JP2018520221A - Chloroprene rubber composition, vulcanized molded article and use thereof - Google Patents
Chloroprene rubber composition, vulcanized molded article and use thereof Download PDFInfo
- Publication number
- JP2018520221A JP2018520221A JP2017557467A JP2017557467A JP2018520221A JP 2018520221 A JP2018520221 A JP 2018520221A JP 2017557467 A JP2017557467 A JP 2017557467A JP 2017557467 A JP2017557467 A JP 2017557467A JP 2018520221 A JP2018520221 A JP 2018520221A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl chloride
- chloroprene rubber
- rubber composition
- polychloroprene
- mass
- 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
- 229920001084 poly(chloroprene) Polymers 0.000 title claims abstract description 128
- 239000000203 mixture Substances 0.000 title claims abstract description 71
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- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 103
- 239000012038 nucleophile Substances 0.000 claims abstract description 23
- -1 thiol compounds Chemical class 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 229920001971 elastomer Polymers 0.000 claims description 25
- 239000005060 rubber Substances 0.000 claims description 25
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 9
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- 239000011248 coating agent Substances 0.000 claims 2
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- 238000006243 chemical reaction Methods 0.000 abstract description 4
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- 239000007795 chemical reaction product Substances 0.000 abstract 1
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- 238000004073 vulcanization Methods 0.000 description 23
- 230000003712 anti-aging effect Effects 0.000 description 17
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- 230000006866 deterioration Effects 0.000 description 1
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- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 229920001519 homopolymer Polymers 0.000 description 1
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- 229910052711 selenium Inorganic materials 0.000 description 1
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- 229920003051 synthetic elastomer Polymers 0.000 description 1
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- PGNWIWKMXVDXHP-UHFFFAOYSA-L zinc;1,3-benzothiazole-2-thiolate Chemical compound [Zn+2].C1=CC=C2SC([S-])=NC2=C1.C1=CC=C2SC([S-])=NC2=C1 PGNWIWKMXVDXHP-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【課題】機械的特性を損なわずに、耐油熱性を向上させた加硫成形体が得られる、ポリ塩化ビニルとポリクロロプレンとを共架橋させた反応物を含むクロロプレンゴム組成物を提供する。
【解決手段】ポリ塩化ビニルと多官能性求核試薬とを化学反応させて得られた改質ポリ塩化ビニルとポリクロロプレンとの共架橋体を含むクロロプレンゴム組成物。改質ポリ塩化ビニルとポリクロロプレンとの共架橋体は、改質ポリ塩化ビニル５〜４５質量部とポリクロロプレン９５〜５５質量部からなるものであることが好ましい。多官能性求核試薬は、チオール化合物から選ばれる少なくとも一種であることが好ましい。
【選択図】なしProvided is a chloroprene rubber composition containing a reaction product obtained by co-crosslinking polyvinyl chloride and polychloroprene, which can obtain a vulcanized molded article having improved oil and heat resistance without impairing mechanical properties.
A chloroprene rubber composition comprising a co-crosslinked product of modified polyvinyl chloride and polychloroprene obtained by chemical reaction of polyvinyl chloride and a polyfunctional nucleophile. The co-crosslinked product of modified polyvinyl chloride and polychloroprene is preferably composed of 5 to 45 parts by mass of modified polyvinyl chloride and 95 to 55 parts by mass of polychloroprene. The multifunctional nucleophile is preferably at least one selected from thiol compounds.
[Selection figure] None
Description
本発明は、ポリ塩化ビニルと多官能性求核試薬とを化学反応させて得られた改質ポリ塩化ビニルとポリクロロプレンとの共架橋体を含むクロロプレンゴム組成物に関する。さらに、本発明は、該クロロプレンゴム組成物を加硫成形して得られた加硫成形体、並びに該加硫成形体を用いた機械用ベルト、防振ゴム、ゴムタイヤなどの各種ゴム製品に関する。 The present invention relates to a chloroprene rubber composition containing a co-crosslinked product of modified polyvinyl chloride and polychloroprene obtained by chemically reacting polyvinyl chloride with a polyfunctional nucleophile. Furthermore, the present invention relates to a vulcanized molded product obtained by vulcanization molding of the chloroprene rubber composition, and various rubber products such as mechanical belts, anti-vibration rubbers and rubber tires using the vulcanized molded product.
クロロプレンゴムは機械特性、耐候性、難燃性などの物性バランスに優れており、加工しやすいことから各種自動車用部品、ベルト、ホース、防振ゴムなどの工業用ゴム部品の原材料として広く使用されている。ポリ塩化ビニルもまた、安価で機械物性や耐候性などに優れた工業用材料として広く使用されている。 Chloroprene rubber is widely used as a raw material for industrial rubber parts such as various automotive parts, belts, hoses, and anti-vibration rubber because it has a good balance of physical properties such as mechanical properties, weather resistance, and flame resistance and is easy to process. ing. Polyvinyl chloride is also widely used as an industrial material that is inexpensive and excellent in mechanical properties and weather resistance.
クロロプレンゴムとポリ塩化ビニルの溶解性パラメータの値は互いに近く、どちらも極性の高い高分子であるため、クロロプレンゴムにポリ塩化ビニルを加えることにより、クロロプレンゴムを用いた各種製品のコストを下げると同時に、耐油性、耐薬性、耐候性、耐火性などを向上させたゴム組成物が得られると期待される。しかしながら、実際にはクロロプレンゴムの結晶性が障害となってこれらの化合物は均一に混合しない。このため、クロロプレンゴムとポリ塩化ビニルを相溶させる技術が検討されてきた。 Since the solubility parameters of chloroprene rubber and polyvinyl chloride are close to each other and both are highly polar polymers, adding polyvinyl chloride to chloroprene rubber can reduce the cost of various products using chloroprene rubber. At the same time, it is expected that a rubber composition having improved oil resistance, chemical resistance, weather resistance, fire resistance and the like can be obtained. However, in practice, the crystallinity of chloroprene rubber is an obstacle, and these compounds do not mix uniformly. For this reason, techniques for compatibilizing chloroprene rubber and polyvinyl chloride have been studied.
クロロプレンゴムとポリ塩化ビニルとを均一に混合させるための技術として、クロロプレンゴムとポリ塩化ビニルの混合物に、特定の化合物を添加して特定温度で複数回の混練する手段が知られている（非特許文献１参照）。
また、使用済みの農業用ポリ塩化ビニルと天然ゴム（又は合成ゴム）とが特定の温度において良好にブレンドできることが知られている（特許文献１参照）。
As a technique for uniformly mixing chloroprene rubber and polyvinyl chloride, a method is known in which a specific compound is added to a mixture of chloroprene rubber and polyvinyl chloride and kneaded a plurality of times at a specific temperature (non-contained). Patent Document 1).
In addition, it is known that used agricultural polyvinyl chloride and natural rubber (or synthetic rubber) can be blended well at a specific temperature (see Patent Document 1).
これらの手段によってポリ塩化ビニルとクロロプレンゴムを相溶させることができる。しかしながら、得られた製品は耐油性が十分でなく、さらなる耐油性の向上が求められていた。 By these means, polyvinyl chloride and chloroprene rubber can be made compatible. However, the obtained product has insufficient oil resistance, and further improvement in oil resistance has been demanded.
