JPH04349307A - Manufacture of nonmetallic ion type antistatic vinyl layer chloride sheet - Google Patents
Manufacture of nonmetallic ion type antistatic vinyl layer chloride sheetInfo
- Publication number
- JPH04349307A JPH04349307A JP3149592A JP14959291A JPH04349307A JP H04349307 A JPH04349307 A JP H04349307A JP 3149592 A JP3149592 A JP 3149592A JP 14959291 A JP14959291 A JP 14959291A JP H04349307 A JPH04349307 A JP H04349307A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride sheet
- sheet
- ammonia
- acrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title 1
- 150000002500 ions Chemical class 0.000 title 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title 1
- 229920002554 vinyl polymer Polymers 0.000 title 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 36
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 33
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 238000010894 electron beam technology Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- 239000010410 layer Substances 0.000 abstract description 11
- 239000002344 surface layer Substances 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 150000002735 metacrylic acids Chemical class 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- -1 methacryloyl group Chemical group 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000010559 graft polymerization reaction Methods 0.000 description 4
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 229910017852 NH2NH2 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Elimination Of Static Electricity (AREA)
Abstract
Description
【００１】001
【産業上の利用分野】本発明は、表層にイオン移動性の
アンモニウム塩の導電層を形成して、帯電性を防止した
塩化ビニルシ−トの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a vinyl chloride sheet which is prevented from being electrostatically charged by forming a conductive layer of an ion-mobile ammonium salt on its surface.
【００２】002]
【従来技術】プラスチック部材を使用する精密産業、例
えば、電子産業、バイオ産業などの分野では、帯電静電
気が半導体素子を破壊したり、塵や埃の付着を招いて歩
留まりを低下させたりするので、大きな問題になってい
る。特に半導体素子にプラスチックのパッケ−ジを使用
する場合などは、プラスチックに高い静電気帯電防止性
が要求される。[Prior Art] In precision industries that use plastic parts, such as the electronic industry and the bio-industry, static electricity can destroy semiconductor elements or attract dust and dirt, reducing yields. It has become a big problem. In particular, when plastic packages are used for semiconductor devices, plastics are required to have high antistatic properties.
【００３】従来、この半導体素子のプラスチックパッケ
−ジとしては、帯電防止処理を施した塩化ビニルシ−ト
を使用していたが、その帯電防止処理は、金属や金属酸
化物などの導電性フィラ−を分散させた塗膜を表面に形
成する方法によっていた。この場合、金属や金属酸化物
にアルカリ金属やアルカリ土類金属などの導電性フィラ
−を用いると、品質の低下を招くので、使用していない
。Conventionally, plastic packages for semiconductor devices have been made of vinyl chloride sheets that have been treated with antistatic treatment. The method used was to form a coating film on the surface in which the particles were dispersed. In this case, if a conductive filler such as an alkali metal or an alkaline earth metal is used for the metal or metal oxide, the quality will deteriorate, so it is not used.
【００４】004
【発明が解決しようとする課題】しかしながら、この方
法で帯電性を防止するには、高価な導電性フィラ−を有
機バインダ−と同重量以上配合しなければならないため
、処理費が高価になり、また、透明性、光線透過性など
が低下したり、塗膜が剥離し易いという問題があった。
本発明は、これらの欠点を解消した帯電防止性塩化ビニ
ルシ−トの製造方法を提供するものである。[Problems to be Solved by the Invention] However, in order to prevent electrification using this method, it is necessary to mix an expensive conductive filler with at least the same weight as the organic binder, which increases processing costs. Further, there were problems in that transparency, light transmittance, etc. were reduced, and the coating film was likely to peel off. The present invention provides a method for producing an antistatic vinyl chloride sheet that eliminates these drawbacks.
