JPS60149602A - Production of self-adhesive polymer - Google Patents
Production of self-adhesive polymerInfo
- Publication number
- JPS60149602A JPS60149602A JP523584A JP523584A JPS60149602A JP S60149602 A JPS60149602 A JP S60149602A JP 523584 A JP523584 A JP 523584A JP 523584 A JP523584 A JP 523584A JP S60149602 A JPS60149602 A JP S60149602A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polymerization
- monomer
- solution
- coated
- 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 11
- 239000002998 adhesive polymer Substances 0.000 title claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 61
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract 3
- -1 ethylene-ethylene Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 229920003169 water-soluble polymer Polymers 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract description 3
- 229920006026 co-polymeric resin Polymers 0.000 abstract description 2
- 229920003002 synthetic resin Polymers 0.000 description 13
- 239000000057 synthetic resin Substances 0.000 description 13
- 239000004809 Teflon Substances 0.000 description 7
- 229920006362 Teflon® Polymers 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- SSONCJTVDRSLNK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;hydrochloride Chemical compound Cl.CC(=C)C(O)=O SSONCJTVDRSLNK-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NSEMPCRVNANTIM-UHFFFAOYSA-N C.NC(=O)C=C Chemical class C.NC(=O)C=C NSEMPCRVNANTIM-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
に詳しくは、粘着性もしくは接着性の強い水溶性重合体
の製法であって、えられた重合体を重合容器から容易に
剥離することができるとともに、重合状態および重合率
の良好な重合体をうろことができる粘着性重合体の製法
に関する。DETAILED DESCRIPTION OF THE INVENTION In detail, it is a method for producing a water-soluble polymer with strong adhesiveness or adhesion, which allows the obtained polymer to be easily peeled from a polymerization container, and also allows for controlling the polymerization state and polymerization. The present invention relates to a method for producing a sticky polymer that can be coated with a good polymer content.
従来より、たとえば（メタ）アクリルアミド；（メタ）
アクリル酸塩： ＮＩＮ−ジアルキルアミノアルキル（
メタ）アクリレートの酸塩または４級塩、Ｎ，Ｎ−ジア
ルキルアミンヒドロキシアルキル（メタ）アクリレート
の酸塩または４級塩などの含チツ素アクリル酸エステル
類；ジアリルアミン酸性塩、ジアリルジアルキルアンモ
ニウム塩すどのジアリルアミン化合物；スルホアルキル
（〆夕）アクリレートｍｌメタ】アクリル酸ンチル、（
メタＪアクリル酸エチル、（メタ）アクリル酸ブチル、
（メタノアクリル酸ヒドロキシエチル、（メタ）アクリ
ル酸ヒドロキシプロピルなどの水不溶性（メタ）アクリ
Ａｌｔ！エステル類；アクリルアミドアルキルスルホン
酸塩、ジアルキル（メタ）アクリルアミドナトの（メタ
ンアクリルアミド誘導体；アクリロニトリル；ビニルス
ルホン酸またはその塩などのビニル基含有単量体を用い
て水溶性重合体を製造するばあい、一般に重合体の重合
度が高いものは比較的硬いゲルを生成するが、重合器壁
面への付着性、接着性が著しく、重合器壁面から重合体
を剥離することは容易ではない。また、重合度の低いも
のにおいてさえ壁面への付着性、接着性は強く、一旦壁
面に付着した生成重合体は実際問題として剥離しえない
ものである。Traditionally, for example, (meth)acrylamide; (meth)
Acrylate: NIN-dialkylaminoalkyl (
Ni-containing acrylic acid esters such as acid salts or quaternary salts of meth)acrylates, acid salts or quaternary salts of N,N-dialkylamine hydroxyalkyl (meth)acrylates; diallylamine acid salts, diallyldialkylammonium salts, etc. Diallylamine compound; sulfoalkyl acrylate ml meta] methyl acrylate, (
Meta J ethyl acrylate, butyl (meth)acrylate,
(Water-insoluble (meth)acrylic Alt! esters such as hydroxyethyl methanoacrylate and hydroxypropyl (meth)acrylate; acrylamide alkyl sulfonate, (methane acrylamide derivative of dialkyl (meth) acrylamide); acrylonitrile; vinyl sulfonic acid When producing water-soluble polymers using vinyl group-containing monomers such as vinyl group-containing monomers or their salts, polymers with a high degree of polymerization generally produce relatively hard gels, but they tend to adhere to the walls of the polymerization vessel. , the adhesion is remarkable, and it is not easy to peel the polymer from the wall of the polymerization vessel.In addition, even with a low degree of polymerization, the adhesion and adhesion to the wall are strong, and once the polymer is attached to the wall, it is difficult to peel off the polymer. As a practical matter, it cannot be peeled off.
