JP4691921B2 - Resin property adjusting agent and property adjusting resin composition using the same - Google Patents
Resin property adjusting agent and property adjusting resin composition using the same Download PDFInfo
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本発明は、樹脂の特性を改善する樹脂用特性調整剤に関し、より具体的には誘電率、導電率、難燃性、密度、離型性、帯電防止性、抗菌性、防臭性等の特性を改善させる目的で樹脂に混合される樹脂用特性調整剤に関する。また、本発明の樹脂用特性調整剤を用いた特性調整化樹脂組成物に関する。 The present invention relates to a resin property modifier that improves the properties of a resin, and more specifically properties such as dielectric constant, conductivity, flame retardancy, density, releasability, antistatic properties, antibacterial properties, and deodorizing properties. It is related with the characteristic regulator for resins mixed with resin for the purpose of improving. Moreover, it is related with the characteristic adjustment resin composition using the characteristic adjustment agent for resins of this invention.
従来、樹脂の特性を調整するには、樹脂に、樹脂の特性を改善させる目的の、樹脂とは異なる物質である特性調整成分を混合し、その混合比率を制御して、樹脂の特性を調整していた。樹脂への混合方法は、調整剤と樹脂と直接接触させる接触的混合、あるいは調整剤の表面を樹脂に対して不活性な材料で被覆した調整剤を樹脂と間接的に接触させる非接触的混合であった。しかし、樹脂と混合する場合、特性調整成分と樹脂とが反応する相互作用等が起き、調整したい特性とは異なる、他の特性の性能を低下させてしまうという問題点があった。このような問題点を回避するため、樹脂に用いることができる特性調整成分の種類は限られ、また樹脂と特性調整成分の組合せの面において制限があった。 Conventionally, in order to adjust the characteristics of the resin, the resin is mixed with a characteristic adjustment component that is a substance different from the resin for the purpose of improving the characteristics of the resin, and the mixing ratio is controlled to adjust the characteristics of the resin. Was. The method of mixing with the resin is contact mixing in which the modifier is in direct contact with the resin, or non-contact mixing in which the modifier whose surface is coated with a material inert to the resin is in contact with the resin indirectly. Met. However, when mixed with a resin, there is a problem that an interaction between the characteristic adjusting component and the resin occurs, and the performance of other characteristics different from the characteristics to be adjusted is deteriorated. In order to avoid such problems, the types of characteristic adjustment components that can be used in the resin are limited, and there are limitations on the combination of the resin and the characteristic adjustment component.
以下に、誘電率の調整を例として、より詳しく説明する。
樹脂の比誘電率の調整は、樹脂と、その樹脂とは比誘電率が異なる材料（誘電率調整剤）とを混合して行っている。接触的混合方法としては、誘電率調整剤を樹脂に均一溶解する方法、誘電率調整剤を樹脂に分散混合させる方法等がある。しかし、これらの方法では、求める比誘電率の調整は可能であるが、他の特性が低下するという問題がある。例えば、均一溶解（相溶化）する場合、樹脂の反応速度（例えば硬化速度）の低下、或いは上昇をまねき、反応制御が困難となる等の化学的特性の面で、加えて耐熱性（ガラス転移温度、熱に対する寸法安定性を含む等）、誘電正接、接着性、機械的強度等の物理特性の面で、樹脂から元来予期される特性の性能が低下し、樹脂に誘電率調整剤を接触的混合させた場合には、所望の性能すべてが得られないという問題があった。粒子分散の場合においても同様な問題があった（特許文献１）。
また、樹脂に非接触的混合させる場合には、樹脂と中空材とを混合する方法が、樹脂に発泡剤を混合して、樹脂の硬化物内に空隙を設ける方法（空隙配設）、誘電率調整剤を樹脂に不活性なコーティング材料で被覆して混合する方法（被覆混合）が挙げられる。しかし、空隙配設の場合には、機械的強度の点で問題があった。また、被覆混合の場合は、樹脂製コーティング材料では特性調整される樹脂との分散性が悪く、均質に特性調整するのが困難であり、またセラミックス製コーティング材料では機械的強度が不十分であると共に、樹脂の加工が困難であるという問題があった。
そのため、樹脂について、特定の特性のみを調整でき、かつ他の特性の性能が特性調整に伴う悪影響を蒙るのを回避する、樹脂用特性調整剤が求められている。
Hereinafter, the adjustment of the dielectric constant will be described in more detail as an example.
Adjustment of the relative dielectric constant of the resin is performed by mixing a resin and a material (dielectric constant adjusting agent) having a relative dielectric constant different from that of the resin. Examples of the contact mixing method include a method in which the dielectric constant adjusting agent is uniformly dissolved in the resin, and a method in which the dielectric constant adjusting agent is dispersed and mixed in the resin. However, these methods can adjust the required dielectric constant, but there is a problem that other characteristics deteriorate. For example, in the case of uniform dissolution (compatibility), the resin reaction rate (for example, the curing rate) decreases or increases, and in terms of chemical properties such as difficulty in controlling the reaction, heat resistance (glass transition) Including the dimensional stability against temperature and heat), dielectric properties, physical properties such as dielectric loss tangent, adhesiveness, mechanical strength, etc. In the case of contact mixing, there is a problem that not all desired performance can be obtained. There was a similar problem in the case of particle dispersion (Patent Document 1).
In addition, when non-contact mixing with the resin, the method of mixing the resin and the hollow material is a method in which a foaming agent is mixed with the resin to provide voids in the cured resin (void arrangement), dielectric A method (coating mixing) in which a rate adjusting agent is coated on a resin with an inert coating material and mixed. However, there is a problem in terms of mechanical strength in the case of the gap arrangement. In the case of coating mixing, the resin coating material has poor dispersibility with the resin whose characteristics are adjusted, and it is difficult to uniformly adjust the characteristics, and the ceramic coating material has insufficient mechanical strength. At the same time, there is a problem that it is difficult to process the resin.
Therefore, there is a need for a resin property modifier that can adjust only specific properties of the resin and avoids the adverse effects of the performance of other properties associated with the property adjustment.
本発明の目的は、樹脂について、特定の特性のみを調整でき、かつ他の特性の性能を維持し得る、樹脂用特性調整剤及びそれを用いた特性調整化樹脂組成物を提供することにある。 An object of the present invention is to provide a resin property adjusting agent capable of adjusting only specific properties and maintaining the performance of other properties, and a property adjusting resin composition using the same. .
本発明者らは上記の課題を解決するために鋭意研究した結果、本発明に到達した。
本発明は、樹脂の特性を改善する樹脂用特性調整剤であって、その表面に保持材と特性調整成分とが露出し、かつ該特性調整成分の露出部各々の面積は、該特性調整成分と特性調整される該樹脂との相互作用を回避させる面積である樹脂用特性調整剤に関する。特性調整成分の各露出点面積が、８．０×１０6 nm2以下であることが好ましい。特性調整成分は、充填、含浸（表面処理含む）等の埋め込み、打ち込み、粒成長等の方法で保持材に埋め込むことができる。
As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
The present invention is a resin property adjusting agent for improving the properties of a resin, wherein the holding material and the property adjusting component are exposed on the surface, and the area of each exposed portion of the property adjusting component is the property adjusting component. Further, the present invention relates to a resin property adjusting agent that has an area that avoids interaction with the resin whose properties are adjusted. The area of each exposure point of the characteristic adjustment component is preferably 8.0 × 10 6 nm 2 or less. The property adjusting component can be embedded in the holding material by a method such as filling, impregnation (including surface treatment), embedding, driving, or grain growth.
