JP3393685B2 - Method for producing hydrogenated NBR latex - Google Patents
Method for producing hydrogenated NBR latexInfo
- Publication number
- JP3393685B2 JP3393685B2 JP22823893A JP22823893A JP3393685B2 JP 3393685 B2 JP3393685 B2 JP 3393685B2 JP 22823893 A JP22823893 A JP 22823893A JP 22823893 A JP22823893 A JP 22823893A JP 3393685 B2 JP3393685 B2 JP 3393685B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogenated nbr
- fatty acid
- nbr latex
- dissolved
- added
- 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 - Fee Related
Links
- 229920000126 latex Polymers 0.000 title claims description 29
- 239000004816 latex Substances 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 14
- 239000000194 fatty acid Substances 0.000 claims description 14
- 229930195729 fatty acid Natural products 0.000 claims description 14
- 150000004665 fatty acids Chemical class 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 4
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical group [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229920000459 Nitrile rubber Polymers 0.000 description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000003995 emulsifying agent Substances 0.000 description 9
- -1 fatty acid salt Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001993 dienes Chemical group 0.000 description 2
- 229960000878 docusate sodium Drugs 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- IJBUWXMVBNUVME-UHFFFAOYSA-N 1,4-di(nonoxy)-1,4-dioxobutane-2-sulfonic acid Chemical compound CCCCCCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCCCCC IJBUWXMVBNUVME-UHFFFAOYSA-N 0.000 description 1
- OMMMUWNDGQFGDV-UHFFFAOYSA-N 1,4-didodecoxy-1,4-dioxobutane-2-sulfonic acid Chemical compound CCCCCCCCCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCCCCCCCC OMMMUWNDGQFGDV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 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
- 239000012074 organic phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、粒子径が小さく静置安
定性に優れた水素化ＮＢＲ（ニトリルブタジエンラバ
ー）ラテックスの製造方法に関する。本発明に係る水素
化ＮＢＲラテックスは、基材のコーティング塗膜を形成
させるときに高い耐熱性、耐油性、老化防止性を有する
ところから、繊維表面処理剤やプラスチック、フィルム
又はシートのコーティング剤として極めて有用である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrogenated NBR (nitrile butadiene rubber) latex having a small particle size and excellent static stability. The hydrogenated NBR latex according to the present invention has high heat resistance, oil resistance, and anti-aging property when forming a coating film for a base material, and therefore, as a coating agent for fiber surface treatment agents, plastics, films or sheets. Extremely useful.
【０００２】[0002]
【従来の技術】水素化ＮＢＲラテックスの製造方法とし
てはこれまで、水素化ＮＢＲをトルエン／ジクロロエタ
ン等の有機溶媒に溶解し、乳化剤を溶解させた水と混合
し、ホモミキサー等を用いて乳化を行い、その後有機溶
剤を除去する方法が知られている（特開昭６２−２０１
９４５号公報）。2. Description of the Related Art As a method for producing hydrogenated NBR latex, until now, hydrogenated NBR was dissolved in an organic solvent such as toluene / dichloroethane, mixed with water in which an emulsifier was dissolved, and emulsified using a homomixer or the like. A method is known in which the organic solvent is removed and then the organic solvent is removed (Japanese Patent Laid-Open No. 62-201).
945).
【０００３】しかしながら、ジクロロエタン等のハロゲ
ン化炭化水素系の溶剤は人体に有害な物質であり、近年
は環境汚染の問題から使用が規制される方向にある。こ
のような溶剤の生産的規模での大量使用を伴うこの方法
には上記の問題点があった。However, halogenated hydrocarbon solvents such as dichloroethane are substances harmful to the human body, and their use has recently been restricted due to the problem of environmental pollution. This method, which involves the large-scale use of such a solvent on a production scale, has the above-mentioned problems.