そこで、本発明では、ダンベル試験片の引張り試験で評価される機械的特性を損なわずに、耐油熱性をさらに向上させたクロロプレンゴム組成物を提供することを課題とする。さらに、該クロロプレンゴム組成物の加硫成形体、並びに該加硫成形体を用いた機械用ベルト、防振ゴム、車両用タイヤなどの各種ゴム製品を提供することを課題とする。 Therefore, an object of the present invention is to provide a chloroprene rubber composition having further improved oil and heat resistance without impairing mechanical properties evaluated by a tensile test of a dumbbell specimen. It is another object of the present invention to provide a vulcanized molded body of the chloroprene rubber composition and various rubber products such as mechanical belts, vibration-proof rubbers, and vehicle tires using the vulcanized molded body.
本発明者らは、係る課題を解決するために、ポリ塩化ビニルとポリクロロプレンとの共架橋体を得るための薬剤の種類、及び操作条件や手順などを種々検討したことにより、機械的特性を損なうことなく、耐油性を向上させたクロロプレンゴム組成物を得ることに成功し、本発明の完成に至った。 In order to solve such problems, the present inventors have studied various kinds of chemicals for obtaining a co-crosslinked product of polyvinyl chloride and polychloroprene, operating conditions, procedures, and the like. The present invention succeeded in obtaining a chloroprene rubber composition with improved oil resistance without impairing it, and completed the present invention.
即ち本発明は、ポリ塩化ビニルと多官能性求核試薬とを化学反応させて得られた改質ポリ塩化ビニルとポリクロロプレンとの共架橋体を含む、クロロプレンゴム組成物である。
改質ポリ塩化ビニルとポリクロロプレンとの共架橋体は、改質ポリ塩化ビニル５〜４５質量部とポリクロロプレン９５〜５５質量部からなるものであることが好ましい。
多官能性求核試薬は、チオール化合物から選ばれる少なくとも一種であることが好ましい。
改質ポリ塩化ビニルは、ポリ塩化ビニルと多官能性求核試薬を１４０〜１６０℃で化学反応させて得られたものであることが好ましく、改質ポリ塩化ビニルとポリクロロプレンとの共架橋体は、改質ポリ塩化ビニルとポリクロロプレンとを１２０〜１４０℃で共架橋させて得られたものであることが好ましい。
That is, the present invention is a chloroprene rubber composition comprising a co-crosslinked product of modified polyvinyl chloride and polychloroprene obtained by chemically reacting polyvinyl chloride and a polyfunctional nucleophile.
The co-crosslinked product of modified polyvinyl chloride and polychloroprene is preferably composed of 5 to 45 parts by mass of modified polyvinyl chloride and 95 to 55 parts by mass of polychloroprene.
The multifunctional nucleophile is preferably at least one selected from thiol compounds.
The modified polyvinyl chloride is preferably obtained by chemically reacting polyvinyl chloride and a polyfunctional nucleophile at 140 to 160 ° C., and a co-crosslinked product of modified polyvinyl chloride and polychloroprene. Is preferably obtained by co-crosslinking modified polyvinyl chloride and polychloroprene at 120 to 140 ° C.
ポリ塩化ビニルは、軟化温度８０〜１６０℃のものであることが好ましく、改質ポリ塩化ビニル中の多官能性求核試薬は、ポリ塩化ビニル１００質量％中、０．１〜１．５質量％であることが好ましい。
クロロプレンゴム組成物は、加硫成形することで加硫成形体とすることができる。
加硫成形体を使用した具体的な製品の例としては、機械用ベルト、防振ゴム、ゴムタイヤ、ワイパー用ブレード、スポンジ、ホース、電線ケーブル用被覆、ゴムライニングなどがある。
The polyvinyl chloride preferably has a softening temperature of 80 to 160 ° C., and the polyfunctional nucleophile in the modified polyvinyl chloride is 0.1 to 1.5 mass in 100 mass% of polyvinyl chloride. % Is preferred.
The chloroprene rubber composition can be made into a vulcanized molded body by vulcanization molding.
Specific examples of products using the vulcanized molded body include mechanical belts, anti-vibration rubbers, rubber tires, wiper blades, sponges, hoses, wire cable coverings, rubber linings, and the like.
本発明の実施により、引張り試験で評価される機械特性を損なわず、かつ従来よりも耐油性がさらに向上した加硫成形体となるクロロプレンゴム組成物及びこれを用いた加硫成形体が得られる。 By carrying out the present invention, a chloroprene rubber composition and a vulcanized molded article using the chloroprene rubber composition that are vulcanized molded articles having improved oil resistance compared with conventional ones without deteriorating mechanical properties evaluated in a tensile test can be obtained. .
＜クロロプレンゴム組成物＞
クロロプレンゴム組成物は、（１）改質ポリ塩化ビニルと（２）ポリクロロプレンとの共架橋体を含むものである。
<Chloroprene rubber composition>
The chloroprene rubber composition contains (1) a co-crosslinked product of modified polyvinyl chloride and (2) polychloroprene.
（１）改質ポリ塩化ビニル
改質ポリ塩化ビニルとは、多官能性求核試薬とポリ塩化ビニルとを混合して加熱することにより、多官能性求核試薬をポリ塩化ビニルに化学的に結合させた化合物である。
(1) Modified polyvinyl chloride Modified polyvinyl chloride is a chemical reaction of polyfunctional nucleophilic reagent to polyvinyl chloride by mixing and heating the polyfunctional nucleophilic reagent and polyvinyl chloride. It is a bound compound.
多官能性求核試薬は、ポリ塩化ビニルとポリクロロプレンの共架橋を促進させるために用いるものである。多官能性求核試薬は、単にポリ塩化ビニルとポリクロロプレンに添加するだけではポリクロロプレンの架橋が進んで、ポリ塩化ビニルとポリクロロプレンの共架橋が進まない。このため、多官能性求核試薬をポリ塩化ビニルと予め化学反応させてポリ塩化ビニルに架橋点として導入し、この架橋点にポリクロロプレンが架橋することによりポリ塩化ビニルとポリクロロプレンとの共架橋を促進させることができる。 The polyfunctional nucleophile is used to promote co-crosslinking of polyvinyl chloride and polychloroprene. When a polyfunctional nucleophile is simply added to polyvinyl chloride and polychloroprene, crosslinking of polychloroprene proceeds, and co-crosslinking of polyvinyl chloride and polychloroprene does not proceed. For this reason, a polyfunctional nucleophile is chemically reacted with polyvinyl chloride in advance and introduced into polyvinyl chloride as a cross-linking point, and polychloroprene is cross-linked to this cross-linking point, thereby co-crosslinking polyvinyl chloride and polychloroprene. Can be promoted.