本発明は、樹脂の特定の特性のみを調整でき、かつ他の特性の性能を維持し得る、樹脂用特性調整剤を達成したものである。また、本発明の樹脂用特性調整剤を用いた特性調整化樹脂組成物を達成したものである。 The present invention achieves a resin property modifier that can adjust only specific properties of a resin and can maintain the performance of other properties. Moreover, the characteristic adjustment resin composition using the characteristic adjustment agent for resins of this invention is achieved.
本発明の実施態様の一つは、多孔性物質と、該多孔性物質内に埋め込まれた特性調整成分とで構成される樹脂用特性調整剤に関する。
本発明によれば、樹脂用特性調整剤は、多孔性物質内に特性調整成分を埋め込むため、特性調整成分を、多孔性物質の細孔内に充填し、固定化して構成される。樹脂用特性調整剤（多孔性物質）外部の樹脂と、特性調整成分とは、特性調整成分と特性調整される樹脂との相互作用を回避させる面積内で接触するため、樹脂の特性を調整しながらも、樹脂の他の特性（耐熱性（ガラス転移温度、熱に対する寸法安定性を含む等）、誘電正接、接着性、機械的強度）の性能は維持される。特性調整成分と特性調整される樹脂との相互作用を回避させる面積内で接触するということは、微視的な見地からは特性調整成分と特性調整される樹脂の一部とは接点で各々接触しており、特性調整成分とその接触している特性調整される樹脂とは相互作用、例えば反応している状態であるが、巨視的な見地、つまり全体として捉えると、特性調整される樹脂に悪い影響を与えておらず、相互作用は全体としてほとんど回避されている状態である。
One of the embodiments of the present invention relates to a property adjusting agent for a resin composed of a porous material and a property adjusting component embedded in the porous material.
According to the present invention, the property adjusting agent for resin is configured by filling the property adjusting component in the pores of the porous material and immobilizing the property adjusting component in order to embed the property adjusting component in the porous material. Resin property adjusting agent (porous material) The resin outside and the property adjusting component are in contact with each other within an area that avoids the interaction between the property adjusting component and the resin to be adjusted. However, the performance of other properties of the resin (heat resistance (including glass transition temperature, dimensional stability against heat, etc.), dielectric loss tangent, adhesion, mechanical strength) is maintained. From the microscopic point of view, contact within the area that avoids the interaction between the characteristic adjustment component and the resin to be adjusted means that the characteristic adjustment component and a part of the resin to be adjusted are in contact with each other at the contact point. The property-adjusting component and the property-adjusted resin in contact with each other are in an interaction state, for example, in a reaction state. It does not have a bad influence, and the interaction is almost avoided as a whole.
ここで、多孔性物質の細孔に、他の物質を充填した複合体が知られている（特開平８−２５３６２５号公報及び特開平６−６２３４６号公報）。特許文献２は、多孔質シリカにシリコーン硬化物を充填して撥水性とした撥水性粉末が開示されている。また、特許文献３は、多孔質シリカに、イオン交換樹脂・キレート樹脂を充填して、複合体の表面積を増大させた、クロマトグラム等の分離・吸着剤が開示されている。これらは、いずれも、多孔性物質の表面又は内部に介在させた作用物質（シリコーン硬化物又はイオン交換樹脂・キレート樹脂）を、対象物質（水又は金属等）と接触させ、対象物質に作用を及ぼすことを目的としている。すなわち、本発明のように、多孔性物質内に作用物質（特性調整成分）を埋め込み、かつ対象物質（樹脂）と相互作用を回避させるように接触をさせるものとは、その構造及び作用・機能が異なる。 Here, composites in which pores of a porous material are filled with other materials are known (Japanese Patent Laid-Open Nos. 8-253625 and 6-62346). Patent Document 2 discloses a water-repellent powder that is made water-repellent by filling a porous silica with a silicone cured product. Patent Document 3 discloses a separation / adsorbent such as a chromatogram in which porous silica is filled with an ion exchange resin / chelate resin to increase the surface area of the composite. All of these are made to contact the target substance (water or metal, etc.) with the active substance (silicone cured product or ion-exchange resin / chelate resin) intervened on the surface or inside of the porous substance. The purpose is to affect. That is, as in the present invention, what is embedded in an active substance (characteristic adjusting component) in a porous substance and makes contact with the target substance (resin) so as to avoid interaction is its structure, action and function. Is different.
本発明の多孔性物質は、細孔を有し、樹脂に対して不活性である材料であれば材質は限定されない。細孔は、独立細孔以外に、多孔性物質外部に通じ、細孔同士が連関していることが好ましい。多孔性物質の材質は、例えばシリカ、シリカゲル、ガラス、アルミナ、ゼオライト、水酸化アルミニウム等の金属水酸化物、珪藻土、ケイ酸カルシウム等のケイ酸塩、リン酸カルシウム等のリン酸塩、炭酸カルシウム等の炭酸塩、活性炭、アクリル樹脂、ポリイミド樹脂、ウレタン樹脂、キトサン樹脂、ポリシロキサン樹脂、シリコーンゴム、酢酸セルロース樹脂等が挙げられる。多孔性物質としては、好ましくは無機多孔性物質であり、多孔質シリカであることがより好ましい。また、多孔性物質の形状も特に限定されるものではなく、球状、鱗片状、針状、無結晶粉末状、板状、ハニカム状等が挙げられる。球状である場合、樹脂の流動性を制御できるので好ましい。表面の平均細孔径は０．５〜１０００nmであることが好ましく、１〜１００nmであることがより好ましく、１〜５０nmであることがより好ましい。表面の平均細孔径が０．５nm以上であると、特性調整成分が充填が容易であり、１０００nm以下であると、低誘電率化成分と樹脂と相互作用が回避される接触面積である。例えば、接触面積８．０×１０6 nm2以下であることが好ましい。多孔性物質への特性調整成分の充填量としては細孔容積の１以上〜１００未満容積％であることが好ましい。充填量は、高充填であるほど、多孔性物質の機械的強度が高くなり、また特性調整剤の添加量が少量で有意な効果を発揮する。特性調整成分の充填量が細孔容積の１００容積％未満であると、多孔性物質の細孔内に特性調整成分が埋め込まれている。細孔容積はＪＩＳ Ｋ ５１０１精製あまに油法の吸油量に換算して１０〜７００ml／１００ｇであることが好ましく、５０〜５００ml／１００ｇであることがより好ましい。吸油量が１０ml／１００ｇ以上であると、例えば誘電率の調整効果が有意であり、７００ml／１００ｇ以下であると、多孔性物質の強度が充分である。本発明における細孔容積は、多孔性物質外部に通じる細孔の容積であり、独立細孔の容積は含まれない。
多孔性物質の材質、形状、平均細孔径、吸油量、平均粒径が異なる、２種類以上の多孔性物質を用いることができる。
The material of the porous material of the present invention is not limited as long as the material has pores and is inert to the resin. In addition to the independent pores, it is preferable that the pores lead to the outside of the porous material and are associated with each other. The material of the porous material is, for example, silica, silica gel, glass, alumina, zeolite, metal hydroxide such as aluminum hydroxide, diatomaceous earth, silicate such as calcium silicate, phosphate such as calcium phosphate, calcium carbonate, etc. Examples thereof include carbonate, activated carbon, acrylic resin, polyimide resin, urethane resin, chitosan resin, polysiloxane resin, silicone rubber, and cellulose acetate resin. The porous material is preferably an inorganic porous material, and more preferably porous silica. Further, the shape of the porous material is not particularly limited, and examples thereof include a spherical shape, a scale shape, a needle shape, an amorphous powder shape, a plate shape, and a honeycomb shape. A spherical shape is preferable because the fluidity of the resin can be controlled. The average pore diameter on the surface is preferably 0.5 to 1000 nm, more preferably 1 to 100 nm, and more preferably 1 to 50 nm. When the average pore diameter on the surface is 0.5 nm or more, the characteristic adjustment component can be easily filled, and when it is 1000 nm or less, the contact area is such that interaction between the low dielectric constant component and the resin is avoided. For example, the contact area is preferably 8.0 × 10 6 nm 2 or less. The filling amount of the characteristic adjusting component into the porous material is preferably 1 to less than 100% by volume of the pore volume. The higher the filling amount, the higher the mechanical strength of the porous material, and the smaller the amount of the property modifier added, the more significant the effect. When the filling amount of the characteristic adjusting component is less than 100% by volume of the pore volume, the characteristic adjusting component is embedded in the pores of the porous material. The pore volume is preferably 10 to 700 ml / 100 g, more preferably 50 to 500 ml / 100 g in terms of oil absorption by the JIS K 5101 refined linseed oil method. When the oil absorption is 10 ml / 100 g or more, for example, the effect of adjusting the dielectric constant is significant, and when it is 700 ml / 100 g or less, the strength of the porous material is sufficient. The pore volume in the present invention is the volume of pores communicating with the outside of the porous material, and does not include the volume of independent pores.