【０００４】また、最近、ラテックス粒子の小粒子径化
及び静置安定性の向上によって、汎用ゴムラテックスの
基本性能を向上させることが求められるようになってき
た。しかしながら、上記製造方法のような公知の方法に
よっては、製造されるラテックス粒子は充分に小さくな
く、また使用する乳化剤の量に比して得られる静置安定
性も充分ではないという問題点を有していた。Recently, it has been required to improve the basic performance of a general-purpose rubber latex by reducing the particle size of latex particles and improving the stationary stability. However, according to known methods such as the above-mentioned production method, the latex particles produced are not sufficiently small, and the stationary stability obtained based on the amount of the emulsifier used is not sufficient. Was.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、上記
に鑑み、有害な物質を使用することなく、ラテックス粒
子の粒子径が充分に小さくかつ充分な静置安定性を有す
る水素化ＮＢＲラテックスを製造する方法を提供するこ
とにある。SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide a hydrogenated NBR latex having a latex particle having a sufficiently small particle size and sufficient stationary stability without using a harmful substance. It is to provide a method of manufacturing.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、水素化Ｎ
ＢＲラテックスを製造する方法において、その処理条
件、乳化剤の種類とその量等について鋭意研究の結果、
ついに本発明に到達したものである。The present inventors have found that hydrogenated N
In the method for producing BR latex, as a result of intensive research on the treatment conditions, the type and amount of emulsifier, etc.,
Finally, the present invention has been reached.
【０００７】本発明の要旨は、即ち、水素化ＮＢＲ及び
炭素数６〜２４のアルキル基を有する脂肪酸を溶解した
有機溶剤溶液並びに水酸化アルカリ金属を溶解した水を
混合後、乳化を行い、その後有機溶剤を留去することに
より水素化ＮＢＲラテックスを製造する方法において、
水酸化アルカリ金属を溶解した水中にジアルキルスルホ
コハク酸塩を添加した後、水素化ＮＢＲ及び炭素数６〜
２４のアルキル基を有する脂肪酸を溶解した有機溶剤溶
液と混合するところにある。The gist of the present invention is that of hydrogenated NBR and
A hydrogenated NBR latex is produced by mixing an organic solvent solution in which a fatty acid having an alkyl group having 6 to 24 carbon atoms is dissolved and water in which an alkali metal hydroxide is dissolved, followed by emulsification, and then distilling off the organic solvent. In the method
After adding a dialkylsulfosuccinate in water in which an alkali metal hydroxide is dissolved, hydrogenated NBR and a carbon number of 6 to
It is about to be mixed with an organic solvent solution in which a fatty acid having 24 alkyl groups is dissolved.
【０００８】以下に本発明を詳述する。本発明において
原料として使用される水素化ＮＢＲとしては、例えば、
不飽和ニトリル−共役ジエン共重合ゴムの共役ジエン単
位を水素化したもの、不飽和ニトリル−共役ジエン−エ
チレン性不飽和モノマー−三元共重合ゴムの共役ジエン
単位を水素化したもの等が挙げられる。これらの共重合
体ゴムは、通常の重合手法及び通常の水素化方法を用い
ることにより得られる。The present invention will be described in detail below. Examples of the hydrogenated NBR used as a raw material in the present invention include:
Hydrogenated conjugated diene units of unsaturated nitrile-conjugated diene copolymer rubber, unsaturated nitrile-conjugated diene-ethylenically unsaturated monomer-hydrogenated conjugated diene units of terpolymer rubber, and the like. . These copolymer rubbers can be obtained by using a usual polymerization method and a usual hydrogenation method.
【０００９】このようなものとして、例えば、ブタジエ
ン−アクリロニトリル共重合ゴム、イソプレン−ブタジ
エン−アクリロニトリル共重合ゴム、ブタジエン−メチ
ルメタクリレート−アクリロニトリル共重合体、ブタジ
エン−エチレン−アクリロニトリル共重合体等を水素化
したものが挙げられる。As such, for example, butadiene-acrylonitrile copolymer rubber, isoprene-butadiene-acrylonitrile copolymer rubber, butadiene-methyl methacrylate-acrylonitrile copolymer, butadiene-ethylene-acrylonitrile copolymer, etc. have been hydrogenated. There are things.
