JPH01190447A - Nonadhesive fluororubber and manufacture thereof - Google Patents
Nonadhesive fluororubber and manufacture thereofInfo
- Publication number
- JPH01190447A JPH01190447A JP1439288A JP1439288A JPH01190447A JP H01190447 A JPH01190447 A JP H01190447A JP 1439288 A JP1439288 A JP 1439288A JP 1439288 A JP1439288 A JP 1439288A JP H01190447 A JPH01190447 A JP H01190447A
- Authority
- JP
- Japan
- Prior art keywords
- fluororubber
- amine
- compound
- weight
- parts
- 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
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- -1 amine salt Chemical class 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 101150009274 nhr-1 gene Proteins 0.000 claims abstract 3
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000002335 surface treatment layer Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- SXKNYNUXUHCUHX-UHFFFAOYSA-N 1,1,2,3,3,4-hexafluorobut-1-ene Chemical compound FCC(F)(F)C(F)=C(F)F SXKNYNUXUHCUHX-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000982822 Ficus obtusifolia Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QDGONURINHVBEW-UHFFFAOYSA-N dichlorodifluoroethylene Chemical group FC(F)=C(Cl)Cl QDGONURINHVBEW-UHFFFAOYSA-N 0.000 description 1
- UPCIBFUJJLCOQG-UHFFFAOYSA-L ethyl-[2-[2-[ethyl(dimethyl)azaniumyl]ethyl-methylamino]ethyl]-dimethylazanium;dibromide Chemical compound [Br-].[Br-].CC[N+](C)(C)CCN(C)CC[N+](C)(C)CC UPCIBFUJJLCOQG-UHFFFAOYSA-L 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の技術分野）
本発明は非粘着性フッ素ゴムおよびその製造方法、さら
に詳細には、非粘着性を改良したフッ素ゴムおよびその
製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a non-stick fluororubber and a method for producing the same, and more particularly to a fluororubber with improved non-stick properties and a method for producing the same.
（発明の従来技術）
フッ素ゴムは、耐油性に優れていることがら、自動車の
エンジンなど内油機関の燃料系の弁体として多く使用さ
れている。(Prior Art to the Invention) Fluororubber has excellent oil resistance and is therefore often used as a valve body in the fuel system of internal oil engines such as automobile engines.
このような弁１は、例えば電磁石２あるいはスプリング
などの（１用によって軸方向に可動可能になっていると
ともに、流体の通路３に開設される弁座４に当接−解除
を行なうことによって流体通路２内を流通する流体の量
を制御したり、又はオン−オフを行なう作用を営むもの
である。Such a valve 1 is movable in the axial direction by means of an electromagnet 2 or a spring (1), for example, and is capable of moving fluid by bringing into and out of contact with a valve seat 4 opened in a fluid passage 3. It functions to control the amount of fluid flowing through the passage 2 or to turn it on and off.
このような弁１は、例えば金属製の弁軸１１とその先端
部に設けられた弁体１２よりなり、この弁体１２として
は耐油性及び耐磨耗性を要求されることからフッ素ゴム
が使用されている。Such a valve 1 is made of, for example, a metal valve stem 11 and a valve body 12 provided at its tip.The valve body 12 is required to have oil resistance and abrasion resistance, so fluororubber is used. It is used.
このような構造の弁１を使用して流体の制御を行なう場
合、前記弁座４と弁体１２は当接−解除を無数繰り返す
ことになる。このように弁体１２を長年使用すると、前
記弁体１２が粘着性を有するようになって、前記弁座４
と弁体１２の接触部Ａが粘着し、弁１が離れにくくなっ
たり、ひどくなると粘着して離れなくなったりする事態
を生じていた。When the valve 1 having such a structure is used to control fluid, the valve seat 4 and the valve body 12 repeatedly come into contact and release from each other countless times. When the valve body 12 is used for many years in this way, the valve body 12 becomes sticky and the valve seat 4 becomes sticky.