Two or more kinds of porous substances having different materials, shapes, average pore diameters, oil absorptions, and average particle diameters of the porous substances can be used.
本発明の特性調整成分は、その特性を調整し得れば、制限されない。樹脂への特性調整成分の溶解を抑制するために２０℃で固体である方が好ましく、２３℃で固体である方がより好ましい。加えて、絶縁性樹脂の溶剤に不溶であることが好ましい。
また、保持材（多孔性物質）に埋め込む際の取扱い性を考慮すると、特性調整成分は、加圧又は加熱により流動性を有することが好ましく、すなわち溶剤を用いずに流動性を得られることが好ましい。これは、溶剤のような揮発性物質を用いて流動性を得ると、加熱・乾燥時、或いは貯蔵時に溶剤が揮発する場合があるので、特性調整成分の固定及び充填の制御を考慮すると、溶剤を用いないことが好ましい。
加熱により流動性を得る場合、流動点又は融点の温度は、保持材（多孔性物質）の機械的強度が維持される温度範囲であることが好ましい。製造環境等を考慮すると、融点は、１００〜２００℃であることが好ましい。
流動点以上の粘度が１００００ポイズ（１ｋPa・ｓ）以下であるとさらに好ましい。
The characteristic adjusting component of the present invention is not limited as long as the characteristic can be adjusted. In order to suppress dissolution of the property adjusting component in the resin, it is preferably a solid at 20 ° C., more preferably a solid at 23 ° C. In addition, it is preferably insoluble in the solvent of the insulating resin.
In consideration of handleability when embedding in a holding material (porous material), the characteristic adjusting component preferably has fluidity by pressurization or heating, that is, it can obtain fluidity without using a solvent. preferable. This is because if the fluidity is obtained by using a volatile substance such as a solvent, the solvent may volatilize during heating / drying or storage, so that the solvent is fixed in consideration of the fixation of the characteristic adjustment component and the control of filling. It is preferable not to use.
When fluidity is obtained by heating, the temperature of the pour point or melting point is preferably in the temperature range in which the mechanical strength of the holding material (porous material) is maintained. Considering the production environment and the like, the melting point is preferably 100 to 200 ° C.
More preferably, the viscosity above the pour point is 10,000 poise (1 kPa · s) or less.
本発明の態様の一つによれば、特性調整成分として、誘電率調整成分、導電率調整成分、難燃性調整成分、密度調整成分、離型性調整成分、帯電防止成分、抗菌性成分、防臭成分等が挙げられる。これらの特性調整成分は、付与する特性を有する成分を適宜選択し、２種以上を介在させる、或いは兼用させることができる。 According to one aspect of the present invention, as a characteristic adjustment component, a dielectric constant adjustment component, a conductivity adjustment component, a flame retardancy adjustment component, a density adjustment component, a release property adjustment component, an antistatic component, an antibacterial component, A deodorizing component etc. are mentioned. As these characteristic adjustment components, components having characteristics to be imparted can be appropriately selected, and two or more kinds can be interposed or used in combination.
例えば、誘電率調整剤としての特性調整成分としては、樹脂と誘電率が異なれば、限定されない。ポリエチレン、ポリプロピレンのようなポリオレフィン、ポリプロピレンエーテル、ポリアミド、ポリアミドイミド、ポリアリレート、熱可塑ポリイミド、ポリエーテルエーテルケトン、ポリエチレンオキシド、ポリエチレンテレフタレート、ポリ塩化ビニリデン、ポリ塩化ビニル、ポリカーボネート、ポリ酢酸ビニル、ポリスチレン、ポリブタジエン、ポリビニルエーテル等の熱可塑樹脂、エポキシ樹脂、キシレン樹脂、グアナミン樹脂、ジアリルフタレート樹脂、不飽和ポリエステル樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ポリイミド、ポリウレタン、マレイン樹脂、メラミン樹脂、ユリア樹脂等の熱硬化性樹脂、エポキシアクリレート等の感光性樹脂が挙げられる。
また、充填する特性調整成分は単一でも、２種類以上用いてもよい。熱硬化性であることが好ましい。あるいは誘電率調整成分が、リン酸エステル又はポリオレフィンであることが好ましい。リン酸エステルとしては、例えば〔（ＣＨ3）2Ｃ6Ｈ3〕2Ｐ（Ｏ）ＯＣ6Ｈ4ＯＰ（Ｏ）〔Ｃ6Ｈ3（ＣＨ3）2〕が挙げられる。
For example, the characteristic adjusting component as the dielectric constant adjusting agent is not limited as long as the dielectric constant is different from that of the resin. Polyolefins such as polyethylene and polypropylene, polypropylene ether, polyamide, polyamideimide, polyarylate, thermoplastic polyimide, polyetheretherketone, polyethylene oxide, polyethylene terephthalate, polyvinylidene chloride, polyvinyl chloride, polycarbonate, polyvinyl acetate, polystyrene, Thermoplastic resin such as polybutadiene and polyvinyl ether, epoxy resin, xylene resin, guanamine resin, diallyl phthalate resin, unsaturated polyester resin, phenol resin, unsaturated polyester resin, polyimide, polyurethane, malein resin, melamine resin, urea resin, etc. Examples thereof include photosensitive resins such as thermosetting resins and epoxy acrylates.
Moreover, the characteristic adjustment component with which it fills may be single, or may use 2 or more types. It is preferably thermosetting. Or it is preferable that a dielectric constant adjustment component is phosphate ester or polyolefin. Examples of the phosphate ester include [(CH 3 ) 2 C 6 H 3 ] 2 P (O) OC 6 H 4 OP (O) [C 6 H 3 (CH 3 ) 2 ].