【００１０】本発明において添加される脂肪酸は、一般
式Ｒ1 ＣＯＯＨ（式中Ｒ1 は炭素数６〜２４のアルキル
を表す。）で表すことができる化合物である。このよう
なものとして、例えば、オレイン酸、ステアリン酸、ラ
ウリン酸、ミリスチン酸、パルミチン酸等を挙げること
ができるが、それらの中で特にオレイン酸を使用した場
合に好ましい結果が得られる。The fatty acid added in the present invention is a compound which can be represented by the general formula R 1 COOH (wherein R 1 represents alkyl having 6 to 24 carbon atoms). Examples of such substances include oleic acid, stearic acid, lauric acid, myristic acid, and palmitic acid. Among them, preferred results are obtained when oleic acid is used.
【００１１】本発明において、上記脂肪酸の使用量とし
ては、水素化ＮＢＲ１００重量部に対して１〜１０重量
部が好ましい。より好ましくは、２〜７重量部である。
１重量部未満の添加量では好ましい乳化状態を得ること
ができず、また１０重量部を越えて用いる場合は、乳化
は容易であっても、乳化剤量が多くなり、経済的でなく
なるばかりでなく、得られる水素化ＮＢＲラテックスの
物性が劣化することが多い。In the present invention, the amount of the fatty acid used is preferably 1 to 10 parts by weight with respect to 100 parts by weight of hydrogenated NBR. More preferably, it is 2 to 7 parts by weight.
If the amount added is less than 1 part by weight, a preferable emulsified state cannot be obtained, and if it is used in excess of 10 parts by weight, not only is the emulsification easy but the amount of emulsifier increases, which is not economical. The physical properties of the obtained hydrogenated NBR latex often deteriorate.
【００１２】本発明において使用される有機溶剤として
は、特に限定されることはないが、例えば、ベンゼン、
トルエン、キシレン等の芳香族炭化水素系溶剤、メチル
エチルケトン、メチルイソブチルケトン等のケトン系溶
剤等から選ばれたものを適宜選定し、単独又は混合して
用いることができる。本発明において使用される水酸化
アルカリ金属としては、例えば、水酸化ナトリウム、水
酸化カリウム等を挙げることができる。使用量は、添加
される脂肪酸に対し０．５〜５倍モル量が好ましい。The organic solvent used in the present invention is not particularly limited, but for example, benzene,
A solvent selected from aromatic hydrocarbon solvents such as toluene and xylene and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be appropriately selected and used alone or in combination. Examples of the alkali metal hydroxide used in the present invention include sodium hydroxide and potassium hydroxide. The amount used is preferably 0.5 to 5 times the molar amount of the fatty acid added.
【００１３】前記した脂肪酸は、乳化の際、水相と有機
相との界面で、水中に溶解された水酸化アルカリ金属と
反応し、脂肪酸塩を形成することにより、乳化剤として
有効に働く。During the emulsification, the above-mentioned fatty acid reacts with the alkali metal hydroxide dissolved in water at the interface between the aqueous phase and the organic phase to form a fatty acid salt, thereby effectively acting as an emulsifier.
【００１４】本発明において使用されるジアルキルスル
ホコハク酸塩は、下記の一般式〔Ｉ〕（式中Ｙはナトリ
ウム又はカリウムを表し、Ｒ2 、Ｒ3 は、同一又は異な
って、炭素数５〜１２のアルキルを表す）で表される化
合物である。The dialkyl sulfosuccinate used in the present invention has the following general formula [I] (wherein Y represents sodium or potassium, R 2 and R 3 are the same or different and have 5 to 12 carbon atoms). Represents an alkyl) of).