通常これらの粘着性、接着性の大きい水溶性重合体を製
造するばあいは、重合器壁面に離型剤を塗布して剥離性
を改良する方法（たとえば特開昭第５３−４１３８６号
明細書］、重合容器壁面の輩擦抵抗を小さくするため、
たとえば電解研磨したステンレススチールを使用する方
法（たとえば特開昭第５４−１０３８７号明細書λ、あ
るいは重合容器壁面を合成樹脂で被覆して剥離性を改良
する方法（たとえば特開昭第５１−７３５８３号明細書
）などの処置を行なうことが広く知られている。Normally, when producing these water-soluble polymers with high adhesiveness and adhesiveness, a method of applying a mold release agent to the wall surface of the polymerization vessel to improve the releasability (for example, Japanese Patent Application Laid-open No. 53-41386) ], in order to reduce the friction resistance on the wall of the polymerization container,
For example, a method using electrolytically polished stainless steel (for example, JP-A No. 54-10387 λ) or a method of coating the polymerization vessel wall with a synthetic resin to improve releasability (for example, JP-A No. 51-73583) It is widely known that the following treatments are performed.
しかしながら上記方法のうち、離型剤を塗布する方法お
よび電解研磨した材質を使用する方法においては、重合
容器からの剥離性を改良するとはいえ、えられた水溶性
重合体の粘着性、接着性が大きいばあいは依然として剥
離が困離なままであり、根本的に改善しうるまでには到
達していない。However, among the above methods, the method of applying a mold release agent and the method of using an electrolytically polished material improve the tackiness and adhesion of the resulting water-soluble polymer, although they improve the releasability from the polymerization container. If it is large, peeling remains difficult, and a fundamental improvement has not yet been achieved.
一方、重合容器の壁面に合成樹脂を被覆する方法におい
ては、粘着性、接着性を有する重合体と重合容器との間
の剥離性が著しく改善されうろことは一般に認められて
いる。On the other hand, in the method of coating the wall surface of a polymerization container with a synthetic resin, it is generally recognized that the releasability between the polymer having adhesive properties and the polymerization container is significantly improved.
かかる合成樹脂としては、ポリエチレン、ゲリプロピレ
ン、ポリエステル、ポリアミド、ポリ四フッ化エチレン
、ポリ三フッ化塩化エチレン、ポリ塩化ビニル、エポキ
シ樹脂などが広く使用されている。なかでも、ポリ四フ
ッ化エチレン、ポリ三フッ化塩化エチレンなどの含７ツ
素系樹脂を使用したばあいの剥離性は優秀であると認め
られている。As such synthetic resins, polyethylene, gellipropylene, polyester, polyamide, polytetrafluoroethylene, polytrifluorochloroethylene, polyvinyl chloride, epoxy resin, etc. are widely used. Among these, it is recognized that the releasability of heptad-containing resins such as polytetrafluoroethylene and polytrifluorochloroethylene is excellent.