本発明によれば、保持材（被埋め込み材）、より具体的には多孔性物質内に、特性調整成分を固定する方法について、埋め込み方法により例示する。埋め込み方法としては、毛細管現象を利用して、充填することが簡便である。充填方法は、例えば、液状の特性調整成分と多孔性物質を撹拌して細孔内に充填する方法、加圧下で液状の特性調整成分と多孔性物質を撹拌して細孔内に充填する方法、減圧してから液状の特性調整成分に多孔性物質を投入し撹拌して細孔内に充填する方法、予め多孔性物質と特性調整成分を混合しておき加熱により特性調整成分を溶解して細孔内に充填する方法、予め多孔性物質と特性調整成分を混合しておき減圧してから加熱により特性調整成分を溶解して細孔内に充填する方法、予め多孔性物質と特性調整成分を混合しておき加圧、加熱により特性調整成分を溶解して細孔内に充填する方法、特性調整成分を溶剤等で溶解して多孔性物質と撹拌し細孔内に充填する方法、特性調整成分を溶剤等で溶解して多孔性物質と撹拌し細孔内に充填した後、加熱により溶剤を除去する方法、特性調整成分を溶剤等で溶解して多孔性物質と撹拌し細孔内に充填した後、減圧加熱により溶剤を除去する方法が挙げられる。いずれの方法を用いてもよい。
特性調整成分の充填が終了した多孔性物質は、特性調整成分として使用する前に多孔性物質外部に残る特性調整成分を除去するために、溶剤等で洗浄してもよい。
また、特性調整成分を充填する前に特性調整成分の充填性を高めるために、オリゴマー又はシランカップリング剤等で多孔性物質の細孔表面を処理してもよい。特性調整成分を充填した誘電率調整剤は、分散性を高めるために、オリゴマー又はシランカップリン剤等で表面処理してもよく、粉砕等の処理を行って粒径を小さくしてもよい。
According to the present invention, a method for fixing a characteristic adjusting component in a holding material (a material to be embedded), more specifically, in a porous material is exemplified by an embedding method. As an embedding method, it is easy to fill using a capillary phenomenon. The filling method includes, for example, a method in which a liquid property adjusting component and a porous substance are stirred and filled into pores, and a method in which a liquid property adjusting component and a porous material are stirred under pressure and filled into pores. A method of charging a porous material into a liquid property adjusting component after reducing the pressure, stirring and filling in the pores, mixing the porous material and the property adjusting component in advance and dissolving the property adjusting component by heating A method of filling the pores, a method of mixing the porous substance and the property adjusting component in advance and reducing the pressure, then dissolving the property adjusting component by heating and filling the pores, a porous material and the property adjusting component in advance A method of dissolving the property adjusting component by pressurization and heating and filling it into the pores, a method of dissolving the property adjusting component with a solvent and stirring it with a porous substance, and filling the pores in the pore Dissolve the adjustment components with a solvent, etc., and stir with the porous material to fill the pores. After, a method of removing the solvent by heating, after filling in the characteristic adjusting component is dissolved in a solvent such as stirring with the porous material pores, a method of removing the solvent by heating under reduced pressure, and the like. Any method may be used.
The porous material that has been filled with the property adjusting component may be washed with a solvent or the like in order to remove the property adjusting component remaining outside the porous material before being used as the property adjusting component.
Further, the surface of the porous material may be treated with an oligomer, a silane coupling agent or the like in order to enhance the filling property of the property adjusting component before filling with the property adjusting component. In order to improve dispersibility, the dielectric constant adjusting agent filled with the characteristic adjusting component may be surface-treated with an oligomer or a silane coupling agent, or may be subjected to a treatment such as pulverization to reduce the particle size.
本発明の態様の一つによれば、樹脂と、本発明の樹脂用特性調整剤とを混合分散させた、特性調整された樹脂組成物（特性調整化樹脂組成物）であることが好ましい。分散させる樹脂用特性調整剤は単一でも、２種類以上用いてもよい。
その際には、樹脂用特性調整剤の分散性を向上するために、ニーダー、ボールミル、ビーズミル、三本ロール、ナノマイザー等既知の混練方法により分散することができ、樹脂用特性調整剤を粉砕し粒径を小さくすることができる。
このように、本発明の樹脂用特性調整剤は、樹脂と樹脂用特性調整剤と物理的に混合するのみで、その機能を発揮するため、従来の製造工程を変更する必要がなく、取扱いが容易である。
According to one aspect of the present invention, it is preferably a property-adjusted resin composition (characteristic-adjusted resin composition) obtained by mixing and dispersing a resin and the resin property-adjusting agent of the present invention. A single resin property modifier may be used, or two or more types may be used.
In that case, in order to improve the dispersibility of the resin property modifier, it can be dispersed by a known kneading method such as a kneader, ball mill, bead mill, triple roll, nanomizer, and the resin property modifier is pulverized. The particle size can be reduced.
As described above, the resin property adjusting agent of the present invention only has to be physically mixed with the resin and the resin property adjusting agent to exert its function. Easy.
樹脂と、本発明の樹脂用特性調整剤とを混合分散する配合率は、所望の特性レベルに併せて適宜設定することができる。例えば、本発明の誘電率調整剤を樹脂中に配合する場合、樹脂１００重量部に対し誘電率調整剤を１〜７００重量部にすることが好ましく、５０〜３００重量部にすることがより好ましい。誘電率調整剤の配合量が１重量部以上であるいと誘電率の調整効果が有意であり、７００重量部以下であると樹脂組成物の取扱いが容易である。 The mixing ratio of mixing and dispersing the resin and the resin property adjusting agent of the present invention can be appropriately set according to a desired property level. For example, when the dielectric constant adjusting agent of the present invention is blended in the resin, the dielectric constant adjusting agent is preferably 1 to 700 parts by weight and more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the resin. . When the blending amount of the dielectric constant adjusting agent is 1 part by weight or more, the effect of adjusting the dielectric constant is significant, and when it is 700 parts by weight or less, the resin composition is easily handled.
本発明で樹脂用特性調整剤を分散する樹脂は特に制限されない。例えば、ポリエチレン、ポリプロピレン、ポリアミド、ポリアミドイミド、ポリアリレート、熱可塑性ポリイミド、ポリエーテルエーテルケトン、ポリエチレンオキサイド、ポリエチレンテレフタレート、ポリ塩化ビニリデン、ポリ塩化ビニル、ポリカーボネート、ポリ酢酸ビニル、ポリスチレン、ポリブタジエン、ポリビニルエーテル等の熱可塑樹脂、エポキシ樹脂、キシレン樹脂、グアナミン樹脂、ジアリルフタレート樹脂、ビニルエステル樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ポリイミド、ポリウレタン、マレイン樹脂、メラミン樹脂、ユリア樹脂等の熱硬化性樹脂、エポキシアクリレート等の感光性樹脂等が挙げられるが特に限定されるものではない。 The resin in which the resin property modifier is dispersed in the present invention is not particularly limited. For example, polyethylene, polypropylene, polyamide, polyamideimide, polyarylate, thermoplastic polyimide, polyether ether ketone, polyethylene oxide, polyethylene terephthalate, polyvinylidene chloride, polyvinyl chloride, polycarbonate, polyvinyl acetate, polystyrene, polybutadiene, polyvinyl ether, etc. Thermosetting resins such as thermoplastic resins, epoxy resins, xylene resins, guanamine resins, diallyl phthalate resins, vinyl ester resins, phenol resins, unsaturated polyester resins, polyimides, polyurethanes, maleic resins, melamine resins, urea resins, and epoxy Examples include photosensitive resins such as acrylates, but are not particularly limited.