【００１５】[0015]
【化１】 [Chemical 1]
【００１６】このような物質として、例えば、ジオクチ
ルスルホコハク酸塩、ジノニルスルホコハク酸塩、ジド
デシルスルホコハク酸塩等を挙げることができる。それ
らの中でも特にジオクチルスルホコハク酸塩を使用した
場合に好ましい結果が得られる。Examples of such substances include dioctyl sulfosuccinate, dinonyl sulfosuccinate, didodecyl sulfosuccinate and the like. Among them, particularly when dioctyl sulfosuccinate is used, preferable results are obtained.
【００１７】また、用いる有機溶剤の種類によっては、
このジアルキルスルホコハク酸塩と併用して、アルキル
ベンゼンスルホン酸ソーダやアルキル硫酸エステルのナ
トリウム塩等のアニオン系乳化剤、ポリオキシエチレン
アルキルエーテル、ポリオキシエチレンアルキルフェニ
ルエーテル等のノニオン系乳化剤を用いることもでき
る。Further, depending on the type of organic solvent used,
Anionic emulsifiers such as sodium alkylbenzene sulfonate and sodium salts of alkyl sulfates, and nonionic emulsifiers such as polyoxyethylene alkyl ethers and polyoxyethylene alkylphenyl ethers can be used in combination with the dialkyl sulfosuccinate.
【００１８】本発明においては、ジアルキルスルホコハ
ク酸塩の添加量は、水素化ＮＢＲ１００重量部に対して
０．３〜７重量部が好ましく、より好ましくは０．５〜
４重量部である。０．３重量部未満の量では好ましい乳
化状態が得られず、７重量部を越えて用いることは、乳
化は容易であっても、経済的でなくなるばかりでなく、
得られる水素化ＮＢＲラテックスの物性が劣化すること
が多いので好ましくない。In the present invention, the amount of the dialkyl sulfosuccinate added is preferably 0.3 to 7 parts by weight, more preferably 0.5 to 7 parts by weight, based on 100 parts by weight of hydrogenated NBR.
4 parts by weight. When the amount is less than 0.3 parts by weight, a preferable emulsified state cannot be obtained, and when it is used in excess of 7 parts by weight, not only is the emulsification easy, but it is not economical.
The hydrogenated NBR latex obtained often deteriorates in physical properties, which is not preferable.
【００１９】本発明においては、乳化は、適当な剪断力
を有する乳化機、例えば、ホモジナイザー、コロイドミ
ル、超音波分散機等を用い、充分に混合を行うことによ
り実施することができる。In the present invention, the emulsification can be carried out by using an emulsifying machine having an appropriate shearing force, for example, a homogenizer, a colloid mill, an ultrasonic disperser, etc. and thoroughly mixing them.
【００２０】本発明においては、乳化を行った後、有機
溶剤を減圧下、加熱等により留去することにより、水素
化ＮＢＲラテックスを得ることができる。In the present invention, after emulsification, the hydrogenated NBR latex can be obtained by distilling off the organic solvent by heating under reduced pressure.
【００２１】また、必要に応じて、ラテックスが所望の
濃度になるまで、加熱濃縮、遠心分離又は湿式分離等の
操作により濃縮することもできる。If necessary, the latex can be concentrated to a desired concentration by an operation such as heat concentration, centrifugation or wet separation.
【００２２】[0022]
【実施例】以下に実施例により本発明を更に詳しく説明
するが、本発明はこれらに限定されるものではない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
【００２３】実施例１
水素化ＮＢＲ（商品名；テルバン１７６７、バイエルジ
ャパン社製、アクリロニトリル含有量３４ｗｔ％、残存
二重結合量５．５％）３０ｇをメチルイソブチルケトン
２７０ｇに溶解後、オレイン酸１．５ｇを添加した。一
方、水酸化カリウム０．３ｇを溶解した水１５０ｇに、
ジオクチルスルホコハク酸ナトリウム０．６ｇを溶かし
たものを用意し、二つの溶液をＴＫホモミキサー（特殊
機化工業社製 Ｍ型）を用いて回転数１２０００ｒｐｍ
で１０分間混合攪拌して乳化した。この乳化液を減圧
下、加熱することにより、メチルイソブチルケトンを留
去し、水素化ＮＢＲのラテックスを得た。中位粒子径は
０．８０μｍであり、相分離もなく安定なものであっ
た。Example 1 30 g of hydrogenated NBR (trade name; Telban 1767, manufactured by Bayer Japan Ltd., acrylonitrile content 34 wt%, residual double bond amount 5.5%) was dissolved in 270 g of methyl isobutyl ketone, and then oleic acid 1 was added. 0.5 g was added. On the other hand, in 150 g of water in which 0.3 g of potassium hydroxide was dissolved,
A solution prepared by dissolving 0.6 g of sodium dioctylsulfosuccinate was prepared, and the two solutions were rotated using a TK homomixer (M type manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotation speed of 12000 rpm.