しかしながら、上記のごとき合成樹脂による被覆を施し
た重合容器を用いて前記ビニル糸単量体水溶液を重合す
るばあい、えられた水溶性重合体ゲルと合成樹脂との境
界面付近における重合状態は著しく不良であり、極端な
ばあいはその付近では反応終了後もビニル系単量体は反
応開始前の状態のままで残存し、重合率の低下および重
合体の収率の低下を惹起する。さらに、アクリルアミド
のごとき毒性の強い単量体や（メタ）アクリル酸エステ
ル類のごとき臭気の強い単量体のばあいにおいては、そ
のように未↑
反応単量体が大量に残存すると環境保全、操業安全性な
どの公害面の問題をもたらすことになる。However, when the vinyl yarn monomer aqueous solution is polymerized using a polymerization container coated with a synthetic resin as described above, the polymerization state near the interface between the resulting water-soluble polymer gel and the synthetic resin is In extreme cases, the vinyl monomer remains in the same state as it was before the reaction started even after the reaction is completed, causing a decrease in the polymerization rate and the yield of the polymer. Furthermore, in the case of highly toxic monomers such as acrylamide and monomers with strong odors such as (meth)acrylic acid esters, if large amounts of un↑-reacted monomers remain, environmental protection This will lead to pollution problems such as operational safety.
上記のような被覆された合成樹脂付近における示合不良
は、フィルム表面に存在する酸素が原因と考えられてい
る。The above-described poor alignment near the coated synthetic resin is thought to be caused by oxygen present on the film surface.
したがって合成樹脂被覆重合容器を使用する方法では、
重合挙動に悪影響を及ぼさない合成樹脂材質を選択する
必要がある。Therefore, in the method using a synthetic resin-coated polymerization container,
It is necessary to select a synthetic resin material that does not adversely affect polymerization behavior.
本発明者らは叙上の実情に鑑み、前記諸問題を排除し、
本質的に粘着性、接着性の大きな水溶性重合体を容易に
重合容器から剥離することができ、かつ重合体収率が改
善された重合体の製法を開発する目的で鋭意研究を重ね
た結果、本発明を完成するに至った。In view of the above-mentioned actual situation, the present inventors have eliminated the above-mentioned problems,
The result of extensive research aimed at developing a method for producing a water-soluble polymer that is inherently sticky and adhesive and that can be easily peeled off from a polymerization vessel and that has an improved polymer yield. , we have completed the present invention.
すなわち本発明は、本質的に粘着性もしくは接着性を有
する重合体もしくは共重合体の製法であって、不飽和二
重結合を有する重合性単量体溶液との接触部を四フッ化
エチレンーエチレン共重合体樹脂で被覆もしくは装着し
た重合装置を用いて重合することを特徴とする粘着性重
合体の製法を要旨とするものである。That is, the present invention is a method for producing a polymer or copolymer that essentially has adhesive or adhesive properties, in which the contact area with a solution of a polymerizable monomer having unsaturated double bonds is replaced with tetrafluoroethylene. The gist of this invention is a method for producing an adhesive polymer characterized by polymerization using a polymerization apparatus coated with or equipped with an ethylene copolymer resin.
本発明は数多くの合成樹脂について、重合に及ぼす影響
、えられる重合体の物性および合成樹脂と生成重合体と
の接着性、剥離性について実験を繰返した結果、四フッ
化エチレンーエチレン共重合体樹脂が重合を阻害するこ
となく優れた剥離性を有し、前記諸欠点を除失しうろこ
とを見出したものである。As a result of repeated experiments on the influence of many synthetic resins on polymerization, the physical properties of the resulting polymer, and the adhesion and peelability between the synthetic resin and the resulting polymer, the present invention was developed using a tetrafluoroethylene-ethylene copolymer. It has been discovered that the resin has excellent releasability without inhibiting polymerization and eliminates the above-mentioned drawbacks.
