JPH0526815B2 - - Google Patents
Info
- Publication number
- JPH0526815B2 JPH0526815B2 JP59122686A JP12268684A JPH0526815B2 JP H0526815 B2 JPH0526815 B2 JP H0526815B2 JP 59122686 A JP59122686 A JP 59122686A JP 12268684 A JP12268684 A JP 12268684A JP H0526815 B2 JPH0526815 B2 JP H0526815B2
- Authority
- JP
- Japan
- Prior art keywords
- treatment
- treated
- polymerizable gas
- low
- gas
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 claims description 12
- 229920003002 synthetic resin Polymers 0.000 claims description 10
- 239000000057 synthetic resin Substances 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 238000004381 surface treatment Methods 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims 2
- 150000003961 organosilicon compounds Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 description 26
- 238000009832 plasma treatment Methods 0.000 description 16
- 239000002344 surface layer Substances 0.000 description 12
- 210000002381 plasma Anatomy 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 229920005672 polyolefin resin Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- OIKHZBFJHONJJB-UHFFFAOYSA-N dimethyl(phenyl)silicon Chemical compound C[Si](C)C1=CC=CC=C1 OIKHZBFJHONJJB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical compound C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
- PKRKCDBTXBGLKV-UHFFFAOYSA-N tris(ethenyl)-methylsilane Chemical compound C=C[Si](C)(C=C)C=C PKRKCDBTXBGLKV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Description
〔技術分野〕
本発明は、合成樹脂成形品、取り分けポリオレ
フイン系樹脂または弗素系樹脂成形品に優れた接
着性を付与するための表面処理方法に関し、更に
詳しくは合成樹脂成形品を初めに非重合性ガスま
たは／および重合性ガスの低温プラズマで処理
し、次いでシリコン系プライマーで処理すること
を特徴とする合成樹脂成形品の表面処理方法に関
する。
〔発明の背景〕
合成樹脂成形品の接着性を改善する手段として
既に幾つかの表面処理方法が開発されている。例
えば酸あるいはアルカリ等の薬品による処理、コ
ロナ処理、フレーム処理等がある。しかし薬品処
理は廃液処理の問題が残り、またコロナ処理、フ
レーム処理は複雑な形状の成形品には適用しにく
いなどの欠点を有している。近年新しい表面処理
方法として低温プラズマ処理が注目され、接着性
改善への利用が試みられているが、特に小さい表
面自由エネルギーをもつポリオレフイン系樹脂や
弗素樹脂では、その効果は未だ十分とは言えなか
つた。本発明者は、低温プラズマ処理に関する研
究を重ねた結果、特定条件のプラズマ処理とシリ
コン系プライマーによる処理を組み合わせること
で合成樹脂成形品の接着性を大巾に改善できるこ
とを見い出し本発明を完成させた。
〔発明の構成〕
本発明は、合成樹脂成形品に初め非重合性ガス
または／および重合性ガスによる低温プラズマ処
理を施し、次いでシリコン系プライマーによる処
理を行うことが特徴である。本発明の処理方法は
いずれの合成樹脂に対しても効果があるが、特に
接着性に問題のあるポリエチレンやポリプロピレ
ン等のポリオレフイン系樹脂や四弗化エチレン樹
脂、四弗化エチレン−六弗化プロピレン共重合体
等の弗素樹脂に大いに推奨される。とりわけ低い
表面自由エネルギーを有し、その接着が極めて困
難な弗素樹脂に好適に利用できる。本発明の実施
は、被処理物を第１に非重合性ガスまたは／およ
びけい素を含む有機化合物からなる重合性ガスの
低温プラズマで処理した後、続いてシリコン系プ
ライマーによる第２の処理を行うことが特徴であ
る。第１工程の低温プラズマ処理は、非重合性ガ
スあるいは重合性ガスいずれでもよく、更に非重
合性ガスの処理と重合性ガスの処理を組み合わせ
たものでもよい。低温プラズマ処理は、低圧下グ
ロー放電により生じる非平衡プラズマを利用して
おり、成形品の表面層のみを改質する。非重合性
ガス−例えば、Ar、He等の不活性ガスあるいは
O2、N2、H2O、CO等のガス−を用いたプラズマ
処理では、成形品がこれら非重合性プラズマに照
射されると、その表面層における分子鎖の切断
や、脱水素化、脱弗素化あるいは酸化反応が行な
われ、不飽和結合の増加、分子量の増大、架橋密
度の増加が進み、一部スパツタリング効果と相ま
つて、接着力が向上すると推定される。これに対
し重合性ガスを用いたプラズマ処理は、成形品の
表面層に高分子薄膜を堆積させることにより、表
面層を改質する。
重合性ガスは、けい素を含む有機化合物が使用
される。特にけい素を含む有機化合物は一般に優
れたブラズマ重合薄膜を基体上に形成し、本発明
に於いても好適に利用できる。例としてヘキサメ
チルジシロキサン１，１，３，３テトラメチルジ
シロキサン、１，３−ジビニル−１，１，３，３
−テトラメチルジシロキサン、１，１，３，３−
テトラメチルジシラザン等のシロキサン、シラザ
ン化合物、ジメチルクロロシラン、ジメチルビニ
ルクロロシラン等のクロロシラン、トリメチルビ
ニルシラン、メチルトリビニルシラン、アリルト
リメチルシラン、エチニールトリメチルシラン等
の不飽和結合を含むシラン、フエニルシランやジ
メチルフエニルシラン等の芳香環を含むシラン、
メトキシトリメチルシランやジメチルエトキシシ
ラン等のアルコキシシラン、更にテトラメチルシ
ラン、ジエチルシランなどを挙げることができ
る。これらガスを用いたプラズマ操作条件は、装
置因子（反応容器の大きさガスの流れ、電極の構
造など）の影響が大きいため、一義的に定めるこ
とはできないが、圧力1paから300pa、放電出力
５〜500watts、処理時間30秒から30分の範囲が
一般的である。圧力が低く、放電出力が高いとス
パツタリング効果も強まり、一般に接着力は向上
する。この低温プラズマ処理は非重合性ガスによ
る処理だけでも、あるいは重合性ガスによる処理
だけでもよく、また非重合性ガスと重合性ガスの
混合ガスによる処理でもよいが、更に非重合性ガ
スの処理に続いて重合性ガスの処理を行うこと
が、より好ましい処理条件である。これは非重合
性ガスによるプラズマ処理が、成形品表面層の汚
れや、低分子量部分の除去に特に効果があり、清
浄な表面層を形成するからであり、その上に重合
性ガスによりプラズマ処理を行うことで、成形品
との密着性により優れた高分子薄膜を堆積させる
ことができるからである。しかしながら、この様
なプラズマ処理を施し成形品表面層の改質を行な
つても、接着性は未だ十分ではない。本発明は、