And mixed and stirred for 10 minutes to emulsify. By heating this emulsion under reduced pressure, methyl isobutyl ketone was distilled off to obtain a hydrogenated NBR latex. The median particle diameter was 0.80 μm, and it was stable without phase separation.
【００２４】実施例２
水素化ＮＢＲ（商品名；テルバン１９０７、バイエルジ
ャパン社製、アクリロニトリル含有量３８ｗｔ％、残存
二重結合量１．０％以下）３０ｇをメチルイソブチルケ
トン２７０ｇに溶解後、オレイン酸１．２ｇを添加し
た。一方、水酸化カリウム０．２４ｇを溶解した水１５
０ｇに、ジオクチルスルホコハク酸ナトリウム０．９ｇ
を溶かしたものを用意し、二つの溶液をＴＫホモミキサ
ー（特殊機化工業社製 Ｍ型）を用いて回転数１２００
０ｒｐｍで１０分間混合攪拌して乳化した。この乳化液
を減圧下、加熱することにより、メチルイソブチルケト
ンを留去し、水素化ＮＢＲのラテックスを得た。中位粒
子径は０．８８μｍであり、相分離もなく安定なもので
あった。Example 2 30 g of hydrogenated NBR (trade name; Telban 1907, manufactured by Bayer Japan Ltd., acrylonitrile content 38 wt%, residual double bond amount 1.0% or less) was dissolved in 270 g of methyl isobutyl ketone, and then oleic acid was added. 1.2 g was added. On the other hand, water 15 in which 0.24 g of potassium hydroxide was dissolved
0 g to 0.9 g of sodium dioctyl sulfosuccinate
Was prepared and the two solutions were rotated using a TK homomixer (M type manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotation speed of 1200.
The mixture was mixed and stirred at 0 rpm for 10 minutes to emulsify. By heating this emulsion under reduced pressure, methyl isobutyl ketone was distilled off to obtain a hydrogenated NBR latex. The median particle diameter was 0.88 μm, and it was stable without phase separation.
【００２５】実施例３
水素化ＮＢＲ（商品名；テルバン１７６７、バイエルジ
ャパン社製、アクリロニトリル含有量３４ｗｔ％、残存
二重結合量５．５％）３０ｇをトルエン３００ｇに溶解
後、オレイン酸１．２ｇを混合した。一方、水酸化カリ
ウム０．２４ｇを溶解した水１６５ｇに、ジオクチルス
ルホコハク酸ナトリウム０．６ｇ、ポリオキシエチレン
オクチルフェニルエーテル硫酸エステルソーダ塩０．２
ｇを溶かしたものを用意し、二つの溶液をＴＫホモミキ
サー（特殊機化工業社製 Ｍ型）を用いて回転数１２０
００ｒｐｍで１０分間混合攪拌して乳化した。この乳化
液を減圧下、加熱することにより、トルエンを留去し、
水素化ＮＢＲのラテックスを得た。得られた乳化物の中
位粒子径は０．９５μｍであり、相分離もなく安定なも
のであった。Example 3 30 g of hydrogenated NBR (trade name: Telban 1767, manufactured by Bayer Japan, acrylonitrile content 34 wt%, residual double bond amount 5.5%) was dissolved in 300 g of toluene, and then 1.2 g of oleic acid was dissolved. Were mixed. On the other hand, in 165 g of water in which 0.24 g of potassium hydroxide was dissolved, 0.6 g of sodium dioctylsulfosuccinate and 0.2 sodium polyoxyethylene octylphenyl ether sulfate ester soda salt were added.