【００５】005]
【課題を解決するための手段】本発明は、塩化ビニルシ
−ト表面にアクリル酸、メタクリル酸の一方または両方
、あるいはこれらを２５ｗｔ％以上含む溶液を塗布した
後、塗布面側から電子線を２０〜１００ｋＧｙ照射して
、塗布モノマ−を塩化ビニルシ−トにグラフト重合させ
、その後、塩化ビニルシ−ト表面に残存するモノマ−ま
たは溶液を洗浄して、塩化ビニルシ−トをアンモニアで
処理するようにした。[Means for Solving the Problems] The present invention involves coating the surface of a vinyl chloride sheet with one or both of acrylic acid and methacrylic acid, or a solution containing 25 wt% or more of these, and then applying an electron beam to the surface of the vinyl chloride sheet for 20 minutes. The applied monomer was graft-polymerized onto the vinyl chloride sheet by irradiation of ~100 kGy, and then the monomer or solution remaining on the surface of the vinyl chloride sheet was washed, and the vinyl chloride sheet was treated with ammonia. .
【００６】006]
【作用】塩化ビニルシ−ト（以下塩ビシ−トという）表
面にアクリル酸、メタクリル酸の一方または両方、ある
いはこれらを含む溶液を塗布した後、塗布面側から電子
線を照射すると、アクリル酸のアクリロイル基やメタク
リル酸のメタクリロイル基の二重結合部分が塩ビシ−ト
にグラフト重合するので、塩ビシ−ト表面にカルボキシ
ル基を有するグラフト層が形成される。このグラフト層
の形成された塩ビシ−トを洗浄して、表面に残存するモ
ノマ−または溶液を除去した後、塩ビシ−トをアンモニ
アで処理すると、グラフト層中のカルボキシル基がアン
モニアと反応して、カルボン酸アンモニウム（−ＣＯＯ
−ＮＨ４＋）になる。[Operation] After applying acrylic acid, methacrylic acid, or both, or a solution containing them, to the surface of a vinyl chloride sheet (hereinafter referred to as vinyl chloride sheet), irradiating an electron beam from the coated surface side causes the acrylic acid to melt. Since the double bond of the acryloyl group or the methacryloyl group of methacrylic acid is graft-polymerized onto the vinyl chloride sheet, a graft layer having carboxyl groups is formed on the surface of the vinyl chloride sheet. After washing the PVC sheet on which the graft layer has been formed to remove the monomer or solution remaining on the surface, the PVC sheet is treated with ammonia, and the carboxyl groups in the graft layer react with the ammonia. , ammonium carboxylate (-COO
-NH4+).
【００７】このカルボン酸アンモニウムのアンモニウム
イオンは、グラフト層のカルボン酸アンモニウムの存在
する層中を自由移動できるので、塩ビシ−ト表面の電気
抵抗が低下し、静電気が漏洩し易くなって帯電防止性が
付与される。このアンモニウムイオンの移動性は、本発
明ではアクリル酸やメタクリル酸をグラフト重合させて
いるため、カルボン酸アンモニウムが連鎖しており、移
動が容易である。[007] The ammonium ions of this ammonium carboxylate can freely move in the layer where ammonium carboxylate is present in the graft layer, so the electrical resistance of the surface of the PVC sheet decreases, making it easier for static electricity to leak and preventing static electricity. gender is given. Regarding the mobility of this ammonium ion, in the present invention, since acrylic acid or methacrylic acid is graft-polymerized, ammonium carboxylates are chained together, making it easy to migrate.