プラズマ処理の後にシリコン系プライマーによる
処理を加えることが特徴であり、これにより成形
品の接着性は飛躍的に向上する。
シリコン系プライマーは、カツプリング剤とし
て巾広く利用されているシランの縮合物などを主
成分としており、成形品に塗布・乾燥させること
で接着性のある表面を形成する。接着対象により
異なるが、その成分はビニル基、エポキシ基、メ
タクリル基、アミノ基、メルカプト基などの有機
官能基と、アルコキシなどの加水分解性基が含ま
れる。プラズマ処理された表面層とシリコン系プ
ライマーは極めて強固に結合する。プラズマ処理
された表面層は、不飽和結合や−CO、−COOH
等の官能基が存在し、また寿命の長いラジカルが
相当残存すると言われ、化学的活性に富む。この
ためプライマー中の反応基とのカツプリングが容
易に進行するのであろう。プラズマ処理された表
面層にシリコン系、プライマーを塗布した後、乾
燥硬化させることで、成形品の表面層は、接着性
に富む界面が形成されることになる。プライマー
は主成分が適当な溶媒に分散されているので、含
浸ハケ塗り、スプレーなどの方法で塗布できる。
塗布後溶媒を揮発・乾燥させ、硬化させる。以下
実施例を示し、本発明を具体的に説明する。
実施例１〜３、比較例１〜３
厚さ50μｍの焼成された四弗化エチレン樹脂フ
イルムをプラズマ処理装置内にセツトし、
13.56MHzの高周波を用い表−１に示す条件でプ
ラズマ処理を行なつた。全ての条件においてガス
導入後の装置内圧力は30pa、放電出力は100W、
ガス流量は15c.c.（STP）／min、処理時間は
15minであつた。次にこのフイルムをシリコン系
プライマー（東芝シリコーン社製商品名ME151）
中に３秒間浸漬した後、100℃、５分間で乾燥さ
せた。得られたフイルムの接着力を評価するた
め、巾15mm、長さ50mmの試験片を採り、その処理
した面の一端にエポキシ系樹脂接着剤（コニシ社
製、商品名コニシクイツクボンド）を塗布し、表
面研摩したアルミ板と貼り合せ、80℃、１時間加
熱して硬化させ接着せしめた。放冷後、引張り試
験機により20mm／minの引張速度で180°ピーリン
グ
[Technical Field] The present invention relates to a surface treatment method for imparting excellent adhesion to synthetic resin molded articles, particularly polyolefin resin or fluorine resin molded articles, and more specifically, the present invention relates to a surface treatment method for imparting excellent adhesion to synthetic resin molded articles, particularly polyolefin resin or fluorine resin molded articles. The present invention relates to a surface treatment method for a synthetic resin molded article, which is characterized in that it is treated with low-temperature plasma of a reactive gas or/and a polymerizable gas, and then treated with a silicone-based primer. [Background of the Invention] Several surface treatment methods have already been developed as means for improving the adhesion of synthetic resin molded articles. Examples include treatment with chemicals such as acid or alkali, corona treatment, flame treatment, and the like. However, chemical treatment has drawbacks such as the problem of waste liquid treatment, and corona treatment and flame treatment are difficult to apply to molded products with complex shapes. In recent years, low-temperature plasma treatment has attracted attention as a new surface treatment method, and attempts have been made to use it to improve adhesion, but its effects are still not sufficient, especially for polyolefin resins and fluororesins, which have small surface free energies. Ta. As a result of repeated research on low-temperature plasma treatment, the present inventor discovered that the adhesion of synthetic resin molded products could be greatly improved by combining plasma treatment under specific conditions and treatment with a silicon-based primer, and completed the present invention. Ta. [Structure of the Invention] The present invention is characterized in that a synthetic resin molded article is first subjected to low-temperature plasma treatment with a non-polymerizable gas and/or a polymerizable gas, and then treated with a silicon-based primer. Although the treatment method of the present invention is effective for any synthetic resin, it is particularly effective for polyolefin resins such as polyethylene and polypropylene, which have adhesive problems, as well as tetrafluoroethylene resin and tetrafluoroethylene-hexafluoropropylene resin. Highly recommended for fluororesins such as copolymers. In particular, it can be suitably used for fluororesins, which have low surface free energy and are extremely difficult to adhere to. In carrying out the present invention, the object to be treated is first treated with low-temperature plasma of a non-polymerizable gas and/or a polymerizable gas made of an organic