【発明の詳細な説明】〔産業上の利用分野〕本発明は高い電磁波遮蔽効果を有する新規な導電性ポリ
マー複合体およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel conductive polymer composite having a high electromagnetic wave shielding effect and a method for producing the same.
近年、電子機器、電波機器の普及はめざましく、電磁波
による障害の問題が各国で大きく取り、トげられている
。プラスチックを構成材料とする電磁波遮蔽体として、
プラスチックの表面を金属または導電性の塗料等でコー
ティングしたものや、金属粉、カーボンブラック、金属
繊維、金属箔等を混和した樹脂などがある。また金属メ
ツシュ等を樹脂てサンドイッチした構造体等もある。In recent years, the spread of electronic devices and radio equipment has been remarkable, and the problem of interference caused by electromagnetic waves has become a major issue in many countries. As an electromagnetic wave shield made of plastic,
There are plastics whose surfaces are coated with metal or conductive paint, and resins mixed with metal powder, carbon black, metal fibers, metal foils, etc. There are also structures made by sandwiching metal mesh or the like with resin.
コーティング法によるものでは衝箪や経時変化、熱など
により電磁波遮蔽層が劣化、剥離するおそれがある。ま
た導電性物質を樹脂に混合したものでは、樹脂本来の性
１１ （例えば曲げ強度、衝７強度等の機械的物性）を
保った状態で高い電磁波遮蔽効果を持たせる事は容易な
事でない。また、これは樹脂全体が導電性を示す。その
ため、絶縁構造体としての役割を兼ねることができず、
電器機器のハウジング、シールドルーム等の壁材として
用いた場合、導線回路などの接触により全体が通電状態
となり感電などのトラブルを容易に引き起こす危険性が
高い。When using a coating method, there is a risk that the electromagnetic wave shielding layer may deteriorate or peel off due to drying, aging, heat, etc. Furthermore, when a conductive substance is mixed with a resin, it is not easy to provide a high electromagnetic wave shielding effect while maintaining the resin's original properties (for example, mechanical properties such as bending strength and impact strength). In addition, the entire resin exhibits electrical conductivity. Therefore, it cannot serve as an insulating structure,
When used as a wall material for housings of electrical appliances, shielded rooms, etc., there is a high risk that contact with conductor circuits will cause the entire body to become energized, easily causing problems such as electric shock.
前記のサンドイッチ構造体では、接着面の強度、すなわ
ち、金属メツシュ等と樹脂との界面における充分な接着
強度を得ることは容易でない。In the sandwich structure described above, it is not easy to obtain sufficient adhesive strength at the adhesive surface, that is, at the interface between the metal mesh or the like and the resin.
また、シールド材料を接地する際、導電層が表面にない
ため、その作業も容易でなく、不確実となる可能性が高
く、ひいては電磁波遮蔽効果を低下させる原因となりつ
る。Further, when grounding the shielding material, since there is no conductive layer on the surface, the work is not easy and is likely to be uncertain, which may lead to a reduction in the electromagnetic wave shielding effect.
本発明の目的は、上記の欠点を解決し、樹脂本来の性質
を劣化させる事なく充分な電磁波遮蔽効果を有すると共
に、絶縁機能をもち、使い勝手の良い構造体を提供する
ことにある。An object of the present invention is to solve the above-mentioned drawbacks, and to provide a structure that has a sufficient electromagnetic wave shielding effect without degrading the original properties of the resin, has an insulating function, and is easy to use.
［課題を解決するための手段］上記の目的は、連続孔構造を有する多孔質体から成るポ
リマー（Ａ）と、その孔内に装填されたポリマー（Ｂ）
とを主体とする複合体であって、ポリマー（Ｂ）全体は
、前記多孔質体内で、導電性充填物質を含イｆする層（
導電層）と、それを実質的に含有しない層（絶縁層）と
に分れていることを特徴とする導電性ポリマー複合体と
、その製法、即ち、連続孔構造を有する多孔質体から成
るポリマー（Ａ）の孔内に、ポリマー（Ｂ）を形成すべ
き液状モノマー、オリゴマー、プレポリマーの一種以上
から成るポリマー（Ｂ）前駆体と、それに分散させた、
該前駆体と比重の異なる導電性充填物質とを充填し、該
前駆体中で導電性充填物質を沈降または浮上させつつ分
散させた状態で、該前駆体を重合または架橋させ、固化
する工程を有する導電性ポリマー複合体の製造方法によ
り達成できる。[Means for Solving the Problems] The above object is to provide a polymer (A) consisting of a porous body having a continuous pore structure and a polymer (B) loaded into the pores.