本発明−ｃ使用Ｔる四フッ化エチレンーエチレン共重合
体樹脂はフッ素系合成樹脂の１つではあるが、いわゆる
テフロン（ポリ四フッ化エチレンまたはポリ三フッ化塩
化エチレン）に比べてフィルム物性が全く異なり、とり
わけビニル系単量体を重合するばあいの重合に対する影
響は全く異質であり、テフロンを使用するばあいでは想
起しえない有用性を有している。Although the tetrafluoroethylene-ethylene copolymer resin used in the present invention-c is one of the fluorine-based synthetic resins, it has better film physical properties than so-called Teflon (polytetrafluoroethylene or polytrifluorochloride ethylene). In particular, when vinyl monomers are polymerized, the effects on polymerization are completely different, and they have usefulness that cannot be imagined when Teflon is used.
また、本発明で使用する四フッ化エチレンーエチレン共
重合体樹脂を今までに重合系に使用したという具体的例
証は見当らない。さらに、一般に使用されるポリ四フッ
化エチレンと比較して重合特性の優れていることを示唆
する文献モ見うれない。四フッ化エチレンーエチレン共
重合体樹脂を使用することは本発明により初めて提供さ
れる新規な技術である。Further, there has been no specific example of the use of the tetrafluoroethylene-ethylene copolymer resin used in the present invention in a polymerization system. Furthermore, no literature has been found suggesting that it has superior polymerization properties compared to commonly used polytetrafluoroethylene. The use of tetrafluoroethylene-ethylene copolymer resin is a novel technology provided for the first time by the present invention.
四フッ化エチレンーエチレン共重合体樹脂のテフロンに
対する優位点としては、たとえばつぎのようなものであ
る。For example, the advantages of tetrafluoroethylene-ethylene copolymer resin over Teflon are as follows.
（１）樹脂成形性が優れていること。したがってフイル
ムトシテ成形でキ、ヒートシール、ゴム、金属との複合
が容易で、重合容器への適用がテフロンより簡単である
こと。(1) Excellent resin moldability. Therefore, it is easy to combine with film adhesive molding, heat sealing, rubber, and metal, and it is easier to apply to polymerization containers than Teflon.
（２）機械特性に優れていること。とりわけ引張強度に
優れ、重合容器としての適用塵が高いこと。(2) Excellent mechanical properties. In particular, it has excellent tensile strength and is suitable for use as a polymerization container.
（８）ガス透過係数（ガス透過率）がテフロンに比べ非
常に小さく、シたがって酸素遮断効果に優れていること
。ならびにフィルム表面における酸素親和性が小さいた
め、テフロン使用における重大な欠点であるフィルム表
面での重合阻害が完全に排除しうろこと。このことは本
発明によってのみ発揮されるものであり、本発明の重要
なポイントである。(8) It has a much smaller gas permeability coefficient (gas permeability) than Teflon, and therefore has excellent oxygen blocking effects. In addition, since the film surface has low oxygen affinity, polymerization inhibition on the film surface, which is a serious drawback when using Teflon, can be completely eliminated. This is achieved only by the present invention, and is an important point of the present invention.
（４）耐候性に優れ、かつ紫外線劣化が殆んどないこと
。ならびに紫外線照射重合に必要な３００〜４００Ｍの
波長の紫外線透過性がテフロンより優れているため、紫
外線重合用容器としての材質に好適であること。(4) Excellent weather resistance and almost no UV deterioration. In addition, it is suitable as a material for a container for ultraviolet polymerization because it has better ultraviolet transmittance than Teflon at wavelengths of 300 to 400 M, which is necessary for ultraviolet irradiation polymerization.
本発明において重合容器は角型、円筒型などノ通常の容
器に四フッ化エチレンーエチレン共重合体樹脂を被覆ま
たは装着したものを用いるか、前記樹脂そのものからな
る袋を用いることができる。共重合体樹脂を被覆または
装着するばあい、そのフィルムの厚さは通常１０〜１０
０μｍ１好ましくは２５〜７５μｍである。In the present invention, the polymerization container may be a conventional container such as a square or cylindrical container coated or fitted with a tetrafluoroethylene-ethylene copolymer resin, or a bag made of the resin itself. When coating or attaching a copolymer resin, the thickness of the film is usually 10 to 10
0 μm, preferably 25 to 75 μm.