compound containing silicon, and then a second treatment with a silicon-based primer is performed. It is characterized by doing. The low temperature plasma treatment in the first step may be performed using either a non-polymerizable gas or a polymerizable gas, or may be a combination of a non-polymerizable gas treatment and a polymerizable gas treatment. Low-temperature plasma treatment uses non-equilibrium plasma generated by glow discharge under low pressure, and modifies only the surface layer of the molded product. Non-polymerizable gas - for example, inert gas such as Ar, He or
In plasma treatment using gases such as O 2 , N 2 , H 2 O, and CO, when a molded product is irradiated with these non-polymerizable plasmas, molecular chains in the surface layer are cut, dehydrogenation, It is presumed that defluorination or oxidation reactions occur, resulting in an increase in unsaturated bonds, an increase in molecular weight, and an increase in crosslinking density, which, combined with the sputtering effect in part, improves adhesive strength. In contrast, plasma treatment using a polymerizable gas modifies the surface layer of a molded article by depositing a thin polymer film on the surface layer. As the polymerizable gas, an organic compound containing silicon is used. In particular, organic compounds containing silicon generally form excellent plasma polymerized thin films on substrates and can be suitably used in the present invention. Examples include hexamethyldisiloxane 1,1,3,3 tetramethyldisiloxane, 1,3-divinyl-1,1,3,3
-tetramethyldisiloxane, 1,1,3,3-
Siloxanes such as tetramethyldisilazane, silazane compounds, chlorosilanes such as dimethylchlorosilane and dimethylvinylchlorosilane, silanes containing unsaturated bonds such as trimethylvinylsilane, methyltrivinylsilane, allyltrimethylsilane, and ethynyltrimethylsilane, phenylsilane and dimethylphenyl Silane containing an aromatic ring such as silane,
Examples include alkoxysilanes such as methoxytrimethylsilane and dimethylethoxysilane, as well as tetramethylsilane and diethylsilane. Plasma operating conditions using these gases cannot be unambiguously determined because they are greatly influenced by equipment factors (reaction vessel size, gas flow, electrode structure, etc.), but they can range from a pressure of 1 to 300 pa, to a discharge output of 5. ~500watts and processing times ranging from 30 seconds to 30 minutes are typical. If the pressure is low and the discharge power is high, the sputtering effect will be stronger and the adhesive strength will generally be improved. This low-temperature plasma treatment may be performed using only a non-polymerizable gas, only a polymerizable gas, or a mixed gas of a non-polymerizable gas and a polymerizable gas. A more preferable treatment condition is to subsequently perform a treatment with a polymerizable gas. This is because plasma treatment with non-polymerizable gas is particularly effective in removing dirt and low molecular weight parts from the surface layer of the molded product, forming a clean surface layer, and then plasma treatment with polymerizable gas This is because by performing this, it is possible to deposit a polymer thin film with better adhesion to the molded product. However, even if the surface layer of the molded article is modified by such plasma treatment, the adhesion is still insufficient. The present invention