A composite body mainly consisting of a layer (f) containing an electrically conductive filler substance in the porous body as a whole, wherein the entire polymer (B) is
A conductive polymer composite characterized by being divided into a conductive layer (conductive layer) and a layer (insulating layer) that does not substantially contain the conductive polymer composite, and its manufacturing method, i.e., consisting of a porous body having a continuous pore structure. In the pores of the polymer (A), a polymer (B) precursor consisting of one or more of liquid monomers, oligomers, and prepolymers to form the polymer (B), and dispersed therein.
A step of filling the precursor with a conductive filling material having a different specific gravity, polymerizing or crosslinking the precursor, and solidifying the precursor while the conductive filling material is sedimented or floated and dispersed in the precursor. This can be achieved by a method for producing a conductive polymer composite having the following methods.
なお、導電層は、２神以上の導電性充填物質が含まれて
いてもよい。その場合、別種の導電性充填物質は、混在
していてもよいし、分離し導電層中でさらに層構造を形
成していてもよい。Note that the conductive layer may contain two or more conductive filling substances. In that case, different types of conductive filling materials may be mixed together or may be separated to form a further layered structure in the conductive layer.
本発明の導電性ポリマー複合体は、ポリマー（Ａ）とポ
リマー（Ｂ）とにより良好な機械的物性を示し、また導
電性充填物質により電磁波遮蔽効果が得られ、しかも層
構造となっていることにより、導電性部分と絶縁性部分
とを有する。The conductive polymer composite of the present invention exhibits good mechanical properties due to the polymer (A) and polymer (B), and has an electromagnetic wave shielding effect due to the conductive filling material, and has a layered structure. Therefore, it has a conductive part and an insulating part.
本発明の導電性ポリマー複合体における、連続孔構造を
有する多孔質体から成るポリマー（Ａ）は、表面に多数
の開口をもち、その開口に連なる内部空隙がいたるとこ
ろで連結しているものであって、しかも内部空隙の多く
が多孔質体の地表面につながっているものであり、材質
に関しては合成樹脂、天然樹脂を問わない。In the conductive polymer composite of the present invention, the polymer (A), which is a porous material having a continuous pore structure, has a large number of openings on the surface, and internal voids connected to the openings are connected everywhere. Moreover, most of the internal voids are connected to the ground surface of the porous body, and the material may be synthetic resin or natural resin.
ポリマー（Ａ）は、どのような製法によってもよいが例
えば発泡剤を添加し、加熱により発泡させる方法や、固
形充填剤を添加した後延伸する方法が利用できる。Polymer (A) may be produced by any method, including a method in which a foaming agent is added and foamed by heating, or a method in which a solid filler is added and then stretched.
ポリマー（Ａ）の孔の孔径は、０．１μ〜１０ｍｍ、そ
の空孔率は５〜９８容禎％とするのが、本発明の導電性
ポリマー複合体の製造上の便宜のため、またその強度、
導電性保持のため好ましい。For convenience in manufacturing the conductive polymer composite of the present invention, the pore diameter of the polymer (A) is 0.1 μ to 10 mm, and the porosity is 5 to 98%. Strength,
Preferable for maintaining conductivity.
ポリマー（Ａ）の材質として、例えばポリエチレン、ポ
リスチレン、ポリウレタン、ポリプロピレン、ポリカー
ボネート、フェノール樹脂、メラミン樹脂、ポリ酢酸ビ
ニル、ホリアクリレート、ポリメタクリレート、ポリ塩
化ビニル、ポリアクリロニトリル、ポリビニルエーテル
、ポリアミド、天然ゴム、セルロース等が挙げられる。Examples of the material of the polymer (A) include polyethylene, polystyrene, polyurethane, polypropylene, polycarbonate, phenol resin, melamine resin, polyvinyl acetate, polyacrylate, polymethacrylate, polyvinyl chloride, polyacrylonitrile, polyvinyl ether, polyamide, natural rubber, Examples include cellulose.