多官能性求核試薬は、求核性の官能基を複数有する化合物であり、公知のものを用いることが可能である。多官能性求核試薬としては、チオール化合物があり、具体的には、チオール化合物としては、チオシアヌル酸、２，５−ジメルカプト−１，３，４−チアジアゾール、１，２−ビス［（２−メルカプトエチル）チオ］−３−メルカプトプロパン、ビス（メルカプトメチル）−３，６，９−トリチア−１，１１−ウンデカンジチオール、ペンタエリスリトールテトラキス（β−メルカプトプロピオネート）、１，１，３，３−テトラキス（メルカプトメチルチオ）プロパンから選ばれる１種又は、２種以上を含み、ポリイソ（チオ）シアナート化合物が、ｍ−キシリレンジイソシアナート、ビス（イソシアナトメチル）ノルボルナン、ビス（イソシアナトメチル）シクロヘキサン、ヘキサメチレンジイソシアナート、ジシクロヘキシルメタンジイソシアナートがある。 The polyfunctional nucleophile is a compound having a plurality of nucleophilic functional groups, and known ones can be used. Examples of multifunctional nucleophiles include thiol compounds. Specifically, examples of thiol compounds include thiocyanuric acid, 2,5-dimercapto-1,3,4-thiadiazole, 1,2-bis [(2- Mercaptoethyl) thio] -3-mercaptopropane, bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol, pentaerythritol tetrakis (β-mercaptopropionate), 1,1,3 1 or 2 or more types selected from 3-tetrakis (mercaptomethylthio) propane, and the polyiso (thio) cyanate compound is m-xylylene diisocyanate, bis (isocyanatomethyl) norbornane, bis (isocyanatomethyl) Cyclohexane, hexamethylene diisocyanate, dicyclohexylmethane There is Soshianato.
これらの多官能性求核試薬は、単独で用いても、複数種類の試薬を併用することも可能である。また、これらの多官能性求核試薬が３個〜１０個重合した重合体を用いることも可能である。 These polyfunctional nucleophiles can be used alone or in combination with a plurality of types of reagents. It is also possible to use a polymer in which 3 to 10 of these polyfunctional nucleophiles are polymerized.
多官能性求核試薬の添加量は、ポリ塩化ビニルの全質量に対して０．１〜１．５質量％の範囲とすると、得られるクロロプレンゴム組成物の耐油性と機械強度のバランスが向上するため好ましい。 When the addition amount of the polyfunctional nucleophile is in the range of 0.1 to 1.5% by mass relative to the total mass of polyvinyl chloride, the balance between oil resistance and mechanical strength of the resulting chloroprene rubber composition is improved. Therefore, it is preferable.
ポリ塩化ビニルは、一般に市販されているポリ塩化ビニルを使用することができ、その分子量、分子量分布、化学的な改質、ポリ塩化ビニルに含まれる可塑剤などの添加剤の種類や添加量は、本発明の効果を阻害しない限り特に限定はない。ポリ塩化ビニルの軟化温度は８０〜１６０℃の範囲とすることが好ましい。ポリ塩化ビニルの軟化温度が８０℃未満であると、改質ポリ塩化ビニルとポリクロロプレンを共架橋させる際に改質ポリ塩化ビニルが熱軟化して目的としたクロロプレンゴム組成物が得られない場合がある。
ポリ塩化ビニルの軟化温度が１６０℃を超えると、必然的に多官能性求核試薬とポリ塩化ビニルとの反応温度が１６０℃を超えてしまう。このため、得られる改質ポリ塩化ビニルに導入される架橋点の数が少なくなってしまい、目的としたクロロプレンゴム組成物が得られなくなる可能性がある。
For polyvinyl chloride, commercially available polyvinyl chloride can be used, and its molecular weight, molecular weight distribution, chemical modification, and types and amounts of additives such as plasticizers contained in polyvinyl chloride are There is no particular limitation as long as the effects of the present invention are not impaired. The softening temperature of polyvinyl chloride is preferably in the range of 80 to 160 ° C. When the polyvinyl chloride softening temperature is less than 80 ° C., when the modified polyvinyl chloride and polychloroprene are co-crosslinked, the modified polyvinyl chloride is thermally softened and the intended chloroprene rubber composition cannot be obtained. There is.
When the softening temperature of polyvinyl chloride exceeds 160 ° C, the reaction temperature between the polyfunctional nucleophile and polyvinyl chloride inevitably exceeds 160 ° C. For this reason, the number of crosslinking points introduced into the resulting modified polyvinyl chloride decreases, and the intended chloroprene rubber composition may not be obtained.
改質ポリ塩化ビニルを得るには、多官能性求核試薬とポリ塩化ビニルとを混合して加熱すればよい。具体的には、公知のバンバリーミキサー、ニーダーミキサー、オープンロールなどの混練装置を用いてポリ塩化ビニルの軟化温度以上に設定した温度でポリ塩化ビニルを混練し、これに多官能性求核試薬を添加し、さらに所定時間混練を続けることにより、多官能性求核試薬とポリ塩化ビニルが化学反応をして改質ポリ塩化ビニルが得られる。
混練装置の混練温度は、１４０〜１６０℃に調整することにより、得られるクロロプレンゴム組成物の機械強度が向上するため好ましい。
In order to obtain modified polyvinyl chloride, a polyfunctional nucleophile and polyvinyl chloride may be mixed and heated. Specifically, polyvinyl chloride is kneaded at a temperature set above the softening temperature of polyvinyl chloride using a kneading apparatus such as a known Banbury mixer, kneader mixer, or open roll, and a polyfunctional nucleophilic reagent is added thereto. By adding and further kneading for a predetermined time, the polyfunctional nucleophile and polyvinyl chloride undergo a chemical reaction to obtain modified polyvinyl chloride.
The kneading temperature of the kneading apparatus is preferably adjusted to 140 to 160 ° C. because the mechanical strength of the resulting chloroprene rubber composition is improved.
（２）ポリクロロプレン
ポリクロロプレンは、クロロプレンの単独重合体又は、クロロプレンと、クロロプレンと共重合可能な他の単量体との共重合体である。クロロプレンと共重合可能な単量体としては、例えば、２，３−ジクロロ−１，３−ブタジエン、１−クロロ−１，３−ブタジエン、スチレン、アクリロニトリル、メタクリロニトリル、イソプレン、ブタジエン、並びにアクリル酸、メタクリル酸及びこれらのエステル類などがあり、本発明の目的を満たす範囲で用いることができる。本発明においては、本発明の効果を阻害しない限り、いずれのポリクロロプレンを用いることが可能である。
(2) Polychloroprene Polychloroprene is a chloroprene homopolymer or a copolymer of chloroprene and another monomer copolymerizable with chloroprene. Examples of monomers copolymerizable with chloroprene include 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, styrene, acrylonitrile, methacrylonitrile, isoprene, butadiene, and acrylic. There are acids, methacrylic acid and esters thereof, and the like can be used as long as the object of the present invention is satisfied. In the present invention, any polychloroprene can be used as long as the effects of the present invention are not impaired.
本発明のポリクロロプレンは、用いる分子量調節剤により、メルカプタン変性タイプ、キサントゲン変性タイプ、硫黄変性タイプに分類される。メルカプタン変性タイプのクロロプレンゴムは、ｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルオクチルメルカプタン、オクチルメルカプタンなどのアルキルメルカプタン類を分子量調節剤に使用して得られるものであり、キサントゲン変性タイプのクロロプレンゴムは、アルキルキサントゲン化合物を分子量調節剤に使用して得られるものである。また、硫黄変成タイプのクロロプレンゴムは、イオウとクロロプレン系単量体を共重合したポリマーをチウラムジスルフィドで可塑化し、所定のムーニー粘度に調整したものである。本発明においては、本発明の効果を阻害しない限り、いずれのポリクロロプレンを用いることが可能である。 The polychloroprene of the present invention is classified into a mercaptan-modified type, a xanthogen-modified type, and a sulfur-modified type depending on the molecular weight regulator used. Mercaptan-modified chloroprene rubber is obtained by using an alkyl mercaptan such as n-dodecyl mercaptan, tert-dodecyl octyl mercaptan, octyl mercaptan as a molecular weight regulator, and xanthogen-modified chloroprene rubber is an alkyl xanthogen. It is obtained by using a compound as a molecular weight regulator. The sulfur-modified chloroprene rubber is obtained by plasticizing a polymer obtained by copolymerizing sulfur and a chloroprene monomer with thiuram disulfide so as to have a predetermined Mooney viscosity. In the present invention, any polychloroprene can be used as long as the effects of the present invention are not impaired.