本発明の特性調整剤を混合した樹脂、すなわち特性調整化樹脂組成物には、本発明の目的の範囲内において、充填剤、添加剤、他の強化繊維材等を添加することができる。例えば、添加剤としては、難燃剤、酸化防止剤、熱安定剤、帯電防止剤、可塑剤、カップリング剤、顔料、染料、着色剤、ゴム等が挙げられる。 Within the range of the object of the present invention, fillers, additives, other reinforcing fiber materials, and the like can be added to the resin mixed with the characteristic modifier of the present invention, that is, the characteristic-adjusted resin composition. For example, examples of the additive include a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, a plasticizer, a coupling agent, a pigment, a dye, a colorant, and rubber.
このような特性調整化樹脂組成物を希釈する溶剤は、樹脂を溶解できれば、限定されない。例えば、メチルエチルケトン、ヘキサン、キシレン、トルエン、アセトン、エチレングリコールモノエチルエーテル、シクロヘキサノン、エチルエトキシプロピオネート、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等が挙げられる。これらの溶剤は、単独あるいは混合系を用いることができる。この溶剤の前記樹脂に対する割合は、樹脂組成物を塗工する設備にあわせてその使用量を調整する。 The solvent for diluting such a property-adjusted resin composition is not limited as long as the resin can be dissolved. Examples thereof include methyl ethyl ketone, hexane, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide and the like. These solvents can be used alone or in a mixed system. The ratio of the solvent to the resin is adjusted according to the equipment for applying the resin composition.
本発明の特性調整化樹脂組成物の用途としては、自動車部品、電子・電気部品等が挙げられる。電子・電気部品としては、例えば回路基板用積層板材料、半導体封止材料等が挙げられる。 Applications of the property-adjusted resin composition of the present invention include automobile parts, electronic / electric parts, and the like. Examples of the electronic / electrical component include circuit board laminate materials and semiconductor sealing materials.
次に、下記の実施例により本発明をさらに詳しく説明するが、これらの実施例は本発明をいかなる意味においても制限するものではない。ここでは、便宜的に、誘電率調整剤を用いて説明する。 Next, the present invention will be described in more detail with reference to the following examples, but these examples are not intended to limit the present invention in any way. Here, for convenience, description will be made using a dielectric constant adjusting agent.
表面処理剤の作製
撹拌装置、コンデンサー及び温度計を備えたガラスフラスコに、ジメトキシジメチルシラン２０ｇ、テトラメトキシシラン２５ｇ及びメタノール１０５ｇを配合した溶液を導入し、その後酢酸０．６０ｇ及び蒸留水１７．８ｇを添加して、５０℃で８時間撹拌した。シロキサン単位の重合度が３０であるシロキサン系表面処理剤を合成した。得られたシロキサン系表面処理剤は、水酸基と反応する末端管能基としてメトキシ基及びシラノール基を有するものである。
Preparation of surface treatment agent A solution containing 20 g of dimethoxydimethylsilane, 25 g of tetramethoxysilane and 105 g of methanol was introduced into a glass flask equipped with a stirrer, a condenser and a thermometer, and then 0.60 g of acetic acid and 17.8 g of distilled water. Was added and stirred at 50 ° C. for 8 hours. A siloxane-based surface treating agent having a siloxane unit polymerization degree of 30 was synthesized. The obtained siloxane-based surface treating agent has a methoxy group and a silanol group as terminal functional groups that react with hydroxyl groups.
実施例１
（１）多孔性物質として多孔質シリカ１[吸油量１５０ml/１００ｇ、表面の平均細孔径５〜１５nm、比重：２．２、平均粒径２．１μm、鈴木油脂工業株式会社製ゴッドボールＥ-２Ｃ（商品名）]と充填する特性調整成分として縮合リン酸エステル[融点９５℃、大八化学工業株式会社製ＰＸ−２００(商品名)]を用い、多孔質シリカ１ ２００重量部、縮合リン酸エステル（ＰＸ−２００）６００重量部を温度計、冷却管、減圧装置、攪拌装置を備えた４つ口セパラブルフラスコに取り、撹拌しながら４つ口セパラブルフラスコ内を減圧した。４つ口セパラブルフラスコ内の圧力が１０mmHg（１．３kPa）以下まで下がった事を確認後、内部温度が１２０℃になるように４つ口セパラブルフラスコを加熱し、温度を保持したまま５時間加熱撹拌して液状の縮合リン酸エステルを多孔質シリカ１内に充填した。
Example 1
(1) Porous silica 1 as a porous material [oil absorption 150 ml / 100 g, surface average pore diameter 5 to 15 nm, specific gravity: 2.2, average particle diameter 2.1 μm, God Ball E- manufactured by Suzuki Oil & Fat Co., Ltd. 2C (trade name)] and condensed phosphoric acid ester [melting point 95 ° C., PX-200 (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.] as a characteristic adjusting component to be filled, 1200 parts by weight of porous silica, condensed phosphorus 600 parts by weight of acid ester (PX-200) was placed in a four-neck separable flask equipped with a thermometer, a condenser, a decompression device, and a stirring device, and the inside of the four-neck separable flask was decompressed while stirring. After confirming that the pressure in the four-neck separable flask has dropped to 10 mmHg (1.3 kPa) or less, heat the four-neck separable flask so that the internal temperature becomes 120 ° C. The porous silica 1 was filled with a liquid condensed phosphate ester by heating and stirring for a period of time.
（２）（１）の４つ口セパラブルフラスコを５０℃まで冷却し、縮合リン酸エステルを固化させた。メチルエチルケトン１４００重量部を４つ口セパラブルフラスコに投入、撹拌して、過剰な縮合リン酸エステルを溶解した。空冷により室温まで冷却後、開孔径０．４５μmのフィルターを用いて、溶解された縮合リン酸エステルの吸引ろ過を行い、過剰な縮合リン酸エステルと充填された多孔質シリカ１とを分離した。 (2) The four-neck separable flask of (1) was cooled to 50 ° C. to solidify the condensed phosphate ester. 1400 parts by weight of methyl ethyl ketone was put into a four-necked separable flask and stirred to dissolve excess condensed phosphate ester. After cooling to room temperature by air cooling, the condensed condensed phosphate ester was suction filtered using a filter having an opening diameter of 0.45 μm to separate excess condensed phosphate ester and filled porous silica 1.