This causes the contact portion A of the valve body 12 to stick, making it difficult to separate the valve 1, or in severe cases, causing the valve 1 to stick and become unable to be removed.
このような欠点を除去するため、前記弁軸１１にフッ素
ゴム製の弁体１２を取り付けた後、前記弁体１２の表面
をアミン又はアミン酸塩で表面処理する方法が開発され
ている（特許出願公開昭和６１年第８１４３７号公報）
。In order to eliminate such drawbacks, a method has been developed in which a fluororubber valve body 12 is attached to the valve stem 11 and then the surface of the valve body 12 is treated with an amine or an amate salt (patented). Application Publication No. 81437 of 1985)
.
このような方法によれば、フッ素ゴムの非粘着化は従来
の表面処理を行なわない場合の３倍程度改良され、良好
な非粘着化を示す。しかしながら、このようなアミン処
理を行なった場合も、非粘着性は十分とはいえず、さら
に良好な非粘着性フッ素ゴムが希求されているのが現状
である。According to such a method, the non-adhesiveness of the fluororubber is improved by about three times compared to the case where no conventional surface treatment is performed, indicating a good non-adhesive property. However, even when such amine treatment is performed, the non-adhesive property is not sufficient, and there is currently a demand for a fluororubber with even better non-adhesive properties.
′（発明の概要）
本発明は上述の点に鑑みなされたものであり、従来に比
較して良好な非粘着性を有するフッ素ゴムおよびその製
造方法を提供すること、さらに詳細にはフッ素ゴム自体
を非粘着化し、さらに表面処理することによって相乗的
に優れた効果を示すフッ素ゴム及びその製造方法を提供
することを目的とするものである。(Summary of the Invention) The present invention has been made in view of the above-mentioned points, and it is an object of the present invention to provide a fluororubber that has better non-adhesiveness than conventional ones and a method for producing the same, and more specifically, to provide a fluororubber that has better non-adhesive properties than conventional ones, and more specifically, to provide a method for producing the same. The object of the present invention is to provide a fluororubber that exhibits synergistically excellent effects by making it non-adhesive and further surface-treating it, and a method for producing the same.
したがって本発明による非粘着性フッ素ゴムは、フッ素
ゴム１００重量部に対し、下記の一般式の化き物を５〜
３０重量部練り込むとともに、アミン又はアミン塩で処
理した表面処理層を設けたことを特徴とする。Therefore, the non-adhesive fluororubber according to the present invention contains 5 to 5 parts of a compound of the following general formula per 100 parts by weight of fluororubber.
It is characterized by having a surface treatment layer treated with amine or amine salt in addition to kneading 30 parts by weight.
ＲＣＯＮＨ（ＣＨ２）ｊｌＮＨｃＯＲ”（ただし、Ｒは
炭素数８〜２０のアルキル基、Ｒ′はＲ１スはＮ ＨＲ
，１であり、Ｒ１は前記Ｒと同−又は異なる炭素数８〜
２０のアルキル基、ｎは１〜８の正の整数を示す）
また、本発明による非粘着性フッ素ゴムの製造方法は、
フッ素ゴム１００重量部に対し、下記の一般式の化合物
を５〜３０重量部練り込んだフッ素ゴム組成物を加硫し
たのち、アミン又はアミン塩で表面処理することを特徴
とする。RCONH(CH2)jlNHcOR" (wherein, R is an alkyl group having 8 to 20 carbon atoms, R' is
, 1, and R1 has 8 to 8 carbon atoms, which is the same as or different from R.
(20 alkyl groups, n is a positive integer of 1 to 8) Furthermore, the method for producing a non-adhesive fluororubber according to the present invention includes:
The method is characterized in that a fluororubber composition in which 5 to 30 parts by weight of a compound of the following general formula is kneaded into 100 parts by weight of fluororubber is vulcanized and then surface-treated with an amine or an amine salt.