改質ポリ塩化ビニルとポリクロロプレンとを共架橋させるには、改質ポリ塩化ビニルとポリクロロプレンとを混合して加熱すればよい。具体的には、上述の方法によって得られた改質ポリ塩化ビニルにポリクロロプレンを加えて１２０〜１４０℃の範囲で所定時間混練すればよい。混練温度をこの範囲に調整することにより、得られるクロロプレンゴム組成物の機械強度が向上するため好ましい。改質ポリ塩化ビニルとポリクロロプレンを混練する装置は、公知のバンバリーミキサー、ニーダーミキサー、オープンロールなどの混練装置を用いればよい。 In order to co-crosslink the modified polyvinyl chloride and polychloroprene, the modified polyvinyl chloride and polychloroprene may be mixed and heated. Specifically, polychloroprene may be added to the modified polyvinyl chloride obtained by the above method and kneaded in the range of 120 to 140 ° C. for a predetermined time. It is preferable to adjust the kneading temperature within this range because the mechanical strength of the resulting chloroprene rubber composition is improved. As a device for kneading the modified polyvinyl chloride and polychloroprene, a kneading device such as a known Banbury mixer, kneader mixer, or open roll may be used.
改質ポリ塩化ビニルとポリクロロプレンとの共架橋体は、ポリ塩化ビニルの組成比が５〜４５質量部、ポリクロロプレンの組成比が９５〜５５質量部の範囲に調整すると、得られるクロロプレンゴム組成物がクロロプレンゴムをマトリックスとした組成物となり、引張り試験で評価される機械特性が維持されるため好ましい。 The co-crosslinked product of modified polyvinyl chloride and polychloroprene is obtained by adjusting the composition ratio of polyvinyl chloride to 5 to 45 parts by mass and the composition ratio of polychloroprene to 95 to 55 parts by mass. The product is preferably a composition using chloroprene rubber as a matrix, and the mechanical properties evaluated by the tensile test are maintained.
クロロプレンゴム組成物は、本発明の効果を損なわない範囲内において、さらに公知の加硫剤、加硫促進剤、加硫助剤、一次老化防止剤、二次老化防止剤、可塑剤、加工助剤を添加してもよい。 The chloroprene rubber composition further includes known vulcanizing agents, vulcanization accelerators, vulcanization aids, primary anti-aging agents, secondary anti-aging agents, plasticizers, processing aids within the range not impairing the effects of the present invention. An agent may be added.
加硫剤は、硫黄、ベリリウム、マグネシウム、亜鉛、カルシウム、バリウム、ゲルマニウム、チタニウム、錫、ジルコニウム、アンチモン、バナジウム、ビスマス、モリブデン、タングステン、テルル、セレン、鉄、ニッケル、コバルト、オスミウムなどの金属単体、及びこれら金属の酸化物や水酸化物を使用することができる。これら添加可能な加硫剤のなかでも、特に硫黄、酸化カルシウムや酸化亜鉛、三酸化鉄、二酸化チタン、酸化鉛、四酸化三鉛、二酸化アンチモン、三酸化アンチモン、酸化マグネシウム、ハイドロタルサイトの加硫効果が高いため好ましい。また、これらの加硫剤は２種以上を併用して用いてもよい。加硫剤の配合量は、クロロプレンゴム組成物中のポリ塩化ビニルとポリクロロプレンの合計１００質量部に対して０．１質量部以上１０質量部以下の範囲で添加することが可能である。 Vulcanizing agents are sulfur, beryllium, magnesium, zinc, calcium, barium, germanium, titanium, tin, zirconium, antimony, vanadium, bismuth, molybdenum, tungsten, tellurium, selenium, iron, nickel, cobalt, osmium, etc. , And oxides and hydroxides of these metals can be used. Among these vulcanizing agents that can be added, especially sulfur, calcium oxide and zinc oxide, iron trioxide, titanium dioxide, lead oxide, trilead tetraoxide, antimony dioxide, antimony trioxide, magnesium oxide and hydrotalcite. It is preferable because of its high sulfur effect. These vulcanizing agents may be used in combination of two or more. The compounding amount of the vulcanizing agent can be added in the range of 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass in total of polyvinyl chloride and polychloroprene in the chloroprene rubber composition.
加硫促進剤は、クロロプレンゴム組成物の加硫を促進させるために添加する化合物であり、クロロプレンゴムの加硫に一般に用いられるチオウレア系、グアニジン系、チウラム系、チアゾール系、過酸化物などがある。 Vulcanization accelerators are compounds that are added to accelerate vulcanization of chloroprene rubber compositions, and include thiourea, guanidine, thiuram, thiazole, and peroxides that are commonly used for vulcanization of chloroprene rubber. is there.
チオウレア系化合物としては、エチレンチオウレア、ジエチルチオウレア、トリメチルチオウレア、トリエチルチオウレア、Ｎ，Ｎ’−ジフェニルチオウレアなどがある。 Examples of the thiourea compound include ethylene thiourea, diethyl thiourea, trimethyl thiourea, triethyl thiourea, N, N′-diphenyl thiourea and the like.
グアニジン系化合物としては、グアニジン、１，３−ジフェニルグアニジン、ジ−ｏ−トリルグアニジン、ジ−ｍ−トリルグアニジン、ジ−ｐ−トリルグアニジン、１−ｏ−トリルビグアニド、１−ｍ−トリルビグアニド、１−ｐ−トリルビグアニド、ジカテコールボレートのジ−ｏ−トリグアニジン塩、ジカテコールボレートのジ−ｍ−トリルグアニジン塩、ジカテコールボレートのジ−ｐ−トリグアニジン塩、塩酸グアニジン、硝酸グアニジン、炭酸グアニジン、りん酸グアニジン、スルファミン酸グアニジン、ホルミルグアニジン、アセチルグアニジン、クロルアセチルグアニジン、１，２−ｎ−ジアセチルグアニジン、１，３−ｎ−ジアセチルグアニジン、１，３−ｎ−ジプロピオニルグアニジン、ヒプリルグアニジン、ベンゼンスルフォニルグアニジンなどがある。 Examples of guanidine compounds include guanidine, 1,3-diphenylguanidine, di-o-tolylguanidine, di-m-tolylguanidine, di-p-tolylguanidine, 1-o-tolylbiguanide, 1-m-tolylbiguanide, 1-p-tolylbiguanide, di-o-triguanidine salt of dicatechol borate, di-m-tolylguanidine salt of dicatechol borate, di-p-triguanidine salt of dicatechol borate, guanidine hydrochloride, guanidine nitrate, carbonic acid Guanidine, guanidine phosphate, guanidine sulfamate, formylguanidine, acetylguanidine, chloroacetylguanidine, 1,2-n-diacetylguanidine, 1,3-n-diacetylguanidine, 1,3-n-dipropionylguanidine, hippuryl Guanidine, benzene Sulfonyl Le guanidine and the like.