Prepare a solution in which g is dissolved, and use two solutions with a TK homomixer (M type manufactured by Tokushu Kika Kogyo Co., Ltd.) to rotate at 120
The mixture was mixed and stirred at 00 rpm for 10 minutes to emulsify. By heating this emulsion under reduced pressure, toluene is distilled off,
A latex of hydrogenated NBR was obtained. The median particle diameter of the obtained emulsion was 0.95 μm, and it was stable without phase separation.
【００２６】比較例１〜３
乳化剤の種類を脂肪酸とジアルキルスルホコハク酸塩の
組み合わせの代わりに表１に示した各種乳化剤を用いた
以外は、実施例１と同様の条件で水素化ＮＢＲラテック
スの製造を行った。いずれの乳化剤を用いた場合も小粒
子径のラテックスは得られず、静置安定性も悪いもので
あった。Comparative Examples 1 to 3 Preparation of hydrogenated NBR latex under the same conditions as in Example 1 except that various emulsifiers shown in Table 1 were used instead of the combination of fatty acid and dialkylsulfosuccinate. I went. When any of the emulsifiers was used, a latex having a small particle size could not be obtained and the stationary stability was poor.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【発明の効果】本発明の方法により、工程の途中で有害
な物質を使用することなく、製造されるラテックス粒子
の粒子径が充分に小さくかつ充分な静置安定性を有する
水素化ＮＢＲラテックスを得ることができる。EFFECTS OF THE INVENTION According to the method of the present invention, a hydrogenated NBR latex having a sufficiently small particle size of latex particles and sufficient stationary stability can be prepared without using harmful substances during the process. Obtainable.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松川 泰治 兵庫県姫路市飾磨区入船町１番地 住友 精化株式会社第２研究所内 (56)参考文献 特開 昭62−141033（ＪＰ，Ａ) 特開 昭62−201945（ＪＰ，Ａ) 特開 平２−199130（ＪＰ，Ａ) 特開 平４−93304（ＪＰ，Ａ) 特開 平７−207069（ＪＰ，Ａ) 特開 平６−263959（ＪＰ，Ａ) 特開 平６−166796（ＪＰ，Ａ) 特開 平５−184900（ＪＰ，Ａ) 特開 昭51−80343（ＪＰ，Ａ) 特開 平１−249846（ＪＰ，Ａ) 特開 平５−222267（ＪＰ，Ａ) 特開 昭58−38734（ＪＰ，Ａ) 特開 昭60−141736（ＪＰ，Ａ) 特開 昭63−280702（ＪＰ，Ａ) 特開 昭50−26893（ＪＰ，Ａ) 国際公開98／48628（ＷＯ，Ａ１) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 3/00 - 3/28 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Taiji Matsukawa, No. 1 Irifune-cho, Shirima-ku, Himeji City, Hyogo Prefecture, Sumitomo Seika Chemical Co., Ltd. 2nd Research Laboratory (56) Reference Japanese Patent Laid-Open No. 62-141033 (JP, A) Kai 62-201945 (JP, A) JP 2-199130 (JP, A) JP 4-93304 (JP, A) JP 7-2007069 (JP, A) JP 6-263959 ( JP, A) JP 6-166796 (JP, A) JP 5-184900 (JP, A) JP 51-80343 (JP, A) JP 1-249846 (JP, A) JP HEI 5-222267 (JP, A) JP 58-38734 (JP, A) JP 60-141736 (JP, A) JP 63-280702 (JP, A) JP 50-26893 (JP , A) International Publication 98/48628 (WO, A1) (58) Fields investigated (Int.Cl. 7 , DB name) C08J 3/00- 3/28
Claims (6)
キル基を有する脂肪酸を溶解した有機溶剤溶液並びに水
酸化アルカリ金属を溶解した水を混合後、乳化を行い、
その後有機溶剤を留去することにより水素化ＮＢＲラテ
ックスを製造する方法において、水酸化アルカリ金属を
溶解した水中にジアルキルスルホコハク酸塩を添加した
後、水素化ＮＢＲ及び炭素数６〜２４のアルキル基を有
する脂肪酸を溶解した有機溶剤溶液と混合すること特徴
とする水素化ＮＢＲラテックスの製造方法。1. A hydrogenated NBR and an alkane having 6 to 24 carbon atoms.
