JPH05320212A - Internally cross-linked fine particle and rubber composition containing the same - Google Patents
Internally cross-linked fine particle and rubber composition containing the sameInfo
- Publication number
- JPH05320212A JPH05320212A JP15153592A JP15153592A JPH05320212A JP H05320212 A JPH05320212 A JP H05320212A JP 15153592 A JP15153592 A JP 15153592A JP 15153592 A JP15153592 A JP 15153592A JP H05320212 A JPH05320212 A JP H05320212A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- rubber composition
- composition containing
- reactive
- radical
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は内部架橋された微粒子及
びそれを配合したゴム組成物に関する。FIELD OF THE INVENTION The present invention relates to internally crosslinked fine particles and a rubber composition containing the fine particles.
【0002】[0002]
【従来の技術】ゴム配合剤の一種として充填剤がある
が、無機系充填剤は比重が大きく、又、本質的にゴムマ
トリツクスとは非相溶である。相溶性を向上させる為
に、表面処理等が行われているが、化学的にゴムマトリ
ツクスと結合するものを得ることは容易ではなかつた。
又、低比重である有機系充填剤も市販されているが、充
分な補強性を持つものはない。2. Description of the Related Art Fillers are one type of rubber compounding agents. Inorganic fillers have a large specific gravity and are essentially incompatible with rubber matrix. Surface treatment and the like have been carried out in order to improve the compatibility, but it has not been easy to obtain a material that chemically bonds to the rubber matrix.
In addition, organic fillers having a low specific gravity are commercially available, but none have sufficient reinforcing properties.
【0003】[0003]
【発明が解決しようとする課題】本発明の目的は上記問
題点を解決するもので、低比重で、かつ十分なゴムに対
する補強性を有する有機系充填剤を提供することにあ
る。SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide an organic filler having a low specific gravity and a sufficient reinforcing property for rubber.
【0004】[0004]
【課題を解決するための手段】本発明は少なくとも1種
のラジカル反応性1官能性モノマーと少なくとも1種の
ラジカル反応性多官能性モノマーを水中に微分散させた
後、重合させて得られる内部架橋された微粒子及びそれ
をゴム成分に配合したゴム組成物に係る。DISCLOSURE OF THE INVENTION The present invention provides an internal structure obtained by finely dispersing at least one radical-reactive monofunctional monomer and at least one radical-reactive polyfunctional monomer in water, and then polymerizing them. The present invention relates to crosslinked fine particles and a rubber composition containing the same as a rubber component.
【0005】本発明においてラジカル反応性1官能性モ
ノマーとしては、例えばスチレン等の芳香族ビニル化合
物、塩化ビニル、酢酸ビニル等の脂肪族ビニル化合物、
メチルアリルエーテル、メチルビニルエーテル等のビニ
ル又はアリルエーテル類、(メタ)アクリル酸エステル
類等が挙げられる。In the present invention, examples of the radical-reactive monofunctional monomer include aromatic vinyl compounds such as styrene, aliphatic vinyl compounds such as vinyl chloride and vinyl acetate,
Examples thereof include vinyl or allyl ethers such as methyl allyl ether and methyl vinyl ether, and (meth) acrylic acid esters.
【0006】ラジカル反応性多官能性モノマーとして
は、例えばジビニルベンゼン、アリル(メタ)アクリレ
ート、エチリデンノルボルネン、ジシクロペンタジエ
ン、多価アクリル酸エステル類、ジアリルフタレート、
トリアリルイソシアヌレート等が挙げられる。Examples of the radical-reactive polyfunctional monomer include divinylbenzene, allyl (meth) acrylate, ethylidene norbornene, dicyclopentadiene, polyvalent acrylic acid esters, diallyl phthalate,
Examples include triallyl isocyanurate.
【0007】1官能性モノマーと多官能性モノマーの使
用比率は特に限定されないが重合後にある程度の二重結
合が残つている必要があり、好ましくは1官能性モノマ
ー:多官能性モノマーのモル比が5:1〜1:5の比率
であり、特に好ましくは3:1から1:3の比率であ
る。The use ratio of the monofunctional monomer and the polyfunctional monomer is not particularly limited, but it is necessary that a certain amount of double bonds remain after the polymerization, and the molar ratio of the monofunctional monomer to the polyfunctional monomer is preferably. The ratio is 5: 1 to 1: 5, particularly preferably 3: 1 to 1: 3.
【0008】製造方法としては、通常のラジカル重合法
でよく、特に重合粒子を微粒子に保つため乳化重合、懸
濁重合方法が好ましい。特に粒子径分布の安定した微粒
子を得るため、乳化重合が好ましい。懸濁重合の場合
は、通常油溶性開始剤を用い、重合温度0〜100℃、重
合時間0.5〜24時間程度が好ましい。The production method may be an ordinary radical polymerization method, and in particular, an emulsion polymerization method or a suspension polymerization method is preferable in order to keep the polymer particles in fine particles. In particular, emulsion polymerization is preferable in order to obtain fine particles having a stable particle size distribution. In the case of suspension polymerization, an oil-soluble initiator is usually used, and the polymerization temperature is preferably 0 to 100 ° C. and the polymerization time is preferably 0.5 to 24 hours.
【0009】ラジカル重合開始剤としては、乳化重合の
場合は、通常の水溶性開始剤を用いることができる。重
合温度は通常約0〜100℃が好ましく、重合時間は通常
約0.5〜24時間程度が好ましい。In the case of emulsion polymerization, a conventional water-soluble initiator can be used as the radical polymerization initiator. The polymerization temperature is usually about 0 to 100 ° C., and the polymerization time is usually about 0.5 to 24 hours.
【0010】上記で得られた微粒子は強固に内部架橋さ
れており、又表面に残つている二重結合のため補強性が
得られやすく、有機系充填剤として有用である。The fine particles obtained as described above are strongly internally crosslinked, and the double bond remaining on the surface easily obtains the reinforcing property, and is useful as an organic filler.
【0011】次に本発明は上記内部架橋された微粒子
(以下、有機系充填剤ともいう)をゴム成分に配合した
ゴム組成物にも係る。ゴム成分としては有機過酸化物加
硫又は硫黄加硫可能なゴムが用いられ、例えばポリブタ
ジエンゴム、SBR、NBR(水素化物を含む)等のブ
タジエン系ゴム、シリコンゴム、EPDM等のオレフイ
ン系ゴム、二重結合を側鎖にもつアクリルゴム、ヨウ素
及び/又は臭素含有フツ素ゴム等が挙げられる。Next, the present invention also relates to a rubber composition containing the above internally crosslinked fine particles (hereinafter, also referred to as an organic filler) in a rubber component. An organic peroxide vulcanizable or sulfur vulcanizable rubber is used as the rubber component. For example, butadiene rubber such as polybutadiene rubber, SBR, NBR (including hydride), silicone rubber, olefin rubber such as EPDM, Examples thereof include acrylic rubber having a double bond in the side chain, iodine and / or bromine-containing fluorine rubber, and the like.
【0012】ゴム成分と有機系充填剤の配合比率は、そ
の系によつて変動するが、ゴム成分がフツ素ゴムの場合
は、フツ素ゴム 100部(重量部、以下同様)に対して有
機系充填剤 5〜40部程度が好ましく、5〜20部が特に
好ましい。5部より少ない場合は、添加効果が少なく、
40部より多い場合は逆に強度低下を引き起こす。The compounding ratio of the rubber component and the organic filler varies depending on the system, but when the rubber component is fluorocarbon rubber, the organic component is added to 100 parts of fluorocarbon rubber (parts by weight, the same applies hereinafter). About 5 to 40 parts are preferable, and 5 to 20 parts are particularly preferable. If it is less than 5 parts, the effect of addition is small,
On the other hand, if it exceeds 40 parts, the strength will decrease.
【0013】本発明では上記有機過酸化物加硫可能な合
成ゴムに上記有機系充填剤を微分散させ、通常の配合剤
を添加し、加硫する。微分散を確保するため、上記のよ
うにラジカル重合により製造した有機系充填剤の乳化液
とゴムの分散液を混合し、共析させたものが好ましい。
配合剤としては、通常のものが使用でき特に限定され
ず、例えば、加工助剤、可塑剤、着色剤、トリアリルイ
ソシアヌレート等の加硫助剤、有機過酸化物系の加硫剤
が挙げられる。カーボンブラツク、シリカ、クレー、珪
藻土、炭酸カルシウム等の無機系充填剤を含んでいても
よい。加硫は上記組成物を、オープンロール又はニーダ
ー等の密閉式混合機を用いて作成し、100〜200℃の温度
で1分〜120分プレス加硫し、必要に応じて、オーブン
加硫する。オーブン加硫の条件としては通常と同じでよ
いが、例えば150〜300℃で10分〜48時間の範囲が採用さ
れる。In the present invention, the above-mentioned organic filler is finely dispersed in the above-mentioned organic peroxide vulcanizable synthetic rubber, and an ordinary compounding agent is added to the rubber for vulcanization. In order to secure the fine dispersion, it is preferable that the emulsion of the organic filler produced by radical polymerization as described above and the dispersion of rubber are mixed and co-deposited.
As the compounding agent, usual compounds can be used and are not particularly limited, and examples thereof include processing aids, plasticizers, colorants, vulcanization aids such as triallyl isocyanurate, and organic peroxide vulcanizing agents. Be done. It may contain an inorganic filler such as carbon black, silica, clay, diatomaceous earth, or calcium carbonate. For vulcanization, the composition is prepared by using an internal mixer such as an open roll or a kneader, press vulcanized at a temperature of 100 to 200 ° C. for 1 to 120 minutes, and optionally oven vulcanized. .. The conditions for oven vulcanization may be the same as usual, but for example, a range of 10 minutes to 48 hours at 150 to 300 ° C is adopted.
【0014】[0014]
【実施例】実施例1〜7 表1に記載のモノマー混合物 100部に界面活性剤(ラウ
リル硫酸ナトリウム)4部を添加し、高圧乳化機を通
し、乳化した後、水溶性重合開始剤(t−ブチルハイド
ロパーオキサイド)1部を用いて窒素気流下70℃で8時
間ラジカル重合した。得られた微粒子の粒子径及び酢酸
水銀法により測定した粒子表面の二重結合の濃度を同様
表1に示す。5FMAはCH2=C(CH3)COOCH
2CF2CF3を示す。Examples 1 to 7 4 parts of a surfactant (sodium lauryl sulfate) was added to 100 parts of the monomer mixture shown in Table 1, and the mixture was passed through a high pressure emulsifying machine to emulsify it, and then a water-soluble polymerization initiator (t -Butyl hydroperoxide) was used for radical polymerization at 70 ° C. for 8 hours under a nitrogen stream. The particle size of the obtained fine particles and the concentration of double bonds on the particle surface measured by the mercury acetate method are also shown in Table 1. 5FMA is CH 2 = C (CH 3) COOCH
2 CF 2 CF 3 is shown.
【0015】[0015]
【表1】 [Table 1]
【0016】実施例8〜16及び比較例1 実施例1〜7で得られた有機系充填剤分散液にダイエル
G−902乳化分散液を表2に示す割合で添加し、塩化マ
グネシウムにより、共析させた。洗浄、乾燥後、この混
合物 100部に対してTAIC 4部及びパーヘキサ 2.5
B 1.5部をオープンロールを用いて配合した後、160℃
で30分間プレス加硫した。得られた加硫物の物性を下記
方法にて測定し、その結果を表2に示した。尚、ダイエ
ルG−902はビニリデンフルオライド(2F)、ヘキサ
フルオロプロペン(6F)及びテトラフルオロエチレン
(4F)の3元系共重合フツ素ゴム、TAICはトリア
リルイソシアヌレート、パーヘキサ 2.5Bは日本油脂製
パーオキサイドである。 100%モジユラス:JIS K6301 引張強度:JIS K6301 伸び :JIS K6301 硬度 :JIS K6301Examples 8 to 16 and Comparative Example 1 Daier G-902 emulsion dispersions were added to the organic filler dispersions obtained in Examples 1 to 7 in the proportions shown in Table 2, and co-dispersed with magnesium chloride. Was allowed to settle. After washing and drying, 4 parts of TAIC and 2.5 parts of perhexaline were added to 100 parts of this mixture.
After blending 1.5 parts of B using an open roll, 160 ° C
And press vulcanized for 30 minutes. The physical properties of the obtained vulcanizate were measured by the following methods, and the results are shown in Table 2. In addition, DAI-EL G-902 is vinylidene fluoride (2F), hexafluoropropene (6F) and tetrafluoroethylene (4F) ternary copolymer fluorine rubber, TAIC is triallyl isocyanurate, and perhexa 2.5B is NOF Corporation. Made of peroxide. 100% Module: JIS K6301 Tensile Strength: JIS K6301 Elongation: JIS K6301 Hardness: JIS K6301
【0017】[0017]
【表2】 [Table 2]
【0018】[0018]
【発明の効果】本発明の有機系充填剤は、有機過酸化物
加硫又は硫黄加硫系ゴムに配合すると、良好な物性の加
硫物が得られる。When the organic filler of the present invention is blended with an organic peroxide vulcanized or sulfur vulcanized rubber, a vulcanized product having good physical properties can be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 C08L 57:00) (72)発明者 白井 善裕 大阪府摂津市西一津屋1−1 ダイキン工 業株式会社淀川製作所内 (72)発明者 南野 悦男 大阪府摂津市西一津屋1−1 ダイキン工 業株式会社淀川製作所内 (72)発明者 友田 正康 大阪府摂津市西一津屋1−1 ダイキン工 業株式会社淀川製作所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Internal reference number FI Technical display location C08L 57:00) (72) Inventor Yoshihiro Shirai 1-1 Nishiichitsuya, Settsu-shi, Osaka Daikin Industrial Co., Ltd. Company Yodogawa Works (72) Inventor Etsushi Minamino 1-1, Nishiichitsuya, Settsu City, Osaka Prefecture Daikin Industrial Co., Ltd. (72) Masayasu Tomoda 1-1, Nishiichitsuya, Settsu City, Osaka Yodogawa Corporation Inside the factory
Claims (2)
性モノマーと少なくとも1種のラジカル反応性多官能性
モノマーを水中に微分散させた後、重合させて得られる
内部架橋された微粒子。1. Internally crosslinked fine particles obtained by finely dispersing at least one radical-reactive monofunctional monomer and at least one radical-reactive polyfunctional monomer in water, and then polymerizing them.
性モノマーと少なくとも1種のラジカル反応性多官能性
モノマーを水中に微分散させた後、重合させて得られる
内部架橋された微粒子をゴム成分に配合したゴム組成
物。2. A rubber component containing internally crosslinked fine particles obtained by finely dispersing at least one radical-reactive monofunctional monomer and at least one radical-reactive polyfunctional monomer in water and then polymerizing them. A rubber composition blended with.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15153592A JP3263973B2 (en) | 1992-05-18 | 1992-05-18 | Internally crosslinked fine particles and rubber composition containing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15153592A JP3263973B2 (en) | 1992-05-18 | 1992-05-18 | Internally crosslinked fine particles and rubber composition containing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05320212A true JPH05320212A (en) | 1993-12-03 |
JP3263973B2 JP3263973B2 (en) | 2002-03-11 |
Family
ID=15520641
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15153592A Expired - Fee Related JP3263973B2 (en) | 1992-05-18 | 1992-05-18 | Internally crosslinked fine particles and rubber composition containing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3263973B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002042338A1 (en) * | 2000-11-22 | 2002-05-30 | Sekisui Chemical Co., Ltd. | Crosslinked resin particles, crosslinked resin particle emulsion for use in producing the crosslinked resin particles, and method for producing the crosslinked resin particles |
-
1992
- 1992-05-18 JP JP15153592A patent/JP3263973B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002042338A1 (en) * | 2000-11-22 | 2002-05-30 | Sekisui Chemical Co., Ltd. | Crosslinked resin particles, crosslinked resin particle emulsion for use in producing the crosslinked resin particles, and method for producing the crosslinked resin particles |
Also Published As
Publication number | Publication date |
---|---|
JP3263973B2 (en) | 2002-03-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7022773B2 (en) | Fluoroelastomer compositions | |
JP4511670B2 (en) | Fluoroelastomer compositions | |
JP2854863B2 (en) | Fluorinated elastomer composition | |
JP6371295B2 (en) | Peroxide curable fluoropolymer compositions containing solvents and methods of use thereof | |
CA1186832A (en) | Composition containing a peroxide vulcanizing agent or coagent and a multi-stage graft copolymer | |
JP4168189B2 (en) | Composite of acrylic rubber and fluororubber, method for producing the same, and vulcanizable rubber composition | |
JP5101770B2 (en) | Blend of fluorinated elastomer and acrylic elastomer | |
JP2001279021A (en) | Vulcanizable nitrile-based rubber composition and vulcanized rubber article | |
JP3263973B2 (en) | Internally crosslinked fine particles and rubber composition containing the same | |
JPS6348314A (en) | Fluorinated copolymer | |
JP2783576B2 (en) | Peroxide vulcanizable fluoroelastomer composition | |
US5698635A (en) | Preparation and use of reactive and processable fluoropolymers | |
JPH0641379A (en) | Free-radical-vulcanizable mixture based on fluororubber and acrylic ester rubber | |
JPH0952956A (en) | Master batch for resin additive | |
JPH01242650A (en) | Fluororubber composition containing fine silicone rubber particle | |
JP3601177B2 (en) | Rubber composite | |
JPS627942B2 (en) | ||
JPH07103267B2 (en) | Gas shielding rubber composition and method for producing the same | |
JP2005343929A (en) | Hydrotalcite suspension, polymer blend composition and ozone-proof warmed rubber composition | |
JPH04100846A (en) | Elastomer composition resistant to heat and oil | |
JPH03109456A (en) | Acrylic rubber composition | |
JPH0386746A (en) | Vinyl chloride resin composition | |
JPH01240552A (en) | Novel fluorine-containing elastomer composition and production thereof | |
JPH05320454A (en) | Fluororubber composition | |
JP2002241561A (en) | Fluororubber composition and formed material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071228 Year of fee payment: 6 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081228 Year of fee payment: 7 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081228 Year of fee payment: 7 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 8 Free format text: PAYMENT UNTIL: 20091228 |
|
LAPS | Cancellation because of no payment of annual fees |