チウラム系化合物としては、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、ジペンタメチルチウラムテトラスルフィド、テトラメチルチウラムモノスルフィド、テトラベンジルチウラムジスルフィド、テトラキス２−エチルヘキシルチウラムジスルフィドなどがある。 Examples of thiuram compounds include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylthiuram tetrasulfide, tetramethylthiuram monosulfide, tetrabenzylthiuram disulfide, and tetrakis-2-ethylhexylthiuram disulfide.
チアゾール系化合物としては、２−メルカプトベンゾチアゾール、ベンゾチアゾリルジスルフィド、ジ−２−ベンゾチアゾリルジスルフィド、２−メルカプトベンゾチアゾール亜鉛塩、２−モルフォリノジチオベンゾチアゾール、Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド、Ｎ，Ｎ−ジシクロヘキシル−２−ベンゾチアゾリルスルフェンアミド、１−（Ｎ，Ｎ−ジエチルチオカルバモイスルファニル）−１，３−ベンゾチアゾールなどがある。 Examples of thiazole compounds include 2-mercaptobenzothiazole, benzothiazolyl disulfide, di-2-benzothiazolyl disulfide, 2-mercaptobenzothiazole zinc salt, 2-morpholinodithiobenzothiazole, N-cyclohexyl-2- Examples include benzothiazolylsulfenamide, N, N-dicyclohexyl-2-benzothiazolylsulfenamide, 1- (N, N-diethylthiocarbamoylsulfanyl) -1,3-benzothiazole.
過酸化物としては、ジクミル過酸化物、バレレート過酸化物、アルキル過酸化物、置換アルキル芳香族過酸化物などがある。 Examples of the peroxide include dicumyl peroxide, valerate peroxide, alkyl peroxide, and substituted alkyl aromatic peroxide.
その他の加硫促進剤として、３−メチルチアゾリジンチオン−２−チアジアゾールとフェニレンジマレイミドとの混合物、ジメチルアンモニウムハイドロジェンイソフタレートあるいは１，２−ジメルカプト−１，３，４−チアジアゾール誘導体などの加硫促進剤も使用することができる。 As other vulcanization accelerators, vulcanization of a mixture of 3-methylthiazolidinethione-2-thiadiazole and phenylene dimaleimide, dimethylammonium hydrogen isophthalate or 1,2-dimercapto-1,3,4-thiadiazole derivative, etc. Accelerators can also be used.
これらの加硫促進剤は上記に挙げたものを二種以上併用して用いてもよい。これらの加硫促進剤の添加量は、本発明のクロロプレンゴム組成物中のポリ塩化ビニルとポリクロロプレンの合計１００質量部に対して０．５〜５質量部とすることが可能である。 These vulcanization accelerators may be used in combination of two or more of those listed above. The addition amount of these vulcanization accelerators can be 0.5 to 5 parts by mass with respect to 100 parts by mass in total of polyvinyl chloride and polychloroprene in the chloroprene rubber composition of the present invention.
加硫助剤は、加硫促進剤の効率を上げるために添加する化合物であり、ステアリン酸、ステアリン酸亜鉛などの脂肪酸やその金属塩がある。過酸化物を用いる場合には、二官能性エステル化合物又は三官能性エステル化合物から選ばれる少なくとも一種の化合物を併用することが好ましい。具体的には、トリメチロールプロパン、エチレングリコールジメタクリレート、トリアリルイソシアネート、フェニレンジマレイミドが用いられる。
これら加硫促進助剤の添加量は、本発明のクロロプレンゴム組成物中のポリ塩化ビニルとポリクロロプレンの合計１００質量部に対して０．５〜５質量部が可能である。
Vulcanization aids are compounds added to increase the efficiency of vulcanization accelerators, and include fatty acids such as stearic acid and zinc stearate and metal salts thereof. When using a peroxide, it is preferable to use together at least 1 type of compound chosen from a bifunctional ester compound or a trifunctional ester compound. Specifically, trimethylolpropane, ethylene glycol dimethacrylate, triallyl isocyanate, and phenylene dimaleimide are used.
The addition amount of these vulcanization acceleration aids can be 0.5 to 5 parts by mass with respect to 100 parts by mass in total of polyvinyl chloride and polychloroprene in the chloroprene rubber composition of the present invention.
一次老化防止剤は、得られるクロロプレンゴム組成物加硫成形体やその防振ゴムが加熱されたときのデュロメータ硬さ、破断伸び、圧縮永久歪みの低下を抑え、耐熱性を向上させるために添加する化合物であり、フェノール系老化防止剤、アミン系老化防止剤、アクリレート系老化防止剤、カルバミン酸金属塩及びワックスがある。これらの一次老化防止剤は、一種類もしくは併用して使用することができる。これら化合物の中でも、アミン系老化防止剤の４，４’−ビス（α，α−ジメチルベンジル）ジフェニルアミンやオクチル化ジフェニルアミンは、耐熱性の改善効果が大きいため好ましい。 The primary anti-aging agent is added to improve the heat resistance by suppressing the decrease in durometer hardness, elongation at break, and compression set when the resulting chloroprene rubber composition vulcanized molded product and its anti-vibration rubber are heated. There are phenolic anti-aging agents, amine-based anti-aging agents, acrylate-based anti-aging agents, carbamic acid metal salts and waxes. These primary antiaging agents can be used alone or in combination. Among these compounds, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine and octylated diphenylamine, which are amine-based antioxidants, are preferable because they have a large effect of improving heat resistance.
一次老化防止剤の配合量は、本発明のクロロプレンゴム組成物中のポリ塩化ビニルとポリクロロプレンの合計１００質量部に対し、０．１〜１０質量部とすることが可能である。一次老化防止剤の配合量をこの範囲に設定することにより、得られる加硫成形体の破断伸び等の機械物性の低下が抑えられ、耐熱性を向上させることができる。 The compounding amount of the primary antiaging agent can be 0.1 to 10 parts by mass with respect to 100 parts by mass in total of polyvinyl chloride and polychloroprene in the chloroprene rubber composition of the present invention. By setting the blending amount of the primary anti-aging agent within this range, deterioration of mechanical properties such as breaking elongation of the obtained vulcanized molded article can be suppressed, and heat resistance can be improved.
二次老化防止剤は、得られるクロロプレンゴム組成物加硫成形体やその防振ゴムが加熱されたときのデュロメータ硬さ、破断伸び、圧縮永久歪みの低下を抑え、耐熱性を向上させるために添加するものであり、リン系老化防止剤、イオウ系老化防止剤、イミダゾール系老化防止剤を挙げることができる。これらの二次老化防止剤は、一種類もしくは併用して使用することができる。これらの化合物の中でも、リン系老化防止剤のトリス（ノニルフェニル）ホスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、イオウ系老化防止剤のチオジオプロピオン酸ジラウリル、ジミスチル−３，３’−チオジプロピオネート、ジステアリル−３，３’−チオジプロピオネート、イミダゾール系老化防止剤の２−メルカプトベンゾイミダゾール、１−ベンジル−２−エチルイミダゾールは、耐熱性改善効果が大きいため好ましい。 The secondary anti-aging agent is to improve the heat resistance by suppressing the decrease in durometer hardness, elongation at break and compression set when the resulting chloroprene rubber composition vulcanized molded article and its anti-vibration rubber are heated. Examples thereof include phosphorus-based anti-aging agents, sulfur-based anti-aging agents, and imidazole-based anti-aging agents. These secondary anti-aging agents can be used alone or in combination. Among these compounds, phosphorus antioxidants such as tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, sulfur antioxidants dilauryl thiodiopropionate, dimystil- 3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, 2-mercaptobenzoimidazole and 1-benzyl-2-ethylimidazole as imidazole anti-aging agents have an effect of improving heat resistance. It is preferable because it is large.