（３）（２）の充填された多孔質シリカ１は、表面にリン酸縮合エステルが付着している場合があるために、２００重量部のメチルエチルケトンに（２）の充填された多孔質シリカ１を投入して、１５分間撹拌して、表面付着リン酸縮エステルを溶解して除去した（多孔質シリカの洗浄）。その後、開孔径０．４５μmのフィルターを用いて、溶解されたリン酸縮合エステルの吸引ろ過を行い、表面付着リン酸縮合エステルと多孔質シリカ１（充填）を分離した。（３）の工程を再度繰り返し多孔質シリカ１（充填）の洗浄を行った。その後、５０℃で１０時間乾燥を行い、誘電率調整剤１（縮合リン酸エステルを多孔質シリカの細孔容積１００％容積で充填した多孔質シリカ１、表面にリン酸縮合エステルが付着していない）を作製した。
得られた低誘電率化剤１において、多孔質シリカ１（充填）が１００％であることを、多孔質シリカ１（充填）と多孔質シリカ（未充填）について顕微鏡観察して確認した。試料は、日立製作所製、ＦＢ２０００Ａ、加速電圧３０ｋＶ、イオン源Gaを用いて、任意の断面を集束イオンビーム（FIB）加工により切り出し（FIB加工後試料）、ＦＩＢ加工後表面を清浄にするため、日立製作所製、Ｅ３２００、加速電圧４ｋＶを用いて、イオンミリング処理した（イオンミリング処理後試料）。イオンミリング処理後試料は、多孔質シリカ（未充填）は細孔が確認されるが、多孔質シリカ１（充填）では隙間なく充填されていること（細孔容積１００％充填）が明らかである。FIB加工後試料及びイオンミリング処理後試料をＳＥＭ（日立製作所製、型番Ｓ−４７００、加速電圧５．０ｋＶ、倍率：１０万倍）で観察した。
図１に、多孔質シリカ１（充填）と多孔質シリカ（未充填）について、FIB加工後試料及びイオンミリング処理後試料の断面観察SEM写真を示す。
(3) Since the porous silica 1 filled with (2) may have phosphoric acid condensed ester attached to the surface thereof, the porous silica 1 filled with 200 parts by weight of methyl ethyl ketone in (2) And stirred for 15 minutes to dissolve and remove the surface-attached phosphoric acid condensed ester (cleaning of porous silica). Subsequently, the dissolved phosphoric acid condensed ester was suction filtered using a filter having an aperture diameter of 0.45 μm to separate the surface-attached phosphoric acid condensed ester and the porous silica 1 (filled). The process of (3) was repeated again to wash the porous silica 1 (filling). Thereafter, drying was performed at 50 ° C. for 10 hours, and dielectric constant adjusting agent 1 (porous silica 1 filled with condensed phosphoric acid ester with a pore volume of 100% of porous silica, phosphoric acid condensed ester adhering to the surface) Not).
In the obtained low dielectric constant agent 1, it was confirmed by microscopic observation of porous silica 1 (filled) and porous silica (unfilled) that the porous silica 1 (filled) was 100%. Sample is made by Hitachi, FB2000A, acceleration voltage 30kV, ion source Ga, cut out any cross section by focused ion beam (FIB) processing (sample after FIB processing), to clean the surface after FIB processing, Ion milling was performed using Hitachi, E3200, and an acceleration voltage of 4 kV (sample after ion milling). In the sample after the ion milling treatment, pores are confirmed in the porous silica (unfilled), but it is clear that the porous silica 1 (filled) is filled without a gap (filled with a pore volume of 100%). . The sample after FIB processing and the sample after ion milling treatment were observed with SEM (manufactured by Hitachi, model number S-4700, acceleration voltage 5.0 kV, magnification: 100,000 times).
FIG. 1 shows cross-sectional observation SEM photographs of the sample after FIB processing and the sample after ion milling for porous silica 1 (filled) and porous silica (unfilled).
（４)誘電率調整剤１は、同重量のメチルエチルケトンに分散させ、上記のシロキサン系表面処理剤を、誘電率調整剤１の重量に対して、表面処理剤の固形分が１ｗｔ％になるように配合して、メチルエチルケトンの還流温度で一時間加熱処理して、表面処理した誘電率調整剤１を得た。 (4) Dielectric constant adjuster 1 is dispersed in the same weight of methyl ethyl ketone so that the above siloxane-based surface treatment agent has a solid content of 1 wt% with respect to the weight of dielectric constant adjuster 1. And heat-treated at the reflux temperature of methyl ethyl ketone for 1 hour to obtain a surface-treated dielectric constant modifier 1.
（５）（４）で作製した誘電率調整剤１を樹脂に配合して、下記の組成で樹脂組成物を作製した（誘電率調整剤：４０．２容積％）。この時のエポキシに対する熱硬化剤の当量は１．０当量とした。この樹脂組成物を銅箔上に塗工し、１００℃−１０分乾燥して膜厚１００±３μmの樹脂フィルムを作製した。
誘電率調整剤１ １５０重量部
樹脂
・ビフェニル系エポキシ樹脂、ＮＣ３０００−Ｈ
(日本化薬株式会社社製、商品名) １１０重量部
・ 熱硬化剤ジシアンジアミド
（日本カーバイド株式会社製、商品名） ４重量部
・ 熱硬化剤ノボラックフェノール樹脂、ＨＰ-８５０
（日立化成工業株式会社製、商品名） ２０重量部
・イミダゾール、２−フェニルイミダゾール（四国化成工業株式会社製、商品名2PZ） ０．５重量部
・溶剤 メチルエチルケトン １５０重量部
（６）次に、銅箔を剥がした後、１８０℃−１２０分の硬化条件で樹脂フィルムを硬化した。
(5) The dielectric constant adjusting agent 1 prepared in (4) was blended with a resin to prepare a resin composition having the following composition (dielectric constant adjusting agent: 40.2% by volume). The equivalent of the thermosetting agent to the epoxy at this time was 1.0 equivalent. This resin composition was applied onto a copper foil and dried at 100 ° C. for 10 minutes to prepare a resin film having a thickness of 100 ± 3 μm.
Dielectric constant adjuster 1 150 parts by weight resin Biphenyl type epoxy resin, NC3000-H
(Nippon Kayaku Co., Ltd., product name) 110 parts by weight Thermosetting agent dicyandiamide (Nihon Carbide Co., Ltd., product name) 4 parts by weight Thermosetting agent novolak phenol resin, HP-850
(Trade name, manufactured by Hitachi Chemical Co., Ltd.) 20 parts by weight • Imidazole, 2-phenylimidazole (trade name 2PZ, manufactured by Shikoku Chemicals Co., Ltd.) 0.5 part by weight • 150 parts by weight of solvent methyl ethyl ketone (6) After peeling off the copper foil, the resin film was cured under curing conditions of 180 ° C.-120 minutes.
実施例２
実施例１において、多孔質シリカ１を、多孔質シリカ２[吸油量３３０ml/１００ｇ、表面の平均細孔径１０nm、比重：２．２、平均粒径２．６μm、富士シリシア化学株式会社製ＳＹＬＹＳＩＡ３１０Ｐ（商品名）]とし、配合量を１００重量部とし、縮合リン酸エステルの配合量は１２００重量部とし、冷却後に４つ口セパラブルフラスコに投入するエチルメチルケトンの量を２６００重量とした以外は、実施例１と同様にして、誘電率調整剤２を作製した(１００％充填)。
Example 2
In Example 1, porous silica 1 was changed to porous silica 2 [oil absorption amount 330 ml / 100 g, surface average pore diameter 10 nm, specific gravity: 2.2, average particle diameter 2.6 μm, SYLYSIA310P manufactured by Fuji Silysia Chemical Ltd. ( Product name)], the blending amount is 100 parts by weight, the blending amount of the condensed phosphate ester is 1200 parts by weight, and the amount of ethyl methyl ketone charged into the four-necked separable flask after cooling is 2600 parts by weight. In the same manner as in Example 1, a dielectric constant adjusting agent 2 was produced (100% filling).