サラに、エンドレスベルトなどの可動式の支持体に四フ
ッ化エチレンーエチレン共重合体樹脂を被覆または装着
した上に薄層状に重合性不飽和二重結合を有する単量体
の水溶液を連続的に供給して重合せしめ、えられた重合
体を前記支持体から連続的に剥離することを特徴とする
粘着性重合体の製法においてはモノマーの連続重合が可
能となる。A movable support such as an endless belt is coated with or attached to a tetrafluoroethylene-ethylene copolymer resin, and then a thin layer of an aqueous solution of a monomer having polymerizable unsaturated double bonds is continuously applied. In the method for producing an adhesive polymer, which is characterized in that the monomer is supplied to the substrate for polymerization and the obtained polymer is continuously peeled off from the support, continuous polymerization of the monomer becomes possible.
本発明において重合は、たとえば過硫酸塩、アゾ系開始
剤、過酸化物などの通常使用される熱開始剤や、過硫酸
塩と亜硫酸カリウムとのレドックス系開始剤、過硫酸塩
とアミン系化合物とのレドックス系開始剤などを用いて
行なうことができる。またベンゾイン、ベンゾインアル
キルエーテル、ベンゾキノン類を用いる紫外線照射重合
法、またはγ線による放射線重合法を採用してもよい。In the present invention, polymerization is carried out using commonly used thermal initiators such as persulfates, azo initiators, peroxides, redox initiators of persulfates and potassium sulfite, persulfates and amine compounds, etc. This can be carried out using a redox initiator such as Further, an ultraviolet irradiation polymerization method using benzoin, benzoin alkyl ether, benzoquinones, or a radiation polymerization method using γ rays may be employed.
以下、実施例に基づいて本発明をさらに詳しく説明する
が、もとより本発明はかかる実施例のみに限定されるも
のではない。Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.
実施例１および比較例１．２
チッ素吹込管および温度計が取付けられ、両側より冷却
水ジャケットが設けられた箱型のステンレス鋼製重合容
器（１００ｍｍ Ｘ １００ｍ＋ｎ Ｘ １００ｍｍ
）の内面に第１表に示す各種合成樹脂フィルム（厚さ５
０μｍ）をそれぞれ被覆した重合容器に、アクリルアミ
ド１００ アクリル酸２５．および水酸化１
ナトリウム１４．を２７０ｍ６の蒸留水に溶解した単騎
体水溶液を仕込み、ついでチッ素ガス置換を行なって溶
存酸素を除去したのち、５％過硫酸カリウム液５ｍ１ｌ
と５％亜硫酸ナトリウム液６ｍｌとを加え、ジャケット
内に２５ｃ）Ｌ３の水を通じながら３時間重合し、合成
樹脂材質の重合挙動に及ぼす影響および生成重合体ゲル
と重合容器表面との接着性を評価した。結果を第１表に
示す。Example 1 and Comparative Example 1.2 A box-shaped stainless steel polymerization vessel (100 mm x 100 m+n
) on the inner surface of the various synthetic resin films shown in Table 1 (thickness 5
Acrylamide 100 and acrylic acid 25. and sodium hydroxide 14. Pour a monomer aqueous solution prepared by dissolving 270 m6 of distilled water, then perform nitrogen gas replacement to remove dissolved oxygen, and add 5 ml of 5% potassium persulfate solution.
and 6 ml of 5% sodium sulfite solution, and polymerized for 3 hours while passing 25 c) L3 of water into the jacket to evaluate the effect on the polymerization behavior of the synthetic resin material and the adhesion between the resulting polymer gel and the surface of the polymerization container. did. The results are shown in Table 1.
なお、第１表中に示す各評価方法はそれぞれつきのよう
であった。It should be noted that each evaluation method shown in Table 1 seemed to be the same.