It is characterized by adding a treatment with a silicone primer after the plasma treatment, which dramatically improves the adhesion of the molded product. Silicone primers are mainly composed of silane condensates, which are widely used as coupling agents, and when applied to molded products and allowed to dry, they form an adhesive surface. The components include organic functional groups such as vinyl groups, epoxy groups, methacrylic groups, amino groups, and mercapto groups, and hydrolyzable groups such as alkoxy, although they vary depending on the object to be bonded. The plasma-treated surface layer and the silicon-based primer bond extremely strongly. The plasma-treated surface layer has unsaturated bonds, -CO, -COOH
It is said that there are functional groups such as, and a considerable amount of long-lived radicals remain, making it highly chemically active. For this reason, coupling with the reactive group in the primer probably proceeds easily. By applying a silicone-based primer to the plasma-treated surface layer and then drying and curing it, a highly adhesive interface is formed in the surface layer of the molded article. Since the main component of the primer is dispersed in a suitable solvent, it can be applied by impregnation brushing, spraying, or other methods.
After coating, the solvent is evaporated and dried to harden. EXAMPLES The present invention will be specifically explained below with reference to Examples. Examples 1 to 3, Comparative Examples 1 to 3 A fired tetrafluoroethylene resin film with a thickness of 50 μm was set in a plasma processing apparatus,
Plasma treatment was performed using a high frequency of 13.56MHz under the conditions shown in Table 1. Under all conditions, the pressure inside the device after gas introduction was 30pa, the discharge output was 100W,
Gas flow rate is 15 c.c. (STP)/min, processing time is
It was hot in 15 minutes. Next, coat this film with a silicone primer (trade name: ME151 manufactured by Toshiba Silicone Co., Ltd.).
After being immersed in the liquid for 3 seconds, it was dried at 100°C for 5 minutes. In order to evaluate the adhesive strength of the obtained film, a test piece with a width of 15 mm and a length of 50 mm was taken, and an epoxy resin adhesive (manufactured by Konishi Co., Ltd., trade name: Konishi Kuitsuku Bond) was applied to one end of the treated surface. Then, it was bonded to an aluminum plate whose surface had been polished, and heated at 80°C for 1 hour to cure and bond. After cooling, 180° peeling was performed using a tensile tester at a tensile speed of 20 mm/min.
【表】
試験を行なつた。結果を同じく表−１に示す。表
−１に比較例を併記するが、これは、プラズマ処
理した後にプライマー処理がない場合である。こ
れらを較べると、いずれの場合もプラマー処理に
より接着性は一段と改善されており、プラズマ処
理だけの場合に較べ約２倍の接着強度向上となつ
ていることがわかる。
〔発明の効果〕
本発明の合成樹脂成形品の表面処理方法は、接
着性を改善し、特に従来接着の困難であつたポリ
オレフイン系樹脂、弗素樹脂にも効果があり、そ
の接着性を大巾に向上させる。更に本方法は、複
雑な形状の成形品にも効果があり、容易に工業的
規模で実施することができる。又本方法はあくま
で表面層の改質に止まり、バルクの機械的、電気
的特性を変えることはない。[Table] Tests were conducted. The results are also shown in Table-1. Comparative examples are also shown in Table 1, which are cases where no primer treatment was performed after plasma treatment. Comparing these results, it can be seen that in all cases, the adhesiveness was further improved by the primer treatment, and the adhesive strength was improved by about twice as much as in the case of only the plasma treatment. [Effects of the Invention] The surface treatment method for synthetic resin molded products of the present invention improves adhesion, and is particularly effective on polyolefin resins and fluororesins, which have been difficult to adhere to in the past, and greatly improves their adhesion. to improve. Furthermore, this method is effective even for molded products with complex shapes, and can be easily implemented on an industrial scale. Furthermore, this method only modifies the surface layer and does not change the bulk mechanical or electrical properties.
Claims (1)
重合性ガスまたは／およびけい素を含む有機化合
物からなる重合性ガスの低温プラズマにさらした
後、シリコン系プライマーで処理することを特徴
とする合成樹脂成形品の表面処理方法。 ２ ポリオレフイン系または弗素樹脂成形品を非
重合性ガスによる低温プラズマで処理した後、続
いて有機けい素化合物による低温プラズマで処理
し、次いでシリコン系プライマーで処理すること
を特徴とする特許請求の範囲第１項記載の合成樹
脂成形品の表面処理方法。[Claims] 1. A polyolefin or fluororesin molded article is exposed to low-temperature plasma of a non-polymerizable gas and/or a polymerizable gas made of an organic compound containing silicon, and then treated with a silicone-based primer. A method for surface treatment of synthetic resin molded products. 2. Claims characterized in that a polyolefin or fluororesin molded article is treated with low-temperature plasma using a non-polymerizable gas, then treated with low-temperature plasma using an organosilicon compound, and then treated with a silicon-based primer. 2. A method for surface treatment of a synthetic resin molded article according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59122686A JPS612738A (en) | 1984-06-13 | 1984-06-13 | Surface treatment of synthetic resin molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59122686A JPS612738A (en) | 1984-06-13 | 1984-06-13 | Surface treatment of synthetic resin molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS612738A JPS612738A (en) | 1986-01-08 |
| JPH0526815B2 true JPH0526815B2 (en) | 1993-04-19 |
Family
ID=14842110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59122686A Granted JPS612738A (en) | 1984-06-13 | 1984-06-13 | Surface treatment of synthetic resin molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS612738A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003111843A (en) * | 2001-10-05 | 2003-04-15 | Awi Mach:Kk | Cap for syringe, syringe, and method of manufacturing for cap for syringe |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0660252B2 (en) * | 1986-02-03 | 1994-08-10 | マツダ株式会社 | Method for manufacturing polyethylene gasoline tank |
| CA1334744C (en) * | 1987-08-03 | 1995-03-14 | Can B. Hu | Method for preparing lubricated surfaces |
| DE4232390A1 (en) * | 1992-09-26 | 1994-03-31 | Roehm Gmbh | Process for producing silicon oxide scratch-resistant layers on plastics by plasma coating |
| US5647939A (en) * | 1994-12-05 | 1997-07-15 | Integrated Liner Technologies, Inc. | Method of bonding a cured elastomer to plastic and metal surfaces |
| JP4626036B2 (en) * | 2000-09-08 | 2011-02-02 | コニカミノルタホールディングス株式会社 | Method for producing protective film for polarizing plate |
| JP4623282B2 (en) * | 2005-03-10 | 2011-02-02 | 信越化学工業株式会社 | Manufacturing method of semiconductor device |
| WO2007119552A1 (en) * | 2006-03-29 | 2007-10-25 | Zeon Corporation | Process for production of resin composite molded article |
| CN107735243A (en) * | 2015-07-02 | 2018-02-23 | 柯尼卡美能达株式会社 | The manufacture method of conjugant and conjugant |
| JPWO2017002973A1 (en) * | 2015-07-02 | 2018-04-12 | コニカミノルタ株式会社 | Bonded body and method of manufacturing the bonded body |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57202323A (en) * | 1981-06-08 | 1982-12-11 | Shin Etsu Chem Co Ltd | Antistatic fluorine-contained resin molded article |
| JPS5930832A (en) * | 1982-08-13 | 1984-02-18 | Shin Etsu Chem Co Ltd | Molded fluororesin article having modified surface characteristic |
-
1984
- 1984-06-13 JP JP59122686A patent/JPS612738A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57202323A (en) * | 1981-06-08 | 1982-12-11 | Shin Etsu Chem Co Ltd | Antistatic fluorine-contained resin molded article |
| JPS5930832A (en) * | 1982-08-13 | 1984-02-18 | Shin Etsu Chem Co Ltd | Molded fluororesin article having modified surface characteristic |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003111843A (en) * | 2001-10-05 | 2003-04-15 | Awi Mach:Kk | Cap for syringe, syringe, and method of manufacturing for cap for syringe |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS612738A (en) | 1986-01-08 |
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