一方、本発明の導電性ポリマー複合体における、ポリマ
ー（Ｂ）は、その原料がポリマー（Ａ）の多孔質内に装
填された状態で重合または架橋され生成されたものであ
り、その原料としては常温で液状のモノマー、オリゴマ
ーおよびプレポリマーのうちの一種以上（ポリマー（Ｂ
）前駆体）または常温で固体だが適当な加熱によって液
状となりつるポリマー（Ｂ）前駆体である。なお、「液
状Ｊとは、ポリマー（Ｂ） 前駆体がポリマー（Ａ）の
孔内に侵入することができる程度に粘性が低い流動体状
態をいうか、その粘性は好ましくは２ポアズ以下である
。On the other hand, in the conductive polymer composite of the present invention, the polymer (B) is produced by polymerizing or crosslinking the raw material loaded into the pores of the polymer (A). One or more types of monomers, oligomers, and prepolymers that are liquid at room temperature (polymer (B)
) precursor) or a polymer (B) precursor that is solid at room temperature but becomes liquid when heated appropriately. Note that "liquid J" refers to a fluid state in which the viscosity is low enough to allow the polymer (B) precursor to penetrate into the pores of the polymer (A), and the viscosity is preferably 2 poise or less. .
ポリマー（Ｂ）の材質として、例えばポリメタクリル酸
メチル、ポリスチレン、ポリ不飽和ポリエステル、ポリ
酢酸ビニル等が挙げられる。Examples of the material for the polymer (B) include polymethyl methacrylate, polystyrene, polyunsaturated polyester, and polyvinyl acetate.
また、本発明で使用される導電性充填物質としては、球
状、繊維状等、いかなる形態のものでもよく、カーボン
ブラック、金属粉末（銀、銅、鉄、アルミニウム、ニッ
ケル等）、金属でコーティングされたガラスピーズや中
空ガラス球、金属コーティングされたセラミック球や中
空セラミック球などが挙げられる。これらの導電性充填
物質は１種類だけでなく２種類以上の組み合わせでも使
用できる。さらに平均粒径または最大長さの異なった物
の組み合せも可能である。それらの平均粒径または最大
長さは０．０１μ〜１０ｍｍ程度のものが適当である。The conductive filling material used in the present invention may be in any form, such as spherical or fibrous, and may be coated with carbon black, metal powder (silver, copper, iron, aluminum, nickel, etc.), or metal. Examples include glass beads, hollow glass spheres, metal-coated ceramic spheres, and hollow ceramic spheres. These conductive filling materials can be used not only alone but also in combination of two or more. Furthermore, combinations of particles with different average particle diameters or maximum lengths are also possible. The average particle size or maximum length of these particles is suitably about 0.01 μm to 10 mm.
ポリマー（Ｂ）に対する導電性充填物質の割合は、通常
３〜８００重量部、好ましくは５〜４００重量部、より
好ましくは５〜２００重量部の範囲で添加される。The proportion of the conductive filler to the polymer (B) is usually 3 to 800 parts by weight, preferably 5 to 400 parts by weight, and more preferably 5 to 200 parts by weight.
導電性充填物質は、それを含存させるポリマー（Ｂ）前
駆体と比重の異なるものから選択する。The conductive filler material is selected from those having a specific gravity different from that of the polymer (B) precursor in which it is contained.
本発明の導電性ポリマー複合体は、電磁波遮蔽体として
のみならず、面状発熱体、導電体（スイッチ等）等に好
適に利用できる。The conductive polymer composite of the present invention can be suitably used not only as an electromagnetic wave shield, but also as a sheet heating element, a conductor (switch, etc.), and the like.
本発明の導電性ポリマー複合体の製造方法は以下の様で
ある。The method for producing the conductive polymer composite of the present invention is as follows.
■液状ポリマー（Ｂ）前駆体の所望量に導電性充填物質
と必要に応じて重合開始剤、架橋剤その他、触媒等を添
加し充分に撹拌し、導電性充填物質を均一に分散し、必
要に応じて脱気する。これをＢ液とする。■Add a conductive filler and, if necessary, a polymerization initiator, crosslinking agent, other catalysts, etc. to the desired amount of liquid polymer (B) precursor, stir thoroughly to uniformly disperse the conductive filler, and add the conductive filler as required. Degas accordingly. This is called liquid B.