【００８】本発明における塩ビシ−トは、主樹脂が塩ビ
ホモポリマ−であるもののほかに、酢酸ビニルエチレン
などのような塩ビと共重合可能なモノマ−と塩ビとの共
重合体、塩ビホモポリマ−と相溶するポリマ−を塩ビに
ブレンドしたものを含む。また、塩ビには、通常、可塑
剤を添加するが、この可塑剤を添加しないものでもよい
。さらに、必要に応じて、エポキシ化合物、安定剤、顔
料、紫外線吸収剤、酸化防止剤などを添加する場合もあ
るが、本発明での塩ビシ−トはこれらの添加有無を問わ
ないものである。[008] In addition to the main resin of the vinyl chloride sheet of the present invention, which is a vinyl chloride homopolymer, a copolymer of vinyl chloride and a monomer copolymerizable with vinyl chloride such as vinyl acetate ethylene, a vinyl chloride homopolymer, etc. Contains blends of PVC with polymers that are compatible with PVC. Furthermore, although a plasticizer is usually added to vinyl chloride, it is also possible to use one without this plasticizer. Furthermore, if necessary, epoxy compounds, stabilizers, pigments, ultraviolet absorbers, antioxidants, etc. may be added, but the vinyl chloride sheet of the present invention does not care whether or not these are added. .
【００９】塩ビシ−ト表面に塗布するモノマ−は、電子
線反応性官能基であるアクリロイルもしくはメタクリロ
イル基と、アンモニアとの反応によりアンモニウムを形
成するカルボキシル基とを備えていることが必要である
が、アクリル酸またはメタクリル酸以外で、これらの官
能基を有するものであっても、アクリル酸やメタクリル
酸以外のもの、例えば、次のようなものはグラフト重合
が十分起こらないので、使用できない。
ＣＨ２＝Ｃ（ＣＨ３）−ＣＯ−ＯＣＨ２ＣＨ２−ＲＲ；
−ＯＣＯ（ＣＨ２）２−ＣＯＯＨ−ＯＣＯＣ６Ｈ４
−ＣＯＯＨ
−ＯＣＨ２ＣＨ２−ＣＯＯＨThe monomer applied to the surface of the vinyl chloride sheet must have an acryloyl or methacryloyl group, which is an electron beam-reactive functional group, and a carboxyl group, which forms ammonium by reaction with ammonia. However, substances other than acrylic acid or methacrylic acid, even those having these functional groups, such as the following, cannot be used because graft polymerization does not occur sufficiently. CH2=C(CH3)-CO-OCH2CH2-RR;
-OCO(CH2)2-COOH-OCOC6H4
-COOH -OCH2CH2-COOH
【０１０】アクリル酸やメタクリル酸は、単独で塗布し
ても、混合して塗布してもよい。また、溶液にして塗布
しても本発明の目的を達成できる。この場合、アクリル
酸やメタクリル酸の濃度は単独または合計で２５ｗｔ％
以上にする必要がある。これより濃度が低いと、グラフ
ト重合が十分起こらないため、十分なる帯電防止性が得
られない。これは、グラフト重合量が少ないと、塩ビシ
−トの表層に導入されたカルボキシル基の濃度が低くな
るため、アンモニア処理で生成するカルボン酸アンモニ
ウム濃度も低くなり、電気抵抗が十分低下しないからで
ある。Acrylic acid and methacrylic acid may be applied alone or in combination. The object of the present invention can also be achieved by applying the solution as a solution. In this case, the concentration of acrylic acid or methacrylic acid is 25 wt% individually or in total.
It is necessary to do more than that. If the concentration is lower than this, sufficient antistatic properties cannot be obtained because graft polymerization does not occur sufficiently. This is because if the amount of graft polymerization is small, the concentration of carboxyl groups introduced into the surface layer of the PVC sheet will be low, so the concentration of ammonium carboxylate produced by ammonia treatment will also be low, and the electrical resistance will not decrease sufficiently. be.
【０１１】アクリル酸、メタクリル酸などの溶液の溶媒
としては、水、有機溶媒、モノマ−、オリゴマ−、ポリ
マ−などあらゆるものを用いることができるが、その選
択にあたっては、粘度調整性、塩ビシ−トへの溶解性、
膨潤能力などを考慮することが重要である。アクリル酸
やメタクリル酸をそのまま、あるいは溶液で塗布するに
しても、アクリル酸やメタクリル酸のホモ重合を抑制す
るために、モ−ル塩などの重合禁止剤を添加してもよい
。[011] As a solvent for solutions of acrylic acid, methacrylic acid, etc., any solvent can be used, including water, organic solvents, monomers, oligomers, and polymers. - solubility in
It is important to consider factors such as swelling ability. Even if acrylic acid or methacrylic acid is applied as it is or as a solution, a polymerization inhibitor such as Mohr's salt may be added to suppress homopolymerization of acrylic acid or methacrylic acid.