二次老化防止剤の配合量は、本発明のクロロプレンゴム組成物中のポリ塩化ビニルとポリクロロプレンの合計１００質量部に対して、０．１〜１０質量部とすることが可能である。二次老化防止剤の配合量をこの範囲にすることにより、得られる加硫成形体の破断伸び等の機械物性の低下が抑えられ、耐熱性を向上させることができる。 The compounding amount of the secondary anti-aging agent can be 0.1 to 10 parts by mass with respect to 100 parts by mass in total of polyvinyl chloride and polychloroprene in the chloroprene rubber composition of the present invention. By making the compounding quantity of a secondary antiaging agent into this range, the fall of mechanical properties, such as breaking elongation of the obtained vulcanized molded object, is suppressed, and heat resistance can be improved.
可塑剤は、得られるクロロプレンゴム組成物を可塑化するために添加する化合物であり、菜種油などの植物油、アマニ油、ヒマシ油、ヤシ油などの植物油、フタレート系可塑剤、ＤＵＰ（フタル酸ジウンデシル）、ＤＯＳ（セバシン酸ジオクチル）、ＤＯＡ（アジピン酸ジオクチル）、エステル系可塑剤、エーテルエステル系可塑剤、チオエーテル系可塑剤、アロマ系オイル、ナフテン系オイル、潤滑油、プロセスオイル、パラフィン、流動パラフィン、ワセリン、石油アスファルトなどの石油系可塑剤がある。クロロプレンゴム組成物に要求される特性に合わせて一種類もしくは複数を併用して使用することができる。可塑剤の配合量は、本発明のクロロプレンゴム組成物中のポリ塩化ビニルとポリクロロプレンの合計１００質量部に対して、５〜５０質量部とすることができる。 The plasticizer is a compound that is added to plasticize the resulting chloroprene rubber composition. Vegetable oil such as rapeseed oil, vegetable oil such as linseed oil, castor oil, coconut oil, phthalate plasticizer, DUP (diundecyl phthalate) , DOS (dioctyl sebacate), DOA (dioctyl adipate), ester plasticizer, ether ester plasticizer, thioether plasticizer, aroma oil, naphthenic oil, lubricating oil, process oil, paraffin, liquid paraffin, There are petroleum plasticizers such as petroleum jelly and petroleum asphalt. One or more types can be used in combination according to the properties required for the chloroprene rubber composition. The compounding quantity of a plasticizer can be 5-50 mass parts with respect to a total of 100 mass parts of polyvinyl chloride and polychloroprene in the chloroprene rubber composition of this invention.
加工助剤は、クロロプレンゴム組成物がロールや成形金型、押出機のスクリューなどから剥離しやすくなるようにするなど、加工特性を向上させるために添加する化合物である。具体的には、ステアリン酸などの脂肪酸あるいはポリエチレンなどのパラフィン系加工助剤、脂肪酸アミドなどがあり、本発明のクロロプレンゴム組成物中のポリ塩化ビニルとポリクロロプレンの合計１００質量部に対して、０．５〜５質量部まで添加できる。 The processing aid is a compound that is added to improve processing characteristics such that the chloroprene rubber composition is easily peeled off from a roll, a molding die, an extruder screw, or the like. Specifically, there is a fatty acid such as stearic acid or a paraffinic processing aid such as polyethylene, a fatty acid amide, etc., and a total of 100 parts by mass of polyvinyl chloride and polychloroprene in the chloroprene rubber composition of the present invention, It can be added up to 0.5-5 parts by mass.
クロロプレンゴム組成物には、本発明の目的を損なわない範囲で、さらに各種の充填剤や補強剤を添加することができる。充填剤や補強剤の例としては、カーボンブラック、シリカ、クレー、タルク、炭酸カルシウムなどがある。これら充填剤、補強剤は使用目的に合わせて、２種以上を併用して用いてもよい。これら充填剤、補強剤の添加量はクロロプレンゴム組成物中のポリ塩化ビニルとポリクロロプレンの合計１００質量部に対して、１〜１００質量部とすることが可能である。 Various fillers and reinforcing agents can be further added to the chloroprene rubber composition as long as the object of the present invention is not impaired. Examples of fillers and reinforcing agents include carbon black, silica, clay, talc, calcium carbonate and the like. These fillers and reinforcing agents may be used in combination of two or more according to the purpose of use. The addition amount of these fillers and reinforcing agents can be 1 to 100 parts by mass with respect to 100 parts by mass in total of polyvinyl chloride and polychloroprene in the chloroprene rubber composition.
＜加硫成形体＞
加硫成形体は、上述の方法によって得られたクロロプレンゴム組成物を加硫成形して得たものである。加硫成形体は、クロロプレンゴム組成物を所望する各種の形状に成形した後に加硫したものでも、又は予めクロロプレンゴム組成物を加硫しておき、その後各種の形状に成形したものであってもよい。クロロプレンゴム組成物や加硫ゴムを成形する方法は、従来のプレス成形、押出成形、カレンダー成形などの方法がある。これらは、通常のゴム工業で用いられている方法を採用すればよい。
<Vulcanized molded body>
The vulcanized molded body is obtained by vulcanizing and molding the chloroprene rubber composition obtained by the above method. The vulcanized molded product may be a chloroprene rubber composition molded into various desired shapes and then vulcanized, or a chloroprene rubber composition previously vulcanized and then molded into various shapes. Also good. Methods for molding the chloroprene rubber composition and vulcanized rubber include conventional press molding, extrusion molding, calendar molding, and the like. For these, a method used in a normal rubber industry may be adopted.
クロロプレンゴム組成物の加硫は特にその方法を選ばないが、一般的なスチーム加硫やＵＨＦ加硫により加硫することができる。スチーム加硫は、未加硫のクロロプレンゴム組成物に、熱媒体としてのスチームガスによって圧力と温度を与えて加硫させる手段であり、ＵＨＦ加硫は、クロロプレンゴム組成物にマイクロ波を照射して加硫させる手段である。また、プレス加硫や射出成形の際に成形用金型の内部にクロロプレンゴム組成物を保持したまま金型温度を加硫温度まで上昇させて加硫させてもよい。加硫温度はクロロプレンゴム組成物の配合や加硫剤の種類によって適宜設定でき、通常は１４０〜２２０℃が好ましく、１５０〜１８０℃の範囲がより好ましい。 The method for vulcanizing the chloroprene rubber composition is not particularly limited, but can be vulcanized by general steam vulcanization or UHF vulcanization. Steam vulcanization is a means for vulcanizing an unvulcanized chloroprene rubber composition by applying pressure and temperature with steam gas as a heat medium, and UHF vulcanization irradiates the chloroprene rubber composition with microwaves. This is a means for vulcanization. Further, at the time of press vulcanization or injection molding, the mold temperature may be raised to the vulcanization temperature while the chloroprene rubber composition is held inside the mold for vulcanization. The vulcanization temperature can be appropriately set depending on the composition of the chloroprene rubber composition and the type of the vulcanizing agent, and is usually preferably 140 to 220 ° C, more preferably 150 to 180 ° C.