■次にＢ液中（導電性充填物質が均一に分散された状態
）に連続孔構造を有するポリマー（Ａ）を浸漬するか、
またはポリマー（Ａ）の孔にＢ液を注入し孔部分にＢ液
を充填させる。この後、適当時間放置することによフて
、導電性充填物質は液状ポリマー（Ｂ）前駆体との密度
の差により、沈降または浮上し、それを含む層と含まな
い層とがポリマー（Ａ）内にできる。■Next, the polymer (A) having a continuous pore structure is immersed in liquid B (in which the conductive filling material is uniformly dispersed), or
Alternatively, the B liquid is injected into the pores of the polymer (A) to fill the pores with the B liquid. Thereafter, by leaving the conductive filling material for an appropriate period of time, the conductive filling material will settle or float due to the difference in density with the liquid polymer (B) precursor, and the layer containing it and the layer not containing it will separate from the polymer (A). ) can be done within.
■ポリマー（Ａ）の孔部分に充填されたＢ液を重合また
は架橋し、固化させポリマー（Ｂ）を生成すると、導電
層と絶縁層とから成る導電性ポリマー複合体ができ上が
る。なお、重合、架橋には加熱、紫外線、放射線、マイ
クロ波、超音波照射等が利用できる。(2) When the B solution filled in the pores of the polymer (A) is polymerized or crosslinked and solidified to produce the polymer (B), a conductive polymer composite consisting of a conductive layer and an insulating layer is completed. Note that heating, ultraviolet rays, radiation, microwaves, ultrasonic irradiation, etc. can be used for polymerization and crosslinking.
重合または架橋の反応時間や上記放置時間を制御する事
でポリマー（Ｂ）中の導電性充填物質の濃度勾配を種々
選択することが可能である。必要に応じてポリマー（Ａ
）およびポリマー（Ｂ）に他の充填物質、例えば、難燃
剤、可塑剤、紫外線吸収剤、安定剤、界面活性剤等を添
加できる。By controlling the reaction time of polymerization or crosslinking and the above-mentioned standing time, it is possible to variously select the concentration gradient of the conductive filler substance in the polymer (B). Polymer (A
) and polymer (B) can be added with other fillers, such as flame retardants, plasticizers, UV absorbers, stabilizers, surfactants, etc.
（発明の効果）本発明により樹脂本来の性質を劣化させることなく充分
な電磁遮蔽効果を有する構造体を得ることができる。し
かも、この構造体は、擾れた導電性を示す導電層だけで
なく、絶縁層をも有するため、電機製品（電子機器）の
ハウジングやシールドルーム等の壁材として用いた場合
、トラブルが生じ導電層に電流が流れても、感電などの
トラブルの発生を防止できる。また、導体として用いた
場合には、通電した状態でも取り扱いが可能である。こ
のため、新たに絶縁体によってシールドすることなしに
、プラスチック導電体として用いることができ、使い勝
手も非常に良いものである。(Effects of the Invention) According to the present invention, a structure having a sufficient electromagnetic shielding effect can be obtained without deteriorating the inherent properties of the resin. Furthermore, since this structure has not only a conductive layer that exhibits poor conductivity but also an insulating layer, problems may occur if it is used as a wall material for housings of electrical products (electronic devices) or shield rooms. Even if current flows through the conductive layer, problems such as electric shock can be prevented. Furthermore, when used as a conductor, it can be handled even when energized. Therefore, it can be used as a plastic conductor without additional shielding with an insulator, and is very easy to use.
実施例１メタクリル酸メチル千ツマー１００重量部に銅粉（平均
粒径１０μ５）５０重量部と重合開始剤１重量部を加え
、充分に撹拌した混合液中にシート状のポリウレタンフ
ォーム（大きさ１８０ｍ＋ｏｘ１８０ｍｍ、厚さ７ ｍ
ｍ、孔数４０個／インチで連続孔構造を有する）を浸漬
した。Example 1 50 parts by weight of copper powder (average particle size 10 μ5) and 1 part by weight of a polymerization initiator were added to 100 parts by weight of methyl methacrylate, and the mixture was thoroughly stirred. , 7 m thick
m, having a continuous pore structure with 40 holes/inch) was immersed.
このシート状フオームを取出し、金型にセットし、数分
間放置後、８０℃で６０分の加熱（熱ブレスでの加熱）
により、混合液を硬化させ、導電層（厚さ：約１．５ｍ
ｍ）と絶縁層（厚さ：約３．５＋ｎｍ）を持つ複合体を
得た。Take out this sheet-like foam, set it in a mold, leave it for a few minutes, and heat it at 80℃ for 60 minutes (heating with a heat breather).
to harden the mixed liquid and form a conductive layer (thickness: approximately 1.5 m).
A composite was obtained having an insulating layer (thickness: approximately 3.5+ nm).