【０１２】アクリル酸、メタクリル酸、その溶液の塩ビ
シ−トへの塗布は、公知方法、例えば、スプレ−法、カ
−テンフロ−法、ロ−ルコ−ト法などで行えばよい。Acrylic acid, methacrylic acid, and their solutions may be applied to the vinyl chloride sheet by any known method, such as a spray method, curtain flow method, or roll coating method.
【０１３】アクリル酸、メタクリル酸の塩ビシ−トへの
グラフト重合は、表層のみに行えば静電気の帯電を防止
できるので、照射電子線は、エネルギ−が一般に低エネ
ルギ−型と呼ばれている３００ｋｅＶ未満の電子線で十
分であるが、それ以上のエネルギ−を有する電子線も使
用でき、またγ線も使用できる。[013] Graft polymerization of acrylic acid or methacrylic acid onto a vinyl chloride sheet can prevent static electricity from being charged if it is carried out only on the surface layer, so the electron beam irradiation is generally called a low-energy type. An electron beam of less than 300 keV is sufficient, but electron beams with higher energies can also be used, and gamma rays can also be used.
【０１４】照射電子線の線量は、２０〜１００ｋＧｙに
するが、これは、２０ｋＧｙ未満であると、アクリル酸
やメタクリル酸が十分グラフト重合しないため、塩ビシ
−ト表層に導入されたカルボキシル基の濃度が低くなり
、アンモニア処理後のカルボン酸アンモニウム濃度が不
足して、電気抵抗が十分低下しないからである。一方、
１００ｋＧｙを越えると、塩ビシ−トに劣化が起こり、
黄変して商品価値が大きく低下し、また、表面にタッキ
ング性が生じてしまう。[014] The dose of the irradiated electron beam is 20 to 100 kGy, but if it is less than 20 kGy, acrylic acid and methacrylic acid will not be graft-polymerized sufficiently. This is because the concentration becomes low and the ammonium carboxylate concentration after ammonia treatment is insufficient, so that the electrical resistance is not lowered sufficiently. on the other hand,
If it exceeds 100kGy, the PVC sheet will deteriorate and
It yellows, greatly reducing its commercial value, and also causes tacking on the surface.
【０１５】電子線照射後は、塩ビシ−ト表面に残存する
モノマ−やその溶液を洗浄し、アンモニアで処理する。
電子線照射後の溶液中にはアクリル酸やメタクリル酸の
ホモポリマ−が含まれているので、洗浄、除去しないと
、タッキング性が残り、また、アルカリ処理であるアン
モニア処理工程に酸を持ち込み、ｐＨの低下、異物の混
入をきたし、アンモニウム塩の形成が困難になる。洗浄
には、通常、水を使用するが、有機溶媒でもよい。After the electron beam irradiation, the monomer and its solution remaining on the surface of the vinyl chloride sheet are washed away and treated with ammonia. The solution after electron beam irradiation contains homopolymers of acrylic acid and methacrylic acid, so if it is not washed and removed, tacking properties will remain, and the acid will be brought into the ammonia treatment process, which is an alkali treatment, and the pH will change. This results in a decrease in the amount of ammonium salt and the contamination of foreign substances, making it difficult to form ammonium salts. Water is usually used for washing, but organic solvents may also be used.
