WO2010147082A1 - Composition de resine a constante dielectrique elevee, feuille de resine a constante dielectrique elevee comprenant cette composition, et tôle en cuivre a resine a constante dielectrique elevee fixee a celle-ci - Google Patents
Composition de resine a constante dielectrique elevee, feuille de resine a constante dielectrique elevee comprenant cette composition, et tôle en cuivre a resine a constante dielectrique elevee fixee a celle-ci Download PDFInfo
- Publication number
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- dielectric constant
- high dielectric
- dielectric
- mass
- Prior art date
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Classifications
-
- 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
-
- 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.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
L'invention concerne une composition de résine à constante diélectrique élevée qui a une constante diélectrique élevée et une tangente diélectrique basse, qui peut obtenir un excellent enrobage de résine dans des circuits, et qui peut être utilisée de façon appropriée dans une couche pour l'isolation entre les circuits. Pour produire la composition de résine, 250 à 900 parts en masse d'une charge d'isolation inorganique à constante diélectrique élevée de diamètre particulaire moyen (D50) d'au moins 0,7μm et de diamètre particulaire maximum n'excédant pas 10μm sont mélangées dans 100 parts en masse d'une résine mélangée (A) préparée par mélange d'un polyphénylène-éther thermodurcissable ayant un terminal modifié par styrène et une masse moléculaire moyenne en nombre de 500 à 3000 avec un élastomère de styrène à un taux de mélange de polyphénylène-éther thermodurcissable à l'élastomère de styrène compris entre 60:40 et 80:20 en masse.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2009-143391 | 2009-06-16 | ||
JP2009143391A JP2011001400A (ja) | 2009-06-16 | 2009-06-16 | 高誘電率樹脂組成物、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 |
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WO2010147082A1 true WO2010147082A1 (fr) | 2010-12-23 |
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PCT/JP2010/060037 WO2010147082A1 (fr) | 2009-06-16 | 2010-06-14 | Composition de resine a constante dielectrique elevee, feuille de resine a constante dielectrique elevee comprenant cette composition, et tôle en cuivre a resine a constante dielectrique elevee fixee a celle-ci |
Country Status (3)
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JP (1) | JP2011001400A (fr) |
TW (1) | TW201114834A (fr) |
WO (1) | WO2010147082A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022009887A1 (fr) * | 2020-07-08 | 2022-01-13 | 昭和電工マテリアルズ株式会社 | Composition de résine, film et produit durci |
Families Citing this family (1)
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CN113614180A (zh) * | 2019-03-27 | 2021-11-05 | 昭和电工材料株式会社 | 树脂组合物、膜及硬化物 |
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JPS63264662A (ja) * | 1986-12-23 | 1988-11-01 | Matsushita Electric Works Ltd | ポリフェニレンオキサイド系樹脂組成物 |
JPH01245053A (ja) * | 1988-03-26 | 1989-09-29 | Matsushita Electric Works Ltd | ポリフェニレンオキサイド系樹脂基板 |
JPH0841247A (ja) * | 1994-07-28 | 1996-02-13 | Otsuka Chem Co Ltd | 電子部品用樹脂組成物 |
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JP2004067889A (ja) * | 2002-08-07 | 2004-03-04 | Toray Ind Inc | 高誘電体組成物 |
JP2004292825A (ja) * | 2004-06-21 | 2004-10-21 | Matsushita Electric Works Ltd | 樹脂組成物、プリプレグ及び積層板 |
JP2005082793A (ja) * | 2003-09-11 | 2005-03-31 | Tdk Corp | ポリフェニレンエーテル系樹脂組成物、その製造方法およびそれを用いた電子回路用基板 |
JP2005105062A (ja) * | 2003-09-29 | 2005-04-21 | Tdk Corp | 樹脂組成物、樹脂付導体箔、プリプレグ、シート、導体箔付シート、積層板およびプリント配線基板 |
JP2007048703A (ja) * | 2005-08-12 | 2007-02-22 | Tdk Corp | 複合誘電体材料及びこれを用いたプリプレグ、金属箔塗工物、成形体、複合誘電体基板、多層基板 |
JP2009040934A (ja) * | 2007-08-10 | 2009-02-26 | Nippon Steel Chem Co Ltd | 硬化性樹脂組成物 |
-
2009
- 2009-06-16 JP JP2009143391A patent/JP2011001400A/ja active Pending
-
2010
- 2010-06-14 WO PCT/JP2010/060037 patent/WO2010147082A1/fr active Application Filing
- 2010-06-15 TW TW099119428A patent/TW201114834A/zh unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS63264662A (ja) * | 1986-12-23 | 1988-11-01 | Matsushita Electric Works Ltd | ポリフェニレンオキサイド系樹脂組成物 |
JPH01245053A (ja) * | 1988-03-26 | 1989-09-29 | Matsushita Electric Works Ltd | ポリフェニレンオキサイド系樹脂基板 |
JPH0841247A (ja) * | 1994-07-28 | 1996-02-13 | Otsuka Chem Co Ltd | 電子部品用樹脂組成物 |
JP2000510639A (ja) * | 1996-05-07 | 2000-08-15 | ヘキスト・セラニーズ・コーポレーション | 温度安定性誘電率を有するポリマー組成物 |
JP2004067889A (ja) * | 2002-08-07 | 2004-03-04 | Toray Ind Inc | 高誘電体組成物 |
JP2005082793A (ja) * | 2003-09-11 | 2005-03-31 | Tdk Corp | ポリフェニレンエーテル系樹脂組成物、その製造方法およびそれを用いた電子回路用基板 |
JP2005105062A (ja) * | 2003-09-29 | 2005-04-21 | Tdk Corp | 樹脂組成物、樹脂付導体箔、プリプレグ、シート、導体箔付シート、積層板およびプリント配線基板 |
JP2004292825A (ja) * | 2004-06-21 | 2004-10-21 | Matsushita Electric Works Ltd | 樹脂組成物、プリプレグ及び積層板 |
JP2007048703A (ja) * | 2005-08-12 | 2007-02-22 | Tdk Corp | 複合誘電体材料及びこれを用いたプリプレグ、金属箔塗工物、成形体、複合誘電体基板、多層基板 |
JP2009040934A (ja) * | 2007-08-10 | 2009-02-26 | Nippon Steel Chem Co Ltd | 硬化性樹脂組成物 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2022009887A1 (fr) * | 2020-07-08 | 2022-01-13 | 昭和電工マテリアルズ株式会社 | Composition de résine, film et produit durci |
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JP2011001400A (ja) | 2011-01-06 |
TW201114834A (en) | 2011-05-01 |
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