重合状態：Ｏ重合容器内全体に均一に重合しているもの
× 重合容器壁面付近において未反応液が多量に残存し
ているもの
重 含率：生成した重合体の中心部を約３ｃｍの厚みに
横断状に切取り、肉挽き機で均一化したのち、ＫＢｒＯ
３法によって測定した。Polymerization state: O Polymerization is uniform throughout the entire interior of the polymerization container × A large amount of unreacted liquid remains near the wall of the polymerization container Polymerization content: The center of the produced polymer is approximately 3 cm thick. After cutting it into a crosswise shape and homogenizing it with a meat grinder, KBrO
It was measured by three methods.
剥 離 性：人 容器を逆さにすると自然剥離するか、
または逆さにした容器の上部を軽くたたくことにより剥
離するもの
Ｂ 多少の人力によって剥離するが、容器を逆さにして
も自然剥離しないもの
実施例２および比較例６．４
Ｎ、Ｎ、Ｎ−１−ツメチルアミノエチルメタクリレート
クロライド８０％水溶液５００．を採取し、１０％塩化
水素水溶液を用いてｐＨ４に調製したのち、蒸留水で全
量を５６５．としたものを実施例１で用いた重合容器に
仕込み、以下実施例１と同様にして重合、測定、評価を
行なった。結果を第１表に示す。Peelability: Human Does it peel off naturally when the container is turned upside down?
Or one that peels off by lightly tapping the top of an inverted container B. One that peels off with some manual force, but does not peel off naturally even if the container is turned upside down. Example 2 and Comparative Example 6.4 N, N, N-1 -Trimethylaminoethyl methacrylate chloride 80% aqueous solution 500. After adjusting the pH to 4 using a 10% aqueous hydrogen chloride solution, the total amount was adjusted to 565% with distilled water. The obtained product was charged into the polymerization container used in Example 1, and polymerization, measurement, and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 1.
実施例３および比較例５．６
アクリルアミド１００ アクリル酸２５ｇおよび１
アクリル酸１チルエステル１５ を６００９の蒸留水り
に溶解し、４０％水酸化ナトリウム水溶液３５．を加え
てＩ）Ｈ７，５に調製した単量体水溶液を実施例１で用
いた重合容器に仕込み、以下実施例１と同様にして重合
、測定、評価を行なった。結果を第１表に示す。Example 3 and Comparative Example 5.6 Acrylamide 100 acrylic acid 25 g and acrylic acid 1 thyl ester 15 were dissolved in 6009 distilled water and 40% sodium hydroxide aqueous solution 35. The aqueous monomer solution prepared by adding I) H7.5 was charged into the polymerization vessel used in Example 1, and polymerization, measurement, and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 1.
第 １ 表
実施例４および比較例７．８
表面に四フッ化エチレンーエチレン共重合゛体フィルム
（厚さ５０μｍ）を装着した幅４５０ｍｍ 、有効長６
．０００ ｍｍのステンレス鋼製のエンドレスベルトの
裏面に温水〜冷水を噴霧しうる構造としたものを重合用
の可動式の支持体として、チッ素ガスで完全に充満され
た室内に設置し、３０ｍｍ／分の定速度で可動せしめ、
ベルトの裏面に６０％の水を噴霧した。Table 1 Example 4 and Comparative Example 7.8 Width 450 mm, effective length 6 with tetrafluoroethylene-ethylene copolymer film (thickness 50 μm) attached to the surface
．． A 000 mm stainless steel endless belt with a structure that allows hot to cold water to be sprayed on the back side was used as a movable support for polymerization, and was installed in a room completely filled with nitrogen gas. Move at a constant speed of minutes,
The back side of the belt was sprayed with 60% water.