得られた複合体の導電層の電気的特性を評価した結果、
第１表に示した様に表面抵抗が小さく、電磁波遮蔽効果
の大きい材料であった。As a result of evaluating the electrical properties of the conductive layer of the obtained composite,
As shown in Table 1, the material had a low surface resistance and a high electromagnetic wave shielding effect.
なお、ポリウレタンフォームとして、厚さ５ｍｍ、１０
ｍｍのものや、孔数２０．３０．５０／インチのものを
用いたり、加熱をオーブンにより実施した場合にも上記
とほぼ同様な特性の複合体ができた。また、導電層と絶
縁層の厚さの比は、ポリウレタンフォームの厚みや空孔
数等を変えることにより、約１：４．２：３等にするこ
ともできた。In addition, as polyurethane foam, thickness 5 mm, 10
Composite materials with substantially the same characteristics as those described above were obtained when using a material with a diameter of 20 mm, a material with a hole count of 20.30.50/inch, and heating in an oven. Further, the ratio of the thickness of the conductive layer to the insulating layer could be set to about 1:4.2:3 by changing the thickness of the polyurethane foam, the number of pores, etc.
実施例２スチレンモノマー１００重量部に銀でコーティングされ
たセラミック中空球（粒径１０〜１００ｕ＋）１０重量
部と重合開始剤０．５〜１重量部を加え、充分に撹拌し
た混合液中にシート状のメラミンフオーム（外形、内部
構造は、実施例１のポリウレタンフォームとほぼ同様）
を浸漬した。Example 2 10 parts by weight of silver-coated ceramic hollow spheres (particle size 10-100U+) and 0.5-1 part by weight of a polymerization initiator were added to 100 parts by weight of styrene monomer, and a sheet was prepared in the thoroughly stirred mixture. melamine foam (external shape and internal structure are almost the same as the polyurethane foam of Example 1)
Soaked.
このシート状フオームを取り出し、金型にセットし、３
０分間放置後、１００℃で４０分の加熱（熱プレスでの
加熱）により、混合液を硬化させ、導電層（厚さ：約１
＋ｎｍ）と絶縁層（厚さ：約４ｍｍ）を持つ複合体を得
た。この場合、実施例１とは逆に複合体の上層部に導電
層が形成された。Take out this sheet-like foam, set it in a mold, and
After being left for 0 minutes, the mixed liquid was cured by heating at 100°C for 40 minutes (heating with a heat press) to form a conductive layer (thickness: approx.
+nm) and an insulating layer (thickness: approximately 4 mm). In this case, contrary to Example 1, a conductive layer was formed on the upper layer of the composite.
この複合体の電気的特性を評価した結果、第１表に示し
た様に導電面では良好な導電性を示し、絶縁面では１０
１２Ω／口以上の抵抗値を示した。As a result of evaluating the electrical properties of this composite, as shown in Table 1, the conductive surface showed good conductivity, and the insulating surface showed good conductivity.
It showed a resistance value of 12Ω/mouth or more.
また、電磁波シールド効果も良好であった。Furthermore, the electromagnetic wave shielding effect was also good.
実施例３酢酸ビニルモノマー１００重量部にニッケル粉（平均粒
径４５間）を５０重量部と重合開始剤０．５重量部を加
え充分に撹拌した混合液を連続孔を有するシート状のポ
リエチレンフオーム（外形、内部構造は実施例１のポリ
ウレタンフォームとほぼ同様）に均一に注入し、孔部分
に混合液を充填した。Example 3 100 parts by weight of vinyl acetate monomer, 50 parts by weight of nickel powder (average particle size: 45%) and 0.5 parts by weight of polymerization initiator were added and thoroughly stirred, and the mixture was mixed to form a sheet-like polyethylene foam having continuous pores. (The external shape and internal structure are almost the same as the polyurethane foam of Example 1), and the pores were filled with the mixed solution.
このシート状フオームを取出し、金型にセットし、数分
間放置後、７０℃で３０分の加熱（熱プレスでの加熱）
により、混合液を硬化させ、導電層（厚さ：約２ｍｍ）
と絶縁層（厚さ：約３１１Ｉａｌ）を持つ複合体を得た
。Take out this sheet form, set it in a mold, leave it for a few minutes, then heat it at 70℃ for 30 minutes (heating with a hot press)
The mixed liquid is cured to form a conductive layer (thickness: approximately 2 mm).
