resin, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
高誘電率無機絶縁フィラーとして平均粒径Ｄ５０が０．８μｍのチタン酸バリウム粉末を、混合樹脂（Ａ）成分１００質量部に対して２００質量部を添加した以外は実施例１と同様にして樹脂シートおよび樹脂付銅箔を得た後、実施例１と同様に誘電率、誘電正接、回路部分の樹脂埋め性を確認した。 Comparative Example 6
Resin in the same manner as in Example 1 except that 200 parts by mass of barium titanate powder having an average particle diameter D50 of 0.8 μm as a high dielectric constant inorganic insulating filler was added to 100 parts by mass of the mixed resin (A) component. After obtaining the sheet and the copper foil with resin, the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion were confirmed in the same manner as in Example 1.
上記実施例及び比較例の樹脂組成物の配合割合、および誘電率、誘電正接、回路部分の樹脂埋め性の結果を表1に示す。
Table 1 shows the blending ratios of the resin compositions of the above examples and comparative examples, and the results of the dielectric constant, dielectric loss tangent, and resin filling property of the circuit portion.
上記表1中、各混合樹脂成分は下記の通りである。
ＰＰＥ樹脂：末端をスチレン変性した熱硬化性ポリフェニレンエーテル
Ａ：数平均分子量１２００
Ｂ：数平均分子量２２００
Ｃ：数平均分子量１６０００
エラストマー
Ａ：ＳＥＢＳ
Ｂ：ＮＢＲ
無機フィラー（高誘電率無機絶縁フィラー）
Ａ：チタン酸バリウム 平均粒径Ｄ５０ ０．８μｍ
最大粒径 ５μｍ
Ｂ：チタン酸ストロンチウム 平均粒径Ｄ５０ ０．９μｍ
最大粒径 ５μｍ
Ｃ：チタン酸ストロンチウム 平均粒径Ｄ５０ ０．３μｍ
最大粒径 １μｍ
In Table 1 above, each mixed resin component is as follows.
PPE resin: Thermosetting polyphenylene ether with styrene-modified terminal A: Number average molecular weight 1200
B: Number average molecular weight 2200
C: Number average molecular weight 16000
Elastomer A: SEBS
B: NBR
Inorganic filler (high dielectric constant inorganic insulating filler)
A: Barium titanate average particle diameter D50 0.8 μm
Maximum particle size 5μm
B: Strontium titanate average particle diameter D50 0.9 μm
Maximum particle size 5μm
C: Strontium titanate average particle diameter D50 0.3 μm
Maximum particle size 1μm
本発明の高誘電率樹脂組成物は、高誘電率、低誘電正接であって、回路部分の樹脂埋め特性に優れるため、回路間絶縁層用途に好適であり、本発明の高誘電率樹脂組成物を用いて、高誘電率樹脂シートおよび高誘電率樹脂付銅箔を形成することにより、電子機器用の基板材料、特に高周波領域で用いられる機器に使用される電子部品および回路基板用として好適に使用される。
The high dielectric constant resin composition of the present invention has a high dielectric constant and a low dielectric loss tangent, and is excellent in resin filling characteristics of a circuit portion. Therefore, the high dielectric constant resin composition of the present invention is suitable for use in an insulating layer between circuits. By using a material, a high dielectric constant resin sheet and a copper foil with a high dielectric constant resin are formed, so that it is suitable as a substrate material for electronic equipment, particularly for electronic components and circuit boards used in equipment used in a high frequency region. Used for.
Claims (3)
- 末端をスチレン変性した数平均分子量５００～３０００の熱硬化性ポリフェニレンエーテルと、スチレン系エラストマーとを、前記熱硬化性ポリフェニレンエーテルと前記スチレン系エラストマーとの混合比が質量比で６０：４０～８０：２０となるよう配合した混合樹脂（Ａ）に、平均粒径Ｄ５０が０．７μｍ以上で最大粒子径１０μｍ以下の高誘電率無機絶縁フィラーを、前記混合樹脂（Ａ）１００質量部に対して２５０～９００質量部となるよう配合した、測定周波数１ＧＨｚでの室温における誘電率が１０以上、誘電正接が０．０１未満であることを特長とする高誘電率樹脂組成物。 A thermosetting polyphenylene ether having a number average molecular weight of 500 to 3000 having a terminal modified with styrene and a styrene elastomer is mixed in a mass ratio of 60:40 to 80:80 by mass ratio of the thermosetting polyphenylene ether and the styrene elastomer. The high dielectric constant inorganic insulating filler having an average particle diameter D50 of 0.7 μm or more and a maximum particle diameter of 10 μm or less is mixed with the mixed resin (A) blended so as to be 250 with respect to 100 parts by mass of the mixed resin (A). A high dielectric constant resin composition characterized by having a dielectric constant of 10 or more and a dielectric loss tangent of less than 0.01 at room temperature at a measurement frequency of 1 GHz, blended so as to be ˜900 parts by mass.