１０％塩化水素水溶液でｐＨ４に調製された７５％濃度
のＮ、Ｎ、Ｎ−）ジメチルアミ７エチルメタクリレート
モノマー水溶液約３０１をチッ素ガスにより充分脱気し
、可動状態にある前記ベルト上に１０１／時間の速度で
該ベルトの一端力）ら定量供給した。Approximately 30 liters of a 75% concentration N,N,N-) dimethylami7ethyl methacrylate monomer aqueous solution adjusted to pH 4 with a 10% aqueous hydrogen chloride solution was thoroughly degassed with nitrogen gas, and 10 1/ A fixed amount was supplied from one end of the belt at a rate of 1 hour.
また、ベルト上部に設置した攪拌機付き一時貯槽（５１
容量ンに重合開始剤として５％過硫酸カリウム溶液およ
び亜硫酸す） ＩＪウム溶液を設置し、それぞれ７０−
７時間の速度で供給し、混合しながら上記モノマー水溶
液に加え、均一混合しながら前記ベルト上に連続的に供
給する。In addition, a temporary storage tank (51
A 5% potassium persulfate solution and a 5% potassium persulfate solution and an IJ solution were placed as polymerization initiators in the tank, and the solution was 70-70% each.
It is fed at a rate of 7 hours, added to the monomer aqueous solution while mixing, and continuously fed onto the belt while being mixed uniformly.
前記条件においては、モノマー水溶液がベルト上で重合
に供される時間は１００分間、重合時におけるモノマー
水溶液層は約１２ｍｍおよび全重合所要時間は２時間で
あった。Under the above conditions, the time during which the monomer aqueous solution was subjected to polymerization on the belt was 100 minutes, the monomer aqueous solution layer during polymerization was about 12 mm, and the total polymerization time was 2 hours.
モノマー水溶液供給開始から１００分後にエンドレスベ
ルトの他端より約１２ｍｍの厚さのソート状の重合体か
えられた。えられた重合体はベルト表面から人力によっ
て容易に剥離される状態にあって約６時間の連続重合が
可能であった。100 minutes after the start of supply of the monomer aqueous solution, a sorted polymer with a thickness of about 12 mm was transferred from the other end of the endless belt. The obtained polymer could be easily peeled off from the belt surface by hand, and continuous polymerization for about 6 hours was possible.
比較のため四フッ化エチレンーエチレン共重合体フィル
ムを装着しない他は全て前記と同様にしてエンドレスベ
ルト上で重合を行なツタ（比較例７）ところ、生成した
重合体はベルト表面から人力ｆは容易に剥離されなかっ
た。また機械を使用して剥離を試みたところ、重合体シ
ートが引裂かれてしまい、連続的剥離が行なえず、連続
重合は不可能であった。For comparison, polymerization was carried out on an endless belt in the same manner as above except that the tetrafluoroethylene-ethylene copolymer film was not attached (Comparative Example 7). was not easily peeled off. When peeling was attempted using a machine, the polymer sheet was torn, making continuous peeling impossible and making continuous polymerization impossible.
また、四フッ化エチレンーエチレン共Ｊ１体フイルムニ
代えて、四フッ化エチレン重合体フィルム（厚さ５０μ
ｍ）を装着した他は全て実施例４に準じて同様の重合を
実施した（比較例８）。In addition, instead of the tetrafluoroethylene-ethylene J1 film, a tetrafluoroethylene polymer film (thickness 50μ
The same polymerization was carried out in accordance with Example 4 except that m) was installed (Comparative Example 8).
えられた重合体ソートは人力により容易に剥離できたが
、該重合体シートと四フッ化エチレン重合体フィルムと
の界面には未重合のモノマー液が多量に存在し、連続重
合の観点からは工業的価値は見出せなかった。The resulting polymer sort could be easily peeled off manually, but a large amount of unpolymerized monomer liquid existed at the interface between the polymer sheet and the tetrafluoroethylene polymer film, making it difficult to perform continuous polymerization. No industrial value was found.