After mixing an organic solvent solution in which a fatty acid having a kill group is dissolved and water in which an alkali metal hydroxide is dissolved, emulsification is performed,
Then, in a method for producing a hydrogenated NBR latex by distilling off an organic solvent, a dialkylsulfosuccinate is added to water in which an alkali metal hydroxide is dissolved, and then a hydrogenated NBR and an alkyl group having 6 to 24 carbon atoms are added. Existence
A method for producing a hydrogenated NBR latex, which comprises mixing the fatty acid with an organic solvent solution in which the fatty acid is dissolved.
重量部に対して１〜１０重量部である請求項１記載の水
素化ＮＢＲラテックスの製造方法。2. The amount of fatty acid added is hydrogenated NBR100.
The method for producing a hydrogenated NBR latex according to claim 1, which is 1 to 10 parts by weight based on parts by weight.
２記載の水素化ＮＢＲラテックスの製造方法。3. The method for producing a hydrogenated NBR latex according to claim 1, wherein the fatty acid is oleic acid.
が、水素化ＮＢＲ１００重量部に対して０．３〜７重量
部である請求項１、２又は３記載の水素化ＮＢＲラテッ
クスの製造方法。4. The method for producing a hydrogenated NBR latex according to claim 1, 2 or 3, wherein the amount of the dialkyl sulfosuccinate added is 0.3 to 7 parts by weight based on 100 parts by weight of the hydrogenated NBR.
ルスルホコハク酸ナトリウムである請求項１、２、３又
は４記載の水素化ＮＢＲラテックスの製造方法。5. The method for producing a hydrogenated NBR latex according to claim 1, 2, 3 or 4, wherein the dialkyl sulfosuccinate is sodium dioctyl sulfosuccinate.
れる脂肪酸に対して０．５〜５倍モル量である請求項
１、２、３、４又は５記載の水素化ＮＢＲラテックスの
製造方法。6. The production of hydrogenated NBR latex according to claim 1, wherein the amount of alkali metal hydroxide added is 0.5 to 5 times the molar amount of the fatty acid added. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22823893A JP3393685B2 (en) | 1993-08-19 | 1993-08-19 | Method for producing hydrogenated NBR latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22823893A JP3393685B2 (en) | 1993-08-19 | 1993-08-19 | Method for producing hydrogenated NBR latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0753724A JPH0753724A (en) | 1995-02-28 |
| JP3393685B2 true JP3393685B2 (en) | 2003-04-07 |
Family
ID=16873330
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22823893A Expired - Fee Related JP3393685B2 (en) | 1993-08-19 | 1993-08-19 | Method for producing hydrogenated NBR latex |
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| Country | Link |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998048628A1 (en) | 1997-04-25 | 1998-11-05 | Ishihara Sangyo Kaisha, Ltd. | Composition for controlling harmful bio-organisms and method for controlling harmful bio-organisms using the same |
-
1993
- 1993-08-19 JP JP22823893A patent/JP3393685B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998048628A1 (en) | 1997-04-25 | 1998-11-05 | Ishihara Sangyo Kaisha, Ltd. | Composition for controlling harmful bio-organisms and method for controlling harmful bio-organisms using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0753724A (en) | 1995-02-28 |
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