【０１６】アンモニア処理は、アンモニアを水、アルコ
−ルなどの溶媒に溶解した溶液に塩ビシ−トを浸漬する
方法、アンモニアガスと接触させる方法などによればよ
いが、溶液に浸漬する場合、溶液のアンモニア濃度、温
度が高い程、また、アンモニアガスと接触させる場合は
アンモニア蒸気圧が高い程短時間にカルボキシル基をカ
ルボン酸アンモニウムにすることができる。[016] The ammonia treatment may be carried out by immersing the PVC sheet in a solution of ammonia dissolved in a solvent such as water or alcohol, or by contacting it with ammonia gas. The higher the ammonia concentration and temperature of the solution, or when contacting with ammonia gas, the higher the ammonia vapor pressure, the faster the carboxyl group can be converted to ammonium carboxylate.
【０１７】017]
【実施例】可塑剤添加量の異なる塩ビシ−トの表面にバ
−コ−タ−＃２０で種々のモノマ−またはその溶液を塗
布して、その塗布面側から電子線を加速電圧２００ｋＶ
で線量を変化させながら照射した。その後、塩ビシ−ト
を水で洗浄して、表面に残存する溶液を除去し、種々の
濃度のアンモニア水（４０℃）に１分間浸漬するか、ア
ンモニア飽和蒸気中に１０分間静置し、水洗、乾燥した
。[Example] Various monomers or their solutions were coated on the surface of PVC sheets with different amounts of plasticizer added using bar coater #20, and an electron beam was applied from the coated surface side at an accelerating voltage of 200 kV.
Irradiation was performed while varying the dose. Thereafter, the PVC sheet was washed with water to remove the solution remaining on the surface, and either immersed in ammonia water (40°C) of various concentrations for 1 minute, or left standing in ammonia saturated steam for 10 minutes, Washed with water and dried.
【０１８】乾燥後、各シ−トの表面固有抵抗（ＪＩＳ
Ｋ ６９１１）、帯電圧（ＪＩＳＬ １０９４）を温度
２３℃、湿度５０％の条件で測定した。また、目視でシ
−トの透明性を評価した。表１、表２に実施例を、表３
、表４に比較例を処理条件とともに示す。なお、比較例
で用いたモノマ−のうち、モノマ−Ａ、ＢおよびＣは次
のものである。
モノマ−Ａ；
ＣＨ２＝Ｃ（ＣＨ３）−ＣＯ−ＯＣＨ２ＣＨ２−ＯＣＯ
（ＣＨ２）２−ＣＯＯＨ モノマ−Ｂ；
ＣＨ２＝Ｃ（ＣＨ３）−ＣＯ−ＯＣＨ２ＣＨ２−ＯＣＯ
Ｃ６Ｈ４−ＣＯＯＨ モノマ−Ｃ；
ＣＨ２＝Ｃ（ＣＨ３）−ＣＯ−ＯＣＨ２ＣＨ２−ＯＣＨ
２ＣＨ２−ＣＯＯＨAfter drying, the surface specific resistance (JIS
K 6911) and charging voltage (JISL 1094) were measured at a temperature of 23° C. and a humidity of 50%. In addition, the transparency of the sheet was visually evaluated. Examples are shown in Table 1 and Table 2, Table 3
, Table 4 shows comparative examples along with processing conditions. In addition, among the monomers used in the comparative example, monomers A, B, and C are as follows. Monomer-A; CH2=C(CH3)-CO-OCH2CH2-OCO
(CH2)2-COOH Monomer-B; CH2=C(CH3)-CO-OCH2CH2-OCO
C6H4-COOH Monomer-C; CH2=C(CH3)-CO-OCH2CH2-OCH
2CH2-COOH
【０１９】また、アンモニア処理で
のアルカリＡ、ＢおよびＣは次のような構造のものであ
る。
アルカリＡ；１０ｗｔ％（ＣＨ３）４Ｎ・ＯＨ水溶液ア
ルカリＢ；４０ｗｔ％Ｃ６Ｈ５ＣＨ２Ｎ（ＣＨ３）３・
ＯＨ水溶液
アルカリＣ；９０ｗｔ％ＮＨ２ＮＨ２・Ｈ２Ｏ水溶液Furthermore, alkalis A, B and C used in the ammonia treatment have the following structure. Alkali A: 10wt% (CH3)4N・OH aqueous solution Alkali B: 40wt%C6H5CH2N(CH3)3・
OH aqueous solution alkaline C; 90wt% NH2NH2・H2O aqueous solution
【
０２０】[
020]
【表１】[Table 1]
【０２１】021]
【表２】[Table 2]
【０２２】022]
【表３】[Table 3]
【０２３】023]
【表４】
（注１）＊印のものは酸臭が残存していた。
（注２）★印のものは黄変していた。
（注２）不透明なものはいずれも表面にタッキング性が
認められた。[Table 4] (Note 1) Items marked with * had a residual acid odor. (Note 2) Items marked with ★ were yellowed. (Note 2) Tacking was observed on the surface of all opaque products.