加硫成形体は、具体的には、機械用ベルト、防振ゴム、ゴムタイヤ、ワイパー用ブレード、スポンジ、ホース、電線ケーブル用被覆、ゴムライニングとして利用される。 Specifically, the vulcanized molded body is used as a mechanical belt, a vibration-proof rubber, a rubber tire, a wiper blade, a sponge, a hose, an electric cable cover, or a rubber lining.
以下、参考例、実施例によりさらに詳細に説明するが、本発明はこれらに限定して解釈されるものではない。なお、以下の参考例、実施例で用いるインターナルミキサー、二本ロール等の装置類、ポリ塩化ビニル、ポリクロロプレン、各種薬剤はすべて共通して使用するものとする。 Hereinafter, although a reference example and an Example demonstrate in detail, this invention is limited to these and is not interpreted. In addition, devices such as an internal mixer and two rolls used in the following reference examples and examples, polyvinyl chloride, polychloroprene, and various drugs are all used in common.
＜改質ポリ塩化ビニルＡの作製＞
インターナルミキサー（装置名：ラボプラストミル７５Ｃ １００型、株式会社東洋精機製作所製）を用い、ポリ塩化ビニル（Shanghai Chlor-Alkali Chemical Co., Ltd.製）２０質量部、チオシアヌル酸（黄岩東海化工有限公司製）０．３質量部、酸化マグネシウム（協和化学工業株式会社製）４質量部を添加し、１３０℃で１２分間混練して改質ポリ塩化ビニルＡを得た。
<Production of modified polyvinyl chloride A>
Using an internal mixer (equipment name: Labo Plast Mill 75C 100, manufactured by Toyo Seiki Seisakusho Co., Ltd.), 20 parts by weight of polyvinyl chloride (manufactured by Shanghai Chlor-Alkali Chemical Co., Ltd.), thiocyanuric acid (Huangyan Tokai Chemical) Co., Ltd.) 0.3 parts by mass and magnesium oxide (manufactured by Kyowa Chemical Industry Co., Ltd.) 4 parts by mass were added and kneaded at 130 ° C. for 12 minutes to obtain modified polyvinyl chloride A.
＜改質ポリ塩化ビニルＢ〜Ｅの作製＞
ポリ塩化ビニルと各添加剤を混練する温度を、それぞれ１４０℃、１５０℃、１６０℃、１７０℃とした他は、全ての条件を改質ポリ塩化ビニルＡの条件に揃え、改質ポリ塩化ビニルＢ〜Ｅを得た。
<Production of modified polyvinyl chlorides B to E>
All the conditions are the same as the conditions of the modified polyvinyl chloride A except that the temperatures at which the polyvinyl chloride and each additive are kneaded are 140 ° C., 150 ° C., 160 ° C. and 170 ° C., respectively. B to E were obtained.
＜改質ポリ塩化ビニルＦ、Ｇの作製＞
ポリ塩化ビニルと各添加剤を混練する時間を、それぞれ８分、及び１６分とした他は、全ての条件を改質ポリ塩化ビニルＣの条件に揃え、改質ポリ塩化ビニルＦ、Ｇを得た。
<Production of modified polyvinyl chloride F and G>
The modified polyvinyl chloride F and G were obtained by aligning all the conditions with the conditions of the modified polyvinyl chloride C except that the time for kneading the polyvinyl chloride and each additive was 8 minutes and 16 minutes, respectively. It was.
＜改質ポリ塩化ビニルＨの作製＞
チオシアヌル酸０．３質量部を、２，５−ジメルカプト−１，３，４−チアジアゾール（Adamas Reagent, Ltd.製）０．３質量部に変更した他は、全ての条件を改質ポリ塩化ビニルＣを作製した条件に揃え、改質ポリ塩化ビニルＨを得た。
改質ポリ塩化ビニルＡ〜Ｈで使用した多官能性求核試薬の種類、混練温度、混練時間をまとめて表１に示す。
<Production of modified polyvinyl chloride H>
Modified polyvinyl chloride in all conditions except that 0.3 parts by weight of thiocyanuric acid was changed to 0.3 parts by weight of 2,5-dimercapto-1,3,4-thiadiazole (manufactured by Adams Reagent, Ltd.) A modified polyvinyl chloride H was obtained in accordance with the conditions for preparing C.
Table 1 summarizes the types of polyfunctional nucleophiles used in the modified polyvinyl chlorides A to H, the kneading temperature, and the kneading time.
＜共架橋体Ａの作製＞
インターナルミキサーを用い、改質ポリ塩化ビニルＡ２０質量部、ポリクロロプレン（電気化学工業株式会社製ＤＣＲ−ＯＭ−４０）８０質量部を配合し、１３０℃で４分間混練して、共架橋体Ａを得た。
<Preparation of co-crosslinked product A>
Using an internal mixer, 20 parts by mass of modified polyvinyl chloride A and 80 parts by mass of polychloroprene (DCR-OM-40, manufactured by Denki Kagaku Kogyo Co., Ltd.) are blended and kneaded for 4 minutes at 130 ° C. Got.
＜共架橋体Ｂ〜Ｈの作製＞
改質ポリ塩化ビニルＡを、それぞれ改質ポリ塩化ビニルＢ〜Ｈに置き換えた他は、全ての条件を共架橋体Ａを作製した条件に揃え、共架橋体Ｂ〜Ｈを得た。
<Preparation of co-crosslinked bodies B to H>
Except that the modified polyvinyl chloride A was replaced with the modified polyvinyl chlorides B to H, all the conditions were aligned with the conditions for producing the co-crosslinked body A to obtain co-crosslinked bodies B to H.
＜共架橋体Ｉ、Ｊの作製＞
改質ポリ塩化ビニルとポリクロロプレンを混練する温度を、それぞれ１２０℃、１４０℃、とした他は、全ての条件を共架橋体Ｃを作製した条件に揃え、共架橋体Ｉ、Ｊを得た。
<Preparation of co-crosslinked bodies I and J>
All the conditions were adjusted to the conditions for preparing the co-crosslinked body C except that the temperatures for kneading the modified polyvinyl chloride and polychloroprene were 120 ° C. and 140 ° C., respectively, to obtain co-crosslinked bodies I and J .
＜共架橋体Ｋ、Ｌの作製＞
改質ポリ塩化ビニルＣ及びポリクロロプレンの配合量を、それぞれ５：９５、４５：５５とした他は、全ての条件を共架橋体Ｃを作製した条件に揃え、共架橋体Ｋ、Ｌを得た。
<Preparation of co-crosslinked bodies K and L>
All the conditions were adjusted to the conditions for preparing the co-crosslinked product C, except that the blending amounts of the modified polyvinyl chloride C and polychloroprene were 5:95 and 45:55, respectively. It was.
＜共架橋体Ｍ、Ｎの作製＞
改質ポリ塩化ビニルとポリクロロプレンを混練する温度を、それぞれ１０５℃、１５５℃、とした他は、全ての条件を共架橋体Ｃを作製した条件に揃え、共架橋体Ｍ、Ｎを得た。
<Preparation of co-crosslinked bodies M and N>
Co-crosslinked bodies M and N were obtained by aligning all the conditions with the conditions for preparing the co-crosslinked body C, except that the temperatures for kneading the modified polyvinyl chloride and polychloroprene were 105 ° C. and 155 ° C., respectively. .