手続補正書（方式）
％式％
１事件の表示
昭和５９年特許願第 ５２３５ 号
２発明の名称
粘着性重合体の製法
３補正をする者
事件との関係 特許出願人
５補正の対象
（１）願 書
６補正の内容
（１）願書の右肩に「（特許法第６８条ただし書の規定
による特許出願）」なる表示を追加する。Procedural amendment (method) % formula % 1 Indication of the case Patent Application No. 5235 of 1982 2 Name of the invention 3 Process for producing adhesive polymer 3 Relationship with the case Patent applicant 5 Subject of amendment (1) Contents of amendment 6 to the application form (1) Add the indication “(Patent application pursuant to the proviso to Article 68 of the Patent Act)” to the right shoulder of the application form.
（２）願書の５行のあとに「特許請求の範囲に記載され
た発明の数２」なる記載を追加する。(2) After line 5 of the application, add the following statement: "Number of inventions stated in the scope of claims: 2".
以 上that's all
Claims (1)
くは共重合体の製法であって、不飽和二重結合を有する
重合性単量体溶液との接触部を四フッ化エチレンーエチ
レン共重合体樹脂で被覆もしくは装着した重合装置を用
いて重合することを特徴とする粘着性重合体の製法。 ２ 重合性の不飽和二重結合を有する単量体の水溶液を
重合することによる強い粘着性を有する水溶性重合体の
製法であって、四フッ化エチレンーエチレン共重合体樹
脂を被覆もしくは装着した可動式の支持体の上に薄層状
に該単量体の水溶液を連続的に供給して重合せしめ、え
られた重合体を前記支持体から連続的に剥離することを
特徴とする粘着性重合体の製法。[Claims] 1. A method for producing a polymer or copolymer that essentially has adhesive or adhesive properties, wherein the contact area with a solution of a polymerizable monomer having an unsaturated double bond is tetrafluorinated. A method for producing an adhesive polymer, which comprises polymerizing using a polymerization device coated with or equipped with an ethylene-ethylene copolymer resin. 2. A method for producing a water-soluble polymer with strong adhesiveness by polymerizing an aqueous solution of a monomer having a polymerizable unsaturated double bond, the method comprising coating or attaching a tetrafluoroethylene-ethylene copolymer resin. adhesive, characterized in that an aqueous solution of the monomer is continuously supplied in a thin layer onto a movable support, polymerized, and the resulting polymer is continuously peeled off from the support. Polymer manufacturing method.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP523584A JPS60149602A (en) | 1984-01-13 | 1984-01-13 | Production of self-adhesive polymer |
| CA000471208A CA1226699A (en) | 1984-01-13 | 1984-12-28 | Process for preparing sticky polymers |
| US06/689,004 US4604411A (en) | 1984-01-13 | 1985-01-04 | Process for preparing sticky polymers |
| DE19853500475 DE3500475A1 (en) | 1984-01-13 | 1985-01-09 | METHOD FOR PRODUCING A TACKY WATER-SOLUBLE POLYMER |
| FI850125A FI81367C (en) | 1984-01-13 | 1985-01-11 | FORMING A FRAME POLYMER FRAMSTAELLNING AV KLIBBIGA POLYMERER. |
| FR8500370A FR2563225B1 (en) | 1984-01-13 | 1985-01-11 | PROCESS FOR THE PREPARATION OF ADHESIVE POLYMERS |
| CN85104556.1A CN1003303B (en) | 1984-01-13 | 1985-06-14 | Process for preparing sticky polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP523584A JPS60149602A (en) | 1984-01-13 | 1984-01-13 | Production of self-adhesive polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60149602A true JPS60149602A (en) | 1985-08-07 |
| JPS645045B2 JPS645045B2 (en) | 1989-01-27 |
Family
ID=11605527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP523584A Granted JPS60149602A (en) | 1984-01-13 | 1984-01-13 | Production of self-adhesive polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60149602A (en) |
-
1984
- 1984-01-13 JP JP523584A patent/JPS60149602A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS645045B2 (en) | 1989-01-27 |
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