- 基材表面に、請求項１記載の高誘電率樹脂組成物からなる１０～１００μｍ厚さの樹脂層を有するＢステージ状の高誘電率樹脂シート。 A B-stage high dielectric constant resin sheet comprising a resin layer having a thickness of 10 to 100 μm comprising the high dielectric constant resin composition according to claim 1 on the surface of the substrate.
- プリント配線板用銅箔の表面に、請求項１記載の高誘電率樹脂組成物からなる１０～１００μｍ厚さの樹脂層を有するＢステージ状の高誘電率樹脂付銅箔。 A B-stage copper foil with a high dielectric constant resin having a resin layer having a thickness of 10 to 100 μm comprising the high dielectric constant resin composition according to claim 1 on the surface of a copper foil for printed wiring boards.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009143391A JP2011001400A (en) | 2009-06-16 | 2009-06-16 | Resin composition with high dielectric constant, and resin sheet with high dielectric constant and copper foil with resin with high dielectric constant obtained by using the same |
| JP2009-143391 | 2009-06-16 |
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| Publication Number | Publication Date |
|---|---|
| WO2010147082A1 true WO2010147082A1 (en) | 2010-12-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2010/060037 WO2010147082A1 (en) | 2009-06-16 | 2010-06-14 | High-dielectric-constant resin composition, high-dielectric-constant resin sheet comprising same, and copper foil having high-dielectric-constant resin attached thereto |
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| Country | Link |
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| JP (1) | JP2011001400A (en) |
| TW (1) | TW201114834A (en) |
| WO (1) | WO2010147082A1 (en) |
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|---|---|---|---|---|
| WO2022009887A1 (en) * | 2020-07-08 | 2022-01-13 | 昭和電工マテリアルズ株式会社 | Resin composition, film, and cured product |
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| CN113614180A (en) * | 2019-03-27 | 2021-11-05 | 昭和电工材料株式会社 | Resin composition, film and cured product |
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| JP2005105062A (en) * | 2003-09-29 | 2005-04-21 | Tdk Corp | Resin composition, conductive foil with resin, prepreg, sheet, sheet with conductive foil, laminated plate and printed wiring board |
| JP2007048703A (en) * | 2005-08-12 | 2007-02-22 | Tdk Corp | Composite dielectric material and prepreg using this, metal foil coated object, molding body, composite dielectric substrate, and multilayer substrate |
| JP2009040934A (en) * | 2007-08-10 | 2009-02-26 | Nippon Steel Chem Co Ltd | Curable resin composition |
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- 2009-06-16 JP JP2009143391A patent/JP2011001400A/en active Pending
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- 2010-06-14 WO PCT/JP2010/060037 patent/WO2010147082A1/en active Application Filing
- 2010-06-15 TW TW099119428A patent/TW201114834A/en unknown
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| JPS63264662A (en) * | 1986-12-23 | 1988-11-01 | Matsushita Electric Works Ltd | Polyphenylene oxide resin composition |
| JPH01245053A (en) * | 1988-03-26 | 1989-09-29 | Matsushita Electric Works Ltd | Polyphenylene oxide based resin substrate |
| JPH0841247A (en) * | 1994-07-28 | 1996-02-13 | Otsuka Chem Co Ltd | Resin composition for electronic part |
| JP2000510639A (en) * | 1996-05-07 | 2000-08-15 | ヘキスト・セラニーズ・コーポレーション | Polymer composition having temperature stable dielectric constant |
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| JP2007048703A (en) * | 2005-08-12 | 2007-02-22 | Tdk Corp | Composite dielectric material and prepreg using this, metal foil coated object, molding body, composite dielectric substrate, and multilayer substrate |
| JP2009040934A (en) * | 2007-08-10 | 2009-02-26 | Nippon Steel Chem Co Ltd | Curable resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022009887A1 (en) * | 2020-07-08 | 2022-01-13 | 昭和電工マテリアルズ株式会社 | Resin composition, film, and cured product |
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| JP2011001400A (en) | 2011-01-06 |
| TW201114834A (en) | 2011-05-01 |
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