A composite body having an insulating layer (thickness: about 311 Ial) was obtained.
この複合体の電気的特性を評価した結果、第１表に示す
様に導電面は高い導電性を示し、絶縁面では充分に高い
抵抗値を示した。As a result of evaluating the electrical properties of this composite, as shown in Table 1, the conductive surface showed high conductivity, and the insulating surface showed a sufficiently high resistance value.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6031988AJPH01234435A (en) | 1988-03-16 | 1988-03-16 | Electrically conductive polymer composite and production thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6031988AJPH01234435A (en) | 1988-03-16 | 1988-03-16 | Electrically conductive polymer composite and production thereof |
| Publication Number | Publication Date |
|---|---|
| JPH01234435Atrue JPH01234435A (en) | 1989-09-19 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6031988APendingJPH01234435A (en) | 1988-03-16 | 1988-03-16 | Electrically conductive polymer composite and production thereof |
| Country | Link |
|---|---|
| JP (1) | JPH01234435A (en) |
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|---|---|---|---|---|
| US5362760A (en)* | 1991-01-17 | 1994-11-08 | Dsm N.V. | Temperature resistant microporous film |
| US5430073A (en)* | 1991-01-17 | 1995-07-04 | Dsm, N.V. | Process for preparing polymers and mouling compounds based thereon |
| JP2003051479A (en)* | 2001-08-03 | 2003-02-21 | Inoac Corp | Stain wiping-off material and manufacturing method therefor |
| US7300861B2 (en)* | 2004-06-24 | 2007-11-27 | Palo Alto Research Center Incorporated | Method for interconnecting electronic components using a blend solution to form a conducting layer and an insulating layer |
| US7351606B2 (en) | 2004-06-24 | 2008-04-01 | Palo Alto Research Center Incorporated | Method for forming a bottom gate thin film transistor using a blend solution to form a semiconducting layer and an insulating layer |
| WO2008096467A1 (en)* | 2007-02-07 | 2008-08-14 | Toagosei Co., Ltd. | Process for production of functional film |
| JP2010089366A (en)* | 2008-10-08 | 2010-04-22 | Kanayama Kasei Kk | Method for producing foamed resin composite structure |
| JP2014162797A (en)* | 2013-02-21 | 2014-09-08 | Toyo Ink Sc Holdings Co Ltd | Re-releasable aqueous pressure-sensitive adhesive |
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| JPS6011519A (en)* | 1983-06-30 | 1985-01-21 | Nisshinbo Ind Inc | Electroconductive porous structure and its production |
| JPS61103947A (en)* | 1984-10-26 | 1986-05-22 | Nitto Electric Ind Co Ltd | conductive foam |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6011519A (en)* | 1983-06-30 | 1985-01-21 | Nisshinbo Ind Inc | Electroconductive porous structure and its production |
| JPS61103947A (en)* | 1984-10-26 | 1986-05-22 | Nitto Electric Ind Co Ltd | conductive foam |
| JPS61218644A (en)* | 1985-03-20 | 1986-09-29 | バスフ アクチェン ゲゼルシャフト | Production of conductive foamed substance |
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5362760A (en)* | 1991-01-17 | 1994-11-08 | Dsm N.V. | Temperature resistant microporous film |
| US5430073A (en)* | 1991-01-17 | 1995-07-04 | Dsm, N.V. | Process for preparing polymers and mouling compounds based thereon |
| JP2003051479A (en)* | 2001-08-03 | 2003-02-21 | Inoac Corp | Stain wiping-off material and manufacturing method therefor |
| US7300861B2 (en)* | 2004-06-24 | 2007-11-27 | Palo Alto Research Center Incorporated | Method for interconnecting electronic components using a blend solution to form a conducting layer and an insulating layer |
| US7351606B2 (en) | 2004-06-24 | 2008-04-01 | Palo Alto Research Center Incorporated | Method for forming a bottom gate thin film transistor using a blend solution to form a semiconducting layer and an insulating layer |
| WO2008096467A1 (en)* | 2007-02-07 | 2008-08-14 | Toagosei Co., Ltd. | Process for production of functional film |
| JP2010089366A (en)* | 2008-10-08 | 2010-04-22 | Kanayama Kasei Kk | Method for producing foamed resin composite structure |
| JP2014162797A (en)* | 2013-02-21 | 2014-09-08 | Toyo Ink Sc Holdings Co Ltd | Re-releasable aqueous pressure-sensitive adhesive |
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