実施例３
実施例１において、多孔質シリカ１を、多孔質シリカ３［吸油量８０ml/１００ｇ、表面の平均細孔径１７mm、比重：２．２、平均粒径３．１μm、旭ガラス株式会社製Ｌ−３１−Ｃ（商品名）］とし、配合量を２００重量部とし、縮合リン酸エステルの配合量は４００重量部とし、冷却後に４つ口セパラブルフラスコに投入するエチルメチルケトンの量を１２００重量とした以外は、実施例１と同様にして、誘電率調整剤３を作製した(１００％充填)。
Example 3
In Example 1, porous silica 1 was changed to porous silica 3 [oil absorption amount 80 ml / 100 g, surface average pore diameter 17 mm, specific gravity: 2.2, average particle diameter 3.1 μm, L-31 manufactured by Asahi Glass Co., Ltd. -C (trade name)], the blending amount is 200 parts by weight, the blending amount of the condensed phosphate ester is 400 parts by weight, and the amount of ethyl methyl ketone charged into the four-necked separable flask after cooling is 1200 parts by weight. A dielectric constant adjuster 3 was produced in the same manner as in Example 1 except that it was filled (100% filling).
比較例１
実施例1の誘電率調整剤と同重量と計算される無孔質シリカとリン酸エステルを、下記の組成で配合し、樹脂組成物を作製した。この時のエポキシに対する熱硬化剤の当量は１．０当量とした。この樹脂組成物を銅箔上に塗工し、１００℃−１０分乾燥して膜厚１００±３μmの樹脂フィルムを作製した。
縮合リン酸エステルリン酸エステル、ＰＸ−２００
（大八化学工業株式会社製、商品名） ９１重量部
無孔質シリカ、ＳＯ−２５Ｒ、平均粒径０．５μm
（株式会社アドマテックス製、商品名） ９重量部
樹脂
・ビフェニル系エポキシ樹脂、ＮＣ３０００−Ｈ
(日本化薬株式会社社製、商品名) １１０重量部
・熱硬化剤ジシアンジアミド
（日本カーバイド株式会社製） ４重量部
・熱硬化剤ノボラックフェノール樹脂、ＨＰ-８５０
（日立化成工業株式会社製、商品名） ２０重量部
・イミダゾール、２−フェニルイミダゾール
（四国化成工業株式会社製、商品名２ＰＺ） ０．５重量部
・溶剤 メチルエチルケトン １５０重量部
（５）次に、銅箔を剥がした後、１８０℃−１２０分の硬化条件で樹脂フィルムを硬化した。
Comparative Example 1
Nonporous silica and phosphate ester calculated to have the same weight as the dielectric constant adjusting agent of Example 1 were blended in the following composition to prepare a resin composition. The equivalent of the thermosetting agent to the epoxy at this time was 1.0 equivalent. This resin composition was applied onto a copper foil and dried at 100 ° C. for 10 minutes to prepare a resin film having a thickness of 100 ± 3 μm.
Condensed phosphate ester phosphate ester, PX-200
(Product name, manufactured by Daihachi Chemical Industry Co., Ltd.) 91 parts by weight nonporous silica, SO-25R, average particle size 0.5 μm
(Product name, manufactured by Admatechs Co., Ltd.) 9 parts by weight resin • Biphenyl epoxy resin, NC3000-H
(Nippon Kayaku Co., Ltd., trade name) 110 parts by weight Thermosetting agent dicyandiamide (Nihon Carbide Co., Ltd.) 4 parts by weight Thermosetting agent novolak phenol resin, HP-850
(Trade name, manufactured by Hitachi Chemical Co., Ltd.) 20 parts by weight • Imidazole, 2-phenylimidazole (trade name 2PZ, manufactured by Shikoku Chemicals Co., Ltd.) 0.5 part by weight • 150 parts by weight of solvent methyl ethyl ketone (5) After peeling off the copper foil, the resin film was cured under curing conditions of 180 ° C.-120 minutes.
比較例２
比較例１において、縮合リン酸エステルを除き、その他は比較例１と同様にして行った。
Comparative Example 2
In Comparative Example 1, the procedure was the same as Comparative Example 1 except for the condensed phosphate ester.
特性試験
誘電率：作製した樹脂フィルムを、ＲＦインピーダンス／マテリアルアナライザ（アジレントテクノロジー社製、ＨＰ ４２９１Ｂ）を用いて１GHzでの誘電率を測定した。
ガラス転移温度：また、樹脂フィルムから試験片を切出して熱機械分析装置（マックサイエンス株式会社製ＴＭＡ−４０００）を用いて昇温；５℃／minの条件でガラス転移温度（Ｔｇ）を測定した。結果を表１に示した。
Characteristic test Dielectric constant: The dielectric constant at 1 GHz was measured for the produced resin film using an RF impedance / material analyzer (manufactured by Agilent Technologies, HP 4291B).
Glass transition temperature: In addition, a test piece was cut out from the resin film and heated using a thermomechanical analyzer (TMA-4000 manufactured by Mac Science Co., Ltd.); the glass transition temperature (Tg) was measured under the condition of 5 ° C./min. . The results are shown in Table 1.
ここで、比較例２は、実施例１〜３の樹脂組成物において誘電率調整剤を、比較例１の樹脂組成物においてリン酸エステルを除いた樹脂組成物とほぼ同様の組成を有する。よって、誘電率調整剤する前の、樹脂の特性を示す（ブランク）である。
表１から明らかなように、本発明の誘電率調整剤を含む特性調整化樹脂組成物を用いた実施例１〜３では、誘電率が３．４未満に低誘電率化された。そして、ガラス転移温度は１５０℃以上であるので、ガラス転移温度、熱に対する寸法安定性は維持された。
一方、本発明の誘電率調整剤を含まない比較樹脂組成物を用いた比較例１については、比較例１ではガラス転移温度、誘電率は悪影響を受けた。
Here, Comparative Example 2 has almost the same composition as the resin composition obtained by removing the dielectric constant adjusting agent in the resin compositions of Examples 1 to 3 and the phosphate ester in the resin composition of Comparative Example 1. Therefore, it is the (blank) which shows the characteristic of resin before making a dielectric constant regulator.
As is clear from Table 1, in Examples 1 to 3 using the property-adjusted resin composition containing the dielectric constant modifier of the present invention, the dielectric constant was lowered to less than 3.4. And since the glass transition temperature is 150 degreeC or more, the glass transition temperature and the dimensional stability with respect to a heat | fever were maintained.
On the other hand, in Comparative Example 1 using the comparative resin composition not containing the dielectric constant adjusting agent of the present invention, the glass transition temperature and the dielectric constant were adversely affected in Comparative Example 1.
表１より、本発明の誘電率調整剤を樹脂に配合することにより、物性への影響を抑えながら誘電率を低減できる。 From Table 1, it is possible to reduce the dielectric constant while suppressing the influence on the physical properties by blending the dielectric constant adjusting agent of the present invention with the resin.
本発明は、特定の特性のみが調整・制御され、かつ他の特性（耐熱性（ガラス転移温度、熱に対する寸法安定性を含む等）、誘電正接、接着性、機械的強度）の性能が維持された、樹脂用特性調整剤及び特性調整樹脂組成物を達成したものである。 In the present invention, only specific characteristics are adjusted and controlled, and other characteristics (heat resistance (including glass transition temperature, dimensional stability against heat, etc.), dielectric loss tangent, adhesiveness, mechanical strength) are maintained. Thus, the resin property adjusting agent and the property adjusting resin composition are achieved.