＜共架橋体Ｏの作製＞
前記インターナルミキサーを用い、前記ポリ塩化ビニル２０質量部と前記ポリクロロプレン８０質量部とを１４分間混練した後、前記チオシアヌル酸を０．３質量部、前記酸化マグネシウムを４質量部添加し、さらに４分間混練を継続して、共架橋体Ｏを得た。
<Preparation of co-crosslinked body O>
Using the internal mixer, 20 parts by mass of polyvinyl chloride and 80 parts by mass of polychloroprene are kneaded for 14 minutes, then 0.3 parts by mass of thiocyanuric acid and 4 parts by mass of magnesium oxide are added. Kneading was continued for 4 minutes to obtain a co-crosslinked product O.
＜共架橋体Ｐの作製＞
チオシアヌル酸０．５質量部を、２，５−ジメルカプト−１，３，４−チアジアゾール（Adamas Reagent, Ltd.製）０．３質量部に変更した他は、全ての条件を共架橋体Ｏを作製した条件に揃え、共架橋体Ｐを得た。
<Preparation of co-crosslinked product P>
Other than changing 0.5 parts by mass of thiocyanuric acid to 0.3 parts by mass of 2,5-dimercapto-1,3,4-thiadiazole (manufactured by Adams Reagent, Ltd.) A co-crosslinked product P was obtained in accordance with the prepared conditions.
＜共架橋体Ｑの作製＞
チオシアヌル酸０．５質量部を、添加しなかった他は、全ての条件を共架橋体Ｏを作製した条件に揃え、共架橋体Ｑを得た。
<Preparation of co-crosslinked product Q>
Except that 0.5 parts by mass of thiocyanuric acid was not added, all the conditions were aligned with the conditions for producing the co-crosslinked body O, and a co-crosslinked body Q was obtained.
共架橋体Ａ〜Ｑの製造条件をまとめて表２に示す。 Table 2 summarizes the production conditions of the co-crosslinked products A to Q.
＜実施例１＞
上述の方法によって得られた共架橋体Ａを１００質量部と、酸化亜鉛（三井金属工業株式会社製）５質量部、エチレンチオウレア（製品名：アクセル２２Ｓ、川口化学工業株式会社製）０．５質量部、ステアリン酸（中国国薬集団化学試剤有限公司製）０．５質量部を加え、直径４インチの二本オープンロールを用いて４０℃で、５分間混練することにより、実施例１のクロロプレンゴム組成物を得た。
<Example 1>
100 parts by mass of the co-crosslinked product A obtained by the above-described method, 5 parts by mass of zinc oxide (Mitsui Kinzoku Kogyo Co., Ltd.), 0.5 of ethylenethiourea (product name: Accel 22S, Kawaguchi Chemical Co., Ltd.) 0.5 By adding 0.5 parts by mass of stearic acid (manufactured by China Pharmaceutical Group Chemical Reagent Co., Ltd.) and kneading at 40 ° C. for 5 minutes using two open rolls having a diameter of 4 inches, A chloroprene rubber composition was obtained.
＜評価＞
上述の方法によって得られた実施例１のクロロプレンゴム組成物を、１６０℃×２０分、圧力０．８ＭＰａの条件でプレス加硫し、厚さ２．０ｍｍの加硫成形体シートを作製した。この加硫成形体シートから試験片を切り出し、試験片作製直後に、ＪＩＳ Ｋ６２５１に準拠して機械的強度試験（引張り強さ、破断伸び、１００％引張り弾性率測定）を行った。具体的には、加硫成形体シートからダンベル３号形をもちいて試験片を切り出し、全自動ゴム引張り試験機（装置名：ＡＧＳ‐Ｈ、島津製作所製）を用いて、雰囲気温度を２３℃、引張り速度５００ｍｍ／分の条件で測定した。
また、切り出した試験片を、ＡＳＴＭ Ｎｏ．３オイルに、１００℃で、７０時間浸漬した後に、ＪＩＳ Ｋ６２５８に準拠して浸漬試験を行い、耐油性試験（体積変化率、重量変化率）を行った。クロロプレンゴム組成物を用いて得た加硫成形体の機械的強度は、引張り強さ７．５ＭＰａ以上、破断伸び２２０％以上、１００％引張り弾性率０．２ＭＰａであれば合格とした。耐油性は、体積変化率８０％以下、重量変化率１００％以下であれば合格とした。得られた結果を表３に示す。
<Evaluation>
The chloroprene rubber composition of Example 1 obtained by the above-described method was press-vulcanized under the conditions of 160 ° C. × 20 minutes and a pressure of 0.8 MPa to prepare a vulcanized molded sheet having a thickness of 2.0 mm. A test piece was cut out from the vulcanized molded sheet, and immediately after the test piece was produced, a mechanical strength test (tensile strength, elongation at break, 100% tensile elastic modulus measurement) was performed in accordance with JIS K6251. Specifically, a test piece was cut out from the vulcanized molded sheet using No. 3 dumbbell, and the atmosphere temperature was 23 ° C. using a fully automatic rubber tensile tester (device name: AGS-H, manufactured by Shimadzu Corporation). The measurement was performed under the condition of a pulling speed of 500 mm / min.
In addition, the cut-out test piece is ASTM No. After dipping in 3 oils at 100 ° C. for 70 hours, an immersion test was conducted in accordance with JIS K6258, and an oil resistance test (volume change rate, weight change rate) was conducted. The mechanical strength of the vulcanized molded body obtained using the chloroprene rubber composition was determined to be acceptable if the tensile strength was 7.5 MPa or more, the breaking elongation was 220% or more, and the 100% tensile modulus was 0.2 MPa. Oil resistance was determined to be acceptable if the volume change rate was 80% or less and the weight change rate was 100% or less. The obtained results are shown in Table 3.
＜実施例２〜１２、比較例１〜５＞
共架橋体Ａを、それぞれ共架橋体Ｂ〜Ｑに置き換えた他は、全ての条件を実施例１の条件に揃え、実施例２〜１２及び比較例１〜５のクロロプレンゴム組成物を作製し、実施例１と同一の条件で評価をおこなった。評価結果を表３に示す。比較例１は、混練温度が低かったため、改質ポリ塩化ビニルとポリクロロプレンが均一に分散せずクロロプレンゴム組成物を得られなかった。比較例２は、混練温度が高かったため、改質ポリ塩化ビニルとポリクロロプレンの一部が加硫してしまい一部が粉状のクロロプレンゴム組成物となってしまった。このため、比較例１と比較例２については、評価を行わなかった。
<Examples 2 to 12, Comparative Examples 1 to 5>
The chloroprene rubber compositions of Examples 2 to 12 and Comparative Examples 1 to 5 were prepared by aligning all the conditions with those of Example 1 except that the co-crosslinked body A was replaced with co-crosslinked bodies B to Q, respectively. Evaluation was performed under the same conditions as in Example 1. The evaluation results are shown in Table 3. In Comparative Example 1, because the kneading temperature was low, the modified polyvinyl chloride and polychloroprene were not uniformly dispersed, and a chloroprene rubber composition could not be obtained. In Comparative Example 2, since the kneading temperature was high, a part of the modified polyvinyl chloride and polychloroprene was vulcanized, and a part thereof became a powdery chloroprene rubber composition. For this reason, Comparative Example 1 and Comparative Example 2 were not evaluated.
本発明のクロロプレンゴム組成物は、表