【０２４】024]
【発明の効果】以上のように、本発明法は、塩ビシ−ト
表層にアクリル酸やメタクリル酸をグラフト重合させた
後、アンモニアで処理して、表層に導電層を形成するの
であるから、従来の導電性フィラ−を充填した塗膜を塩
ビシ−ト表面に形成する場合に比べて、処理費が安価で
、塩ビシ−トの透明は保持される。また、導電層は、塩
ビシ−トと化学結合しているので、剥離することがなく
、塩ビシ−トの物性は、導電層を形成してもほとんど変
化しない。As described above, the method of the present invention involves graft polymerizing acrylic acid or methacrylic acid on the surface layer of a PVC sheet, and then treating it with ammonia to form a conductive layer on the surface layer. Compared to the conventional case where a coating film filled with conductive filler is formed on the surface of a vinyl chloride sheet, the processing cost is lower and the transparency of the vinyl chloride sheet is maintained. Furthermore, since the conductive layer is chemically bonded to the PVC sheet, it will not peel off, and the physical properties of the PVC sheet will hardly change even after the conductive layer is formed.
Claims (1)
メタクリル酸の一方または両方、あるいはこれらを２５
ｗｔ％以上含む溶液を塗布した後、塗布面側から電子線
を２０〜１００ｋＧｙ照射して、塗布モノマ−を塩化ビ
ニルシ−トにグラフト重合させ、その後、塩化ビニルシ
−ト表面に残存するモノマ−または溶液を洗浄して、塩
化ビニルシ−トをアンモニアで処理することを特徴とす
る非金属イオン型帯電防止性塩化ビニルシ−トの製造方
法。[Claim 1] Acrylic acid on the surface of vinyl chloride sheet,
one or both of methacrylic acid, or 25
After applying a solution containing % wt% or more, 20 to 100 kGy of electron beam is irradiated from the coated surface side to graft-polymerize the coated monomer onto the vinyl chloride sheet, and then the monomer remaining on the surface of the vinyl chloride sheet or 1. A method for producing a nonmetallic ion type antistatic vinyl chloride sheet, which comprises washing the solution and treating the vinyl chloride sheet with ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3149592A JP3043836B2 (en) | 1991-05-24 | 1991-05-24 | Method for producing non-metal ion type antistatic vinyl chloride sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3149592A JP3043836B2 (en) | 1991-05-24 | 1991-05-24 | Method for producing non-metal ion type antistatic vinyl chloride sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04349307A true JPH04349307A (en) | 1992-12-03 |
| JP3043836B2 JP3043836B2 (en) | 2000-05-22 |
Family
ID=15478576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3149592A Expired - Lifetime JP3043836B2 (en) | 1991-05-24 | 1991-05-24 | Method for producing non-metal ion type antistatic vinyl chloride sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3043836B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160119841A (en) | 2014-03-07 | 2016-10-14 | 후지필름 가부시키가이샤 | Organic thin film transistor |
-
1991
- 1991-05-24 JP JP3149592A patent/JP3043836B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160119841A (en) | 2014-03-07 | 2016-10-14 | 후지필름 가부시키가이샤 | Organic thin film transistor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3043836B2 (en) | 2000-05-22 |
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