Claims (9)
前記樹脂組成物が、樹脂と前記誘電率調整剤とを混合して得られ、
前記誘電率調整剤が、
保持材と、前記樹脂の誘電率と異なる誘電率を有する誘電率調整成分とから構成され、
前記保持材が、多孔性無機物質であり、
前記誘電率調整成分が、前記保持材に充填されており、
前記誘電率調整成分が、２０℃で固体であり、下記標準試験における樹脂フィルム２のガラス転移点が、樹脂フィルム１のガラス転移点よりも低い誘電率調整剤。
〔標準試験〕
下記の樹脂フィルム１及び２から試験片を切出して熱機械分析装置（マックサイエンス株式会社製ＴＭＡ−４０００）を用いて昇温；５℃／minの条件で測定したガラス転移温度をそれぞれ樹脂フィルム１及び２のガラス転移点とする。
（１）樹脂フィルム１
下記の配合組成１で樹脂組成物１を作製し、この樹脂組成物１を銅箔上に塗工し、１００℃、１０分乾燥して膜厚１００±３μmの樹脂フィルムを作製し、さらに前記樹脂フィルムから銅箔を剥がした後、１８０℃、１２０分の硬化条件で樹脂フィルムを硬化して樹脂フィルム１を得る。
（１−１）配合組成１
前記誘電率調整成分 ９１重量部
無孔質シリカ、ＳＯ−２５Ｒ、平均粒径０．５μm
（株式会社アドマテックス製、商品名） ９重量部
ビフェニル系エポキシ樹脂、ＮＣ３０００−Ｈ
（日本化薬株式会社社製、商品名） １１０重量部
熱硬化剤ジシアンジアミド
（日本カーバイド株式会社製） ４重量部
熱硬化剤ノボラックフェノール樹脂、ＨＰ-８５０
（日立化成工業株式会社製、商品名） ２０重量部
イミダゾール、２−フェニルイミダゾール
（四国化成工業株式会社製、商品名２ＰＺ） ０．５重量部
溶剤 メチルエチルケトン １５０重量部
（２）樹脂フィルム２
下記の配合組成２で樹脂組成物２を樹脂組成物１と同じ条件で作製し、この樹脂組成物２を銅箔上に塗工し、１００℃、１０分乾燥して膜厚１００±３μmの樹脂フィルムを作製し、さらに前記樹脂フィルムから銅箔を剥がした後、１８０℃、１２０分の硬化条件で樹脂フィルムを硬化して樹脂フィルム２を得る。
（２−１）配合組成２
無孔質シリカ、ＳＯ−２５Ｒ、平均粒径０．５μm
（株式会社アドマテックス製、商品名） ９重量部
ビフェニル系エポキシ樹脂、ＮＣ３０００−Ｈ
（日本化薬株式会社社製、商品名） １１０重量部
熱硬化剤ジシアンジアミド
（日本カーバイド株式会社製） ４重量部
熱硬化剤ノボラックフェノール樹脂、ＨＰ-８５０
（日立化成工業株式会社製、商品名） ２０重量部
イミダゾール、２−フェニルイミダゾール
（四国化成工業株式会社製、商品名２ＰＺ） ０．５重量部
溶剤 メチルエチルケトン １５０重量部 A dielectric constant adjusting agent for adjusting the dielectric constant of the resin composition ,
The resin composition is obtained by mixing a resin and the dielectric constant adjusting agent,
The dielectric constant adjusting agent is
It is composed of a holding material and a dielectric constant adjusting component having a dielectric constant different from that of the resin ,
It said holding material, Ri porous inorganic substance der,
The dielectric constant adjusting component is filled in the holding material,
The permittivity adjusting component, Ri solid der at 20 ° C., a glass transition point of the resin film 2 in the following standard tests, low dielectric constant adjusting agent than the glass transition point of the resin film 1.
[Standard test]
Test pieces were cut out from the following resin films 1 and 2 and heated using a thermomechanical analyzer (TMA-4000 manufactured by Mac Science Co., Ltd.); the glass transition temperatures measured under the condition of 5 ° C./min were the resin films 1 respectively. And the glass transition point of 2.
(1) Resin film 1
A resin composition 1 is prepared with the following composition 1, and the resin composition 1 is coated on a copper foil and dried at 100 ° C. for 10 minutes to produce a resin film having a thickness of 100 ± 3 μm. After peeling the copper foil from the resin film, the resin film is cured under a curing condition of 180 ° C. for 120 minutes to obtain a resin film 1.
(1-1) Formulation composition 1
91 parts by weight of the dielectric constant adjusting component
Nonporous silica, SO-25R, average particle size 0.5 μm
(Product name, manufactured by Admatechs Co., Ltd.) 9 parts by weight
Biphenyl epoxy resin, NC3000-H
(Nippon Kayaku Co., Ltd., trade name) 110 parts by weight
Thermosetting agent dicyandiamide
(Nippon Carbide Corporation) 4 parts by weight
Thermosetting agent novolac phenolic resin, HP-850
(Trade name, manufactured by Hitachi Chemical Co., Ltd.) 20 parts by weight
Imidazole, 2-phenylimidazole
(Product name 2PZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.5 parts by weight
Solvent Methyl ethyl ketone 150 parts by weight
(2) Resin film 2
A resin composition 2 having the following composition 2 was prepared under the same conditions as the resin composition 1. The resin composition 2 was coated on a copper foil, dried at 100 ° C. for 10 minutes, and a film thickness of 100 ± 3 μm. After producing a resin film and peeling a copper foil from the resin film, the resin film is cured under a curing condition of 180 ° C. for 120 minutes to obtain a resin film 2.
(2-1) Formulation composition 2
Nonporous silica, SO-25R, average particle size 0.5 μm
(Product name, manufactured by Admatechs Co., Ltd.) 9 parts by weight
Biphenyl epoxy resin, NC3000-H
(Nippon Kayaku Co., Ltd., trade name) 110 parts by weight
Thermosetting agent dicyandiamide
(Nippon Carbide Corporation) 4 parts by weight
Thermosetting agent novolac phenolic resin, HP-850
(Trade name, manufactured by Hitachi Chemical Co., Ltd.) 20 parts by weight
Imidazole, 2-phenylimidazole
(Product name 2PZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.5 parts by weight
Solvent Methyl ethyl ketone 150 parts by weight
樹脂と前記誘電率調整剤とを混合する工程２とを有する、
前記樹脂と前記誘電率調整剤とを含有する樹脂組成物の製造方法であって、
前記誘電率調整成分が、前記樹脂の誘電率と異なる誘電率を有し、２０℃で固体であり、
請求項１記載の標準試験における樹脂フィルム２のガラス転移点が、樹脂フィルム１のガラス転移点よりも低い樹脂組成物の製造方法。 Step 1 for producing a dielectric constant adjusting agent in which a dielectric constant adjusting component is filled in a porous inorganic substance and the dielectric constant adjusting component is filled in the porous inorganic substance;
Step 2 of mixing a resin and the dielectric constant adjusting agent,
A method for producing a resin composition comprising the resin and the dielectric constant modifier,
The dielectric constant adjusting component has a dielectric constant different from that of the resin and is solid at 20 ° C .;
A method for producing a resin composition, wherein the glass transition point of the resin film 2 in the standard test according to claim 1 is lower than the glass transition point of the resin film 1 .
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| JP2010280924A (en) * | 2010-09-30 | 2010-12-16 | Hitachi Chem Co Ltd | Characteristic adjusting agent for resin and resin composition having been characteristic adjusted using the same |
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| JP5040548B2 (en) * | 2006-11-21 | 2012-10-03 | 日立化成工業株式会社 | Thermosetting resin composition, method for producing the same, prepreg and laminate using the same |
| CN111001388B (en) * | 2019-12-30 | 2022-05-03 | 中国科学院城市环境研究所 | Preparation method and application of bamboo-based biochar phosphorus removal adsorbent |
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| JP2006036922A (en) | 2006-02-09 |
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