ＲＣＯＮＨ（ＣＨ２）ｎＮＨｃＯＲ’
（ただし、Ｒは炭素数８〜２０のアルキル基、Ｒ′はＲ
１又はＮＨＲＩであり、Ｒ１は前記Ｒと同−又は異なる
炭素数８〜２０のアルキル基、ｎは１〜８の正の整数を
示す）
本発明者らは、フッ素ゴムの非粘着化について鋭意研究
した結果、所定の酸ビスアミドないしはアルキルウレア
化合物をを所定量添加することによって、フッ素ゴムの
非粘着性が１００倍以上改良されることを見いだし、本
発明に至った乙のである。RCONH(CH2)nNHcOR' (where, R is an alkyl group having 8 to 20 carbon atoms, R' is R
1 or NHRI, R1 is an alkyl group having 8 to 20 carbon atoms that is the same as or different from R, and n is a positive integer of 1 to 8.) The present inventors have worked hard to make fluororubber non-stick. As a result of research, it was discovered that the non-stick properties of fluororubber can be improved by more than 100 times by adding a specified amount of a specified acid bisamide or alkyl urea compound, leading to the present invention.
（発明の詳細な説明） 本発明をさらに詳しく説明する。(Detailed description of the invention) The present invention will be explained in more detail.
本発明によれば、フッ素ゴムに対し、下記の一般式の化
合物を添加する。According to the present invention, a compound having the following general formula is added to fluororubber.
ＲＣＯＮＨ（ＣＨ２）ｎＮＨｃＯＲ’
（ただし、Ｒは炭素数８〜２０のアルキル基、Ｒ′はＲ
１又はＮＨＲＩであり、Ｒ１は前記Ｒと同−又は異なる
炭素数８〜２０のアルキル基、ｎは１〜８の正の整数を
示す）
前記−最大において、Ｒ及びＲ１は炭素数８へ−２０の
アルキル基であるが、前記Ｒ及びＲ１の炭素数が８より
小さいと、融点が低くなり過ぎて取り扱いが困難になり
、一方２０を越すと、粘度が大きくなり過ぎ、混練が困
難になるからである。RCONH(CH2)nNHcOR' (where, R is an alkyl group having 8 to 20 carbon atoms, R' is R
1 or NHRI, R1 is an alkyl group having 8 to 20 carbon atoms that is the same as or different from R, and n is a positive integer of 1 to 8.) At maximum, R and R1 have 8 carbon atoms. 20 alkyl groups, but if the number of carbon atoms in R and R1 is less than 8, the melting point will be too low and it will be difficult to handle, while if it exceeds 20, the viscosity will be too high and kneading will be difficult. It is from.
ｎは１〜８の正の整数であるが、８より大きいと、粘着
防止効果が充分でない恐れを生じるからである。This is because n is a positive integer of 1 to 8, but if it is larger than 8, the anti-adhesive effect may not be sufficient.
Ｒ′はＲ１又は−ＮＨＲ，であり、このＲ１は前述のＲ
と同−又は異なる炭素数８〜２０のアルキル基を示す。R' is R1 or -NHR, and this R1 is the above-mentioned R
represents an alkyl group having 8 to 20 carbon atoms that is the same as or different from .
前記のような化合物の具体例としては、例えばＣＩＩＨ
，２３ＣＯＮＨ（ＣＨ２）、２ Ｃ０ＮＨＣＩＩＨ２３
、Ｃｌ７Ｈ３ｓＣＯＮＨＣＨ２Ｃ０ＮＨＣＩ７Ｈ３Ｓ、
Ｃｌ８８ａｙＣＯＮＨ（ＣＨ２）ＣＯＮＨＣ１１！８３
７等の酸ビスアミド類およびＣｌ７Ｈ３５ＮＨＣＯＮＨ
（ＣＨ２）ＮＨＣＯＮＨＣＩ７Ｈ３Ｓ等のアルキルウレ
ア類等の一種以上であることができる。Specific examples of the above-mentioned compounds include, for example, CIIH
,23CONH(CH2),2 C0NHCIH23
, Cl7H3sCONHCH2C0NHCI7H3S,
Cl88ayCONH(CH2)CONHC11!83
Acid bisamides such as 7 and Cl7H35NHCONH
It can be one or more types of alkylureas such as (CH2)NHCONHCI7H3S.
この化合物の添加量は、フッ素ゴム１００重量部に対し
、５〜３０重量部である。５重量部未満であると、充分
な非粘着化が達成できない恐れがあり、一方３０重量部
を越えると、諸物性が低下するという欠点を生じる恐れ
があるからである。The amount of this compound added is 5 to 30 parts by weight per 100 parts by weight of fluororubber. If the amount is less than 5 parts by weight, sufficient non-tackiness may not be achieved, while if it exceeds 30 parts by weight, there is a risk of deterioration of various physical properties.
本発明において使用されるフッ素ゴムは、基本的に限定
されるものではない。二元系及び三元系など、種々のフ
ッ素ゴムを使用することができる。The fluororubber used in the present invention is basically not limited. Various fluororubbers can be used, including binary and ternary types.
具体例を上げれば、ヘキサフルオロプロペン、１．１．
１．２．３−ペンタフルオロプロペン、テトラフルオロ
エチレン、トリフルオロエチレン、１゜２−ジフルオロ
エチレン、ジクロルジフルオロエチレ・ン、タロルトリ
フルオロエチレン、八、キサフルオロブテン、フッ素化
ビニルエーテル類、パーフルオロアクリル酸エステルな
どの共重合体を挙げることができる。Specific examples include hexafluoropropene, 1.1.
1.2.3-pentafluoropropene, tetrafluoroethylene, trifluoroethylene, 1゜2-difluoroethylene, dichlorodifluoroethylene, thaloltrifluoroethylene, hexafluorobutene, fluorinated vinyl ethers, perfluoro Copolymers such as acrylic esters can be mentioned.
このような本発明のフッ素ゴムには、そのほかに加硫剤
、加硫促進剤、老化防止剤。充填剤、加工助剤などを適
量添加することができるのは、明らかである。The fluororubber of the present invention also contains a vulcanizing agent, a vulcanization accelerator, and an anti-aging agent. Obviously, suitable amounts of fillers, processing aids, etc. can be added.
本発明においては前述のようなゴム組成物を使用して、
加硫成形し、成形品形状としたのちに、アミン又はアミ
ン塩でその表面を処理し、処理層を形成している。In the present invention, using the rubber composition as described above,
After vulcanization and molding to form a molded article, the surface is treated with an amine or an amine salt to form a treated layer.
表面処理に用いられるこれらのアミン類は、１級乃至３
級の脂肪族モノ又はポリアミン、ポリアルキレンポリア
ミン縮金物、芳香族ポリアミン、環状アミンなど任意の
ものを使用することができ、それらのいくつかを−最大
または具体的な化合物名で示すと、次のごとしである。These amines used for surface treatment are primary to tertiary amines.
Any of the following can be used: aliphatic mono- or polyamines, polyalkylene polyamine condensates, aromatic polyamines, cyclic amines, etc., some of which are listed below by maximum or specific compound name. That's how it is.
（１）モノアルキルアミン
トリアルキルアミン
（ ２ ） Ｒ２ Ｒ３ Ｎ （Ｏ Ｒ２ ） ｎ
Ｎ Ｒ４ ＪＲ２ ”Ｒ５ ：水素原子またはアル
キル基ｎ：２以上の整数
（３）Ｒ２ Ｒ３ Ｎ （ＯＨ２ ） ９ ＮＨ
（ＯＨ２）ＩＩＩＮＲ３Ｒ４
Ｒ１−Ｒ４：水素原子またはアルキル基ｍ，Ｊ２：２ま
たは６
（４）トリエチレンテトラミン等のテトラミン、テトラ
エチレンペンタミン等のペンタミン（５）Ｒ２ Ｎ
Ｒ６ ＮＲ２
Ｒ６ ：
これらの芳香族ポリアミンは、脂肪族アミンと比較して
、成形品の表面処理反応の速度が遅いので、これをあら
かじめ１００°Ｃに加熱して熱処理したり、あるいはア
ンモニウム１ヒ合物又はホスホニウム化合物を微量添加
して用いると、表面処理時間を短くすることができる。(1) Monoalkyl amine trialkyl amine (2) R2 R3 N (OR2) n
N R4 JR2 "R5: Hydrogen atom or alkyl group n: An integer of 2 or more (3) R2 R3 N (OH2) 9 NH
(OH2)IIINR3R4 R1-R4: hydrogen atom or alkyl group m, J2: 2 or 6 (4) Tetramine such as triethylenetetramine, pentamine such as tetraethylenepentamine (5) R2 N
R6 NR2 R6: Compared to aliphatic amines, these aromatic polyamines have a slower surface treatment reaction rate for molded products, so they are heat-treated by heating to 100°C in advance, or ammonium By adding a small amount of a compound or a phosphonium compound, the surface treatment time can be shortened.
（６）１、８−ジアザビシクロ（５、４、０）ーウンデ
ク−７−エン
１、５−ジアザビシクロ（４、３、０）−ノン−５−エ
ン
ピペラジン
ヘキサメチレンテトラミン
４−ジアルキルアミノピリジン
（７）以上のアミンの塩類、例えば炭酸塩、塩酸塩、ア
ンモニウム塩など
これらのアミン塩を用いる場合には、あらかじめ、約５
０〜１５０°Ｃ程度の温度に加熱して、熱処理しておく
と、成形品の表面処理反応の速度が高められ、表面処理
時間を短くすることができる。(6) 1,8-diazabicyclo(5,4,0)-undec-7-ene 1,5-diazabicyclo(4,3,0)-non-5-enpiperazinehexamethylenetetramine 4-dialkylaminopyridine (7) When using the above amine salts, such as carbonate, hydrochloride, ammonium salt, etc., approximately 5
If the molded article is heated to a temperature of about 0 to 150° C. for heat treatment, the speed of the surface treatment reaction of the molded article can be increased and the surface treatment time can be shortened.
これらアミン類による加硫フッ素ゴム成形品の表面処理
は、アミン類又はその溶液、例えばメタノール、エタノ
ール、アセトン溶液中への浸漬、刷毛塗り、スプレー、
塗布、蒸気中への浸漬など任意の方法を用い、室温乃至
約３００°Ｃ程度の温度で行なわれ、処理終了後は水洗
、乾燥（室温〜２５０°Ｃで約５〜６０分間）が行なわ
れる。Surface treatment of vulcanized fluororubber molded products with these amines can be carried out by dipping in amines or their solutions, such as methanol, ethanol, or acetone solutions, brushing, spraying,
It is carried out using any method such as coating or dipping in steam at a temperature between room temperature and about 300°C, and after the treatment is finished, it is washed with water and dried (at room temperature to 250°C for about 5 to 60 minutes). .
以下、実施例について説明する。Examples will be described below.
実施例１
下記の第１表に示すような酸ビスアミドおよびアルキル
ウレア化合物を配合した三元系フッ素ゴム（ほかにカー
ボンブラック、２０重量部、架橋助剤５．５重量部、架
橋剤（過酸化物）２重量部、を含む）よりフッ素ゴム組
成物を製造し、加硫してフッ素ゴムにしたのち、エチレ
ンジアミン中に６０°Ｃで３０分間浸漬し、水洗した。Example 1 A ternary fluororubber blended with an acid bisamide and an alkyl urea compound as shown in Table 1 below (in addition, carbon black, 20 parts by weight, crosslinking aid 5.5 parts by weight, crosslinking agent (peroxide) A fluororubber composition was prepared from 2 parts by weight of fluorine rubber, which was vulcanized to form fluororubber, and then immersed in ethylenediamine at 60°C for 30 minutes and washed with water.
このようなフッ素ゴムの粘着性を測定した。The tackiness of such fluororubber was measured.
第１表
このようなフッ素ゴムを使用して、第２図に示すような
粘着試験機によって粘着性を試験した。Table 1 Using such fluororubbers, the adhesion was tested using an adhesion tester as shown in FIG.
すなわち鉄＋Ｎｉ鍍金のプランジャ５の先端部に前記組
成物試料６を貼付し、バルブシート７上に載置し、プッ
シュプルゲージ８によって上方に前記プランジャ５を持
ち上げるときの力（ｇ）を測定した。試料６とプランジ
ャ５の自重は２ｇであった。That is, the composition sample 6 was attached to the tip of the iron + Ni-plated plunger 5, placed on the valve seat 7, and the force (g) when lifting the plunger 5 upward was measured using the push-pull gauge 8. . The weight of sample 6 and plunger 5 was 2 g.
測定は、前記プランジャ５に取り付けられた試料５に５
０ｇの荷重をかけ、バルブシート７に試料を押しつけた
状態で、４０°Ｃ１湿度８０％の状態で２０時間保持し
た後、さらに２５°Ｃ１湿度６５％で４時間放置した後
に行なった。In the measurement, a sample 5 attached to the plunger 5 is
After applying a load of 0 g and holding the sample pressed against the valve seat 7 at 40° C. and 80% humidity for 20 hours, the test was further left at 25° C. and 65% humidity for 4 hours.
この試験方法より明らかなように、持ち上げる力が小さ
いほど粘着性は小さくなる。また、実際の粘着性は、測
定値より２ｇ引いた値である。As is clear from this test method, the lower the lifting force, the lower the stickiness. Further, the actual tackiness is a value obtained by subtracting 2 g from the measured value.
結果を下記の第２表に示す。The results are shown in Table 2 below.
第２表
比較例として前記組成物に使用したフッ素ゴムの粘着性
を試験を行なった。As a comparative example in Table 2, the tackiness of the fluororubber used in the above composition was tested.
この第２表より明らかなように、通常のアミン処理のみ
のフッ素ゴムに比較して、平均値で１０倍前後、非粘着
効果が改良されて得いることがわがすな。As is clear from Table 2, it can be seen that the non-adhesive effect is improved by about 10 times on average compared to the conventional fluororubber treated with amine only.
最大値でも、５〜１３倍の効果があると共に、最小値に
おいては３０倍以上の効果が出たものもあった。Even at the maximum value, it was 5 to 13 times more effective, and at the minimum value, there were some that were more than 30 times more effective.
実施例２
フッ素ゴム（三元系フッ素ゴム）に対し、上記実施例４
のアルキルウレア系化合物の添加量を変化させた本発明
のフッ素ゴムを製造し、同様に粘着性を測定した。Example 2 For fluororubber (ternary fluororubber), the above Example 4
Fluororubbers of the present invention were produced in which the amount of the alkyl urea compound added was varied, and the tackiness was measured in the same manner.
また比較例として、特開昭６１−８１４３７号に開示さ
れているアミンによる表面処理のみを行なったフッ素ゴ
ムについての粘着性も測定した。In addition, as a comparative example, the tackiness of a fluororubber subjected to only surface treatment with amine as disclosed in JP-A-61-81437 was also measured.
まず、実施例４の化合物を所定量添加し、練り込んだ後
、プランジャに焼き付け、１７０°Ｃ×１０分（−次加
硫）の条件で一次加硫した後、フッ素ゴム表面をメタノ
ールで洗浄すると共に、超音波によって２分間洗浄を行
ない、アミン溶液（Ｄｉａｋ Ｎｏ、１；商標名、デ
ュポン（株））２０％水溶液に０〜２４時間浸漬し、乾
燥した後、二次加硫したものを試料とした。First, after adding a predetermined amount of the compound of Example 4 and kneading it, it was baked into a plunger and primary vulcanized at 170°C x 10 minutes (-post vulcanization), and then the fluororubber surface was washed with methanol. At the same time, it was washed with ultrasonic waves for 2 minutes, immersed in a 20% aqueous solution of amine solution (Diak No. 1; trade name, DuPont Co., Ltd.) for 0 to 24 hours, dried, and then subjected to secondary vulcanization. It was used as a sample.
比較例の試料は、同一のフッ素ゴムをプランジャに焼き
付けた後、水洗し、上記と同一条件でメタノール、超音
波洗浄をした後、アミン溶液（ＤｉａｋＮｏ、１；商標
名、デュポン（株））２０％水溶液に１〜２４時間浸漬
して、−次加硫し、表面処理を行なった後、二次加硫を
したものを試料とした。For the comparative example, the same fluororubber was baked into the plunger, washed with water, washed with methanol and ultrasonic waves under the same conditions as above, and then treated with an amine solution (Diak No. 1; trade name, DuPont Co., Ltd.) 20. % aqueous solution for 1 to 24 hours, secondary vulcanization, surface treatment, and secondary vulcanization were used as samples.
結果を第３表に示す。The results are shown in Table 3.
第３表
この第３表より明らかなように、アミン表面処理を２４
時間したフッ素ゴムは平均粘着力が１０７ｇであり、非
粘着処理を行なっていないフッ素ゴムの粘着力（５７３
ｇ）よりも４倍以上の非粘着性を示す。しかしながら、
本発明による平均値は、３ｇであり、非粘着処理をして
いないフッ素ゴムの１５０倍以上、アミン表面処理をし
た場合の３５倍以上の効果があった。Table 3 As is clear from Table 3, the amine surface treatment was
The average adhesive strength of the fluororubber that has been aged is 107g, and the adhesive strength of the fluororubber that has not been treated with non-adhesive treatment (573g).
It exhibits 4 times or more non-adhesiveness than g). however,
The average value according to the present invention was 3 g, which was more than 150 times as effective as the fluororubber without non-adhesive treatment, and more than 35 times as effective as in the case of amine surface treatment.
この粘着性のデータ（平均値）をグラフにしたものを第
３図に示す。図中、黒丸はアミン表面処理を行なったフ
ッ素ゴム、白丸は本発明による組成物より製造されたフ
ッ素ゴムをアミン処理したものを示している。A graph of this tackiness data (average value) is shown in FIG. In the figure, black circles indicate fluororubber that has been surface-treated with an amine, and white circles indicate fluororubber that has been produced from the composition of the present invention and has been treated with an amine.
（発明の効果）
以上説明したように、本発明によれば酸ビスアミドない
しアルキルウレア系化合物を添加し、且つアミン又はア
ミン塩で表面処理したため、著しく良好な非粘着性のフ
ッ素ゴムを得ることができる。このため、信頼性の高い
弁体などを製造することができるという利点がある。(Effects of the Invention) As explained above, according to the present invention, since an acid bisamide or alkyl urea compound is added and the surface is treated with an amine or an amine salt, a fluororubber with extremely good non-stick properties can be obtained. can. Therefore, there is an advantage that highly reliable valve bodies and the like can be manufactured.
第１図は弁機構を模式的に示した図、第２図は粘着性を
試験するための機構を示した図、第３図は本発明による
実施例４の化合物の添加量と粘着性の関係及びアミド表
面処理時間と粘着性を示したグラフ（粘着性のデータは
平均値）である。
１２・・・弁体。Figure 1 is a diagram schematically showing the valve mechanism, Figure 2 is a diagram showing the mechanism for testing tackiness, and Figure 3 is a diagram showing the amount of addition of the compound of Example 4 according to the present invention and the tackiness. This is a graph showing the relationship between amide surface treatment time and tackiness (the tackiness data is an average value). 12...Valve body.
Claims (2)
化合物を５〜３０重量部練り込むとともに、アミン又は
アミン塩で表面処理した表面処理層を設けたことを特徴
とする非粘着性フッ素ゴム。 ＲＣＯＮＨ（ＣＨ＿２）＿ｎＮＨＣＯＲ′ （ただし、Ｒは炭素数８〜２０のアルキル基、Ｒ′はＲ
＿１又はＮＨＲ＿１であり、Ｒ＿１は前記Ｒと同一又は
異なる炭素数８〜２０のアルキル基、ｎは１〜８の正の
整数を示す）(1) Non-adhesive fluorine rubber characterized by kneading 5 to 30 parts by weight of a compound of the following general formula into 100 parts by weight of fluororubber and providing a surface treatment layer treated with amine or amine salt. rubber. RCONH(CH_2)_nNHCOR' (where, R is an alkyl group having 8 to 20 carbon atoms, R' is R
_1 or NHR_1, R_1 is an alkyl group having 8 to 20 carbon atoms that is the same as or different from R, and n is a positive integer of 1 to 8)
化合物を５〜３０重量部練り込んだフッ素ゴム組成物を
加硫したのち、アミン又はアミン塩で表面処理すること
を特徴とする非粘着性フッ素ゴムの製造方法。 ＲＣＯＮＨ（ＣＨ＿２）＿ｎＮＨＣＯＲ′ （ただし、Ｒは炭素数８〜２０のアルキル基、Ｒ′はＲ
＿１又はＮＨＲ＿１であり、Ｒ＿１は前記Ｒと同一又は
異なる炭素数８〜２０のアルキル基、ｎは１〜８の正の
整数を示す）(2) After vulcanizing a fluororubber composition in which 5 to 30 parts by weight of a compound of the following general formula is kneaded into 100 parts by weight of fluororubber, the composition is surface-treated with an amine or an amine salt. Method for producing adhesive fluororubber. RCONH(CH_2)_nNHCOR' (where, R is an alkyl group having 8 to 20 carbon atoms, R' is R
_1 or NHR_1, R_1 is an alkyl group having 8 to 20 carbon atoms that is the same as or different from R, and n is a positive integer of 1 to 8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1439288A JP2668693B2 (en) | 1988-01-27 | 1988-01-27 | Non-adhesive fluororubber and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1439288A JP2668693B2 (en) | 1988-01-27 | 1988-01-27 | Non-adhesive fluororubber and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01190447A true JPH01190447A (en) | 1989-07-31 |
| JP2668693B2 JP2668693B2 (en) | 1997-10-27 |
Family
ID=11859786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1439288A Expired - Fee Related JP2668693B2 (en) | 1988-01-27 | 1988-01-27 | Non-adhesive fluororubber and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2668693B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1095973A1 (en) * | 1999-10-25 | 2001-05-02 | Honeywell B.V. | Rubber compound for gas valves |
| WO2013123156A1 (en) | 2012-02-15 | 2013-08-22 | 3M Innovative Properties Company | Fluoropolymer composition comprising a cross - linkable fluorinated elastomer and a ptfe of low melting point |
-
1988
- 1988-01-27 JP JP1439288A patent/JP2668693B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1095973A1 (en) * | 1999-10-25 | 2001-05-02 | Honeywell B.V. | Rubber compound for gas valves |
| WO2013123156A1 (en) | 2012-02-15 | 2013-08-22 | 3M Innovative Properties Company | Fluoropolymer composition comprising a cross - linkable fluorinated elastomer and a ptfe of low melting point |
| US9458314B2 (en) | 2012-02-15 | 2016-10-04 | 3M Innovative Properties Company | Fluoropolymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2668693B2 (en) | 1997-10-27 |
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