JP2751366B2 - Method for producing gas barrier sheet - Google Patents
Method for producing gas barrier sheetInfo
- Publication number
- JP2751366B2 JP2751366B2 JP1094231A JP9423189A JP2751366B2 JP 2751366 B2 JP2751366 B2 JP 2751366B2 JP 1094231 A JP1094231 A JP 1094231A JP 9423189 A JP9423189 A JP 9423189A JP 2751366 B2 JP2751366 B2 JP 2751366B2
- Authority
- JP
- Japan
- Prior art keywords
- gas barrier
- nbr
- barrier sheet
- vinylidene chloride
- sheet
- 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
- 230000004888 barrier function Effects 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- 239000004636 vulcanized rubber Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 15
- 229920000459 Nitrile rubber Polymers 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 238000005452 bending Methods 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920013648 Perbunan Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 allyl peroxycarbonate Chemical compound 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、ガスバリヤー性シートの製造方法に関す
る。更に詳しくは、NBRと塩化ビニリデン系樹脂とから
なるガスバリヤー性シートの製造方法に関する。The present invention relates to a method for producing a gas barrier sheet. More specifically, the present invention relates to a method for producing a gas barrier sheet comprising NBR and a vinylidene chloride-based resin.
〔従来の技術〕 ゴムは、一般にガスバリヤー性の点で樹脂に比較して
劣るとされているが、弾性、柔軟性の点ですぐれてお
り、この性質の故にパッキン、プラダー、ダイアフラ
ム、ホースなどの製造に欠くことのできない材料とされ
ている。[Prior art] Rubber is generally considered to be inferior to resin in terms of gas barrier properties, but is superior in elasticity and flexibility, and because of this property, packing, pladder, diaphragm, hose, etc. It is considered an indispensable material for the manufacture of
ところで、各種のゴムの内、汎用のガスバリヤー性ゴ
ムとしては、NBR、ブチルゴムを挙げることができる。
特に、NBRは耐油性が良好なので多くの工業材料として
用いられている。かかるNBRに、ガスバリヤー性にすぐ
れた塩化ビニリデン系樹脂を複合化させ、良好なガスバ
リヤー性を保持しつつ弾性にもすぐれた材料を求めるこ
とが検討されたが、そこに得られた複合材料はNBRが用
いられているにもかかわらず、屈曲条件下ではガスバリ
ヤー性を著しく低下させることが見出された。By the way, among various rubbers, NBR and butyl rubber can be cited as general-purpose gas barrier rubbers.
In particular, NBR is used as many industrial materials because of its good oil resistance. Such NBR was compounded with a vinylidene chloride resin having excellent gas barrier properties, and it was studied to find a material having excellent elasticity while maintaining good gas barrier properties, but the composite material obtained there was considered. It was found that, despite the use of NBR, the gas barrier properties were significantly reduced under bending conditions.
〔発明が解決しようとする課題〕 本発明の目的は、耐屈曲性にすぐれ、屈曲条件下に置
かれてもガスバリヤー性を低下させることのないNBRと
塩化ビニリデン系樹脂とからなるシートの製造方法を提
供することにある。[Problem to be Solved by the Invention] An object of the present invention is to produce a sheet comprising NBR and vinylidene chloride-based resin, which has excellent bending resistance and does not lower gas barrier properties even under bending conditions. It is to provide a method.
かかる本発明の目的は、次のいずれかの方法によりガ
スバリヤー性シートを製造することにより達成される。The object of the present invention is achieved by producing a gas barrier sheet by any of the following methods.
（１）NBR加硫ゴムシート上に、ポリイソシアネート含
有塩化ビニリデン系樹脂コーティング液をコーティング
し、乾燥させる方法 （２）塩化ビニリデン系樹脂フィルム上に、ポリイソシ
アネートまたは有機過酸化物含有NBR加硫配合物溶液を
コーティングし、加熱加硫する方法 これら両者の方法で用いられる塩化ビニリデン系樹脂
は、少なくとも60モル％以上の塩化ビニリデンと他のビ
ニル単量体、例えば塩化ビニル、アクリロニトリル、ア
クリル酸、アクリル酸エステル、メタクリル酸、メタク
リル酸エステルなどとの共重合体である。(1) A method of coating a polyisocyanate-containing vinylidene chloride-based resin coating solution on an NBR vulcanized rubber sheet and drying it. (2) A polyisocyanate or organic peroxide-containing NBR vulcanization compounded on a vinylidene chloride-based resin film. A method of coating a product solution and heating and vulcanizing The vinylidene chloride resin used in both of these methods is at least 60 mol% or more of vinylidene chloride and other vinyl monomers, for example, vinyl chloride, acrylonitrile, acrylic acid, acrylic It is a copolymer with an acid ester, methacrylic acid, methacrylic acid ester and the like.
前記（１）の方法では、NBR加硫ゴムシート上に、塩
化ビニリデン系樹脂およびそれに対して約0.5〜10重量
％、好ましくは約１〜５重量％のポリイソシアネート、
例えばヘキサメチレンジイソシアネート、トリアリルイ
ソシアネートなどを固型分濃度が約0.5〜３重量％とな
るような量で、テトラヒドロフラン、ジオキサン、メチ
ルエチルケトンなどの有機溶媒中に溶解させた溶液をコ
ーティング液としてコーティングし、乾燥させて、ガス
バリヤー性シートが製造される。In the method (1), a vinylidene chloride-based resin and about 0.5 to 10% by weight, preferably about 1 to 5% by weight of a polyisocyanate are added on the NBR vulcanized rubber sheet.
For example, a solution obtained by dissolving hexamethylene diisocyanate, triallyl isocyanate, or the like in an organic solvent such as tetrahydrofuran, dioxane, or methyl ethyl ketone in an amount such that the solid component concentration is about 0.5 to 3% by weight is coated as a coating solution. After drying, a gas barrier sheet is produced.
また、前記（２）の方法では、塩化ビニリデン系樹脂
フィルム上に、イオウまたはイオウ系化合物を加硫剤と
するNBRの加硫配合物にNBRに対して約0.5〜４重量％、
好ましくは約0.8〜２重量％の上記の如きポリイソシア
ネートまたはジクミルパーオキサイド、アリルペルオキ
シカーボネート、2,5−ジメチル−2,5−（第３ブチルペ
ルオキシ）ヘキサンなどを添加し、固型分濃度が約0.5
〜５重量％となるような量で塩化メチレン、メリルエチ
ルケトンなどの有機溶媒中に溶解させたゴム糊をコーテ
ィングし、NBRの加硫温度で加熱加硫して、ガスバリヤ
ー性シートの製造が行われる。In the method (2), a vulcanizing compound of sulfur or a sulfur compound is used as a vulcanizing agent on a vinylidene chloride-based resin film.
Preferably, about 0.8 to 2% by weight of the above polyisocyanate or dicumyl peroxide, allyl peroxycarbonate, 2,5-dimethyl-2,5- (tert-butylperoxy) hexane or the like is added. Is about 0.5
A coating of rubber paste dissolved in an organic solvent such as methylene chloride or meryl ethyl ketone in an amount of up to 5% by weight, and vulcanization by heating at the vulcanization temperature of NBR to produce a gas barrier sheet. Done.
本発明方法で得られるポリイソシアネートまたは有機
過酸化物で共架橋させたガスバリヤー性シートは、耐屈
曲性にすぐれており、屈曲条件下に置かれてもガスバリ
ヤー性を低下させることがない。従って、前記（１）の
方法で得られたガスバリヤー性シートは、チューブ、ダ
イアフラムなどの成形に、また前記（２）の方法で得ら
れたガスバリヤー性シートは、チューブ、ダイヤフラ
ム、パッキンなどの成形に、それぞれ有効に用いられ
る。The gas barrier sheet co-crosslinked with the polyisocyanate or the organic peroxide obtained by the method of the present invention has excellent bending resistance, and does not lower the gas barrier property even under bending conditions. Therefore, the gas barrier sheet obtained by the method (1) is used for forming a tube, a diaphragm and the like, and the gas barrier sheet obtained by the method (2) is used for a tube, a diaphragm and a packing. Each is effectively used for molding.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例１ NBR（バイエル社製品perbunan N3807NS） 100重量部 MTカーボンブラック 30 酸化亜鉛 ３ ステアリン酸 １ テトラメチルチウラムジスルフィド ２ イオウ 0.8 ジオクチルフタレート ５ 以上の配合成分よりなる配合物を150℃で20分間加硫
し、厚さ2mmのNBR加硫シートを成形した。Example 1 100 parts by weight of NBR (Bayer's product perbunan N3807NS) MT carbon black 30 zinc oxide 3 stearic acid 1 tetramethylthiuram disulfide 2 sulfur 0.8 dioctyl phthalate 5 Then, an NBR vulcanized sheet having a thickness of 2 mm was formed.
この加硫シート上に、次の組成（重量部）を有するコ
ーティング液ＡまたはＢを、それぞれ20μｍの乾燥膜厚
になるようにコーティングし、40℃で30分間乾燥させ
た。The vulcanized sheet was coated with a coating liquid A or B having the following composition (parts by weight) to a dry film thickness of 20 μm and dried at 40 ° C. for 30 minutes.
これらのコーティングNBR加硫シートについて、1000
回屈曲（長さ50mmのシートを両端を25mm間隔に縮めて屈
曲させる操作を毎分50回の割合で20分間行った）前後の
窒素透過速度PN2（単位:cc・mm/24hrs・atm・m2）で測
定すると共に、屈曲試験後の状態を観察した。 For these coated NBR vulcanized sheets, 1000
Nitrogen permeation velocity PN 2 before and after bending (the operation of bending a 50 mm long sheet by shortening both ends to 25 mm intervals at 50 times per minute for 20 minutes) (unit: cc · mm / 24hrs · atm ·) m 2 ) and the state after the bending test was observed.
実施例２ 塩化ビニリデン系樹脂フィルム（旭化成製品サランUB
フィルム、厚さ25μｍ）上に、次の各成分からなる組成
（重量部）を有するゴム糊Ａ、ＢまたはＣを、それぞれ
７μｍの加硫膜厚になるようにコーティングし、150℃
で20分間加硫した。 Example 2 Vinylidene chloride resin film (Saran UB manufactured by Asahi Kasei Corporation)
A film, 25 μm thick) was coated with a rubber paste A, B or C having a composition (parts by weight) composed of the following components so as to have a vulcanized film thickness of 7 μm each.
For 20 minutes.
これらの加硫膜コーティングフィルムについて、実施
例１と同様の測定を行った。 The same measurement as in Example 1 was performed for these vulcanized film coating films.
Claims (2)
ート含有塩化ビニリデン系樹脂コーティング液をコーテ
ィングし、乾燥させることを特徴とするガスバリヤー性
シートの製造方法。1. A method for producing a gas barrier sheet, comprising coating an NBR vulcanized rubber sheet with a polyisocyanate-containing vinylidene chloride-based resin coating solution and drying.
イソシアネートまたは有機過酸化物含有NBR加硫配合物
溶液をコーティングし、加熱加硫することを特徴とする
ガスバリヤー性シートの製造方法。2. A method for producing a gas barrier sheet, comprising coating a vinylidene chloride-based resin film with an NBR vulcanizing compound solution containing a polyisocyanate or an organic peroxide, followed by heating and vulcanizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1094231A JP2751366B2 (en) | 1989-04-13 | 1989-04-13 | Method for producing gas barrier sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1094231A JP2751366B2 (en) | 1989-04-13 | 1989-04-13 | Method for producing gas barrier sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02270548A JPH02270548A (en) | 1990-11-05 |
| JP2751366B2 true JP2751366B2 (en) | 1998-05-18 |
Family
ID=14104537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1094231A Expired - Lifetime JP2751366B2 (en) | 1989-04-13 | 1989-04-13 | Method for producing gas barrier sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2751366B2 (en) |
-
1989
- 1989-04-13 JP JP1094231A patent/JP2751366B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02270548A (en) | 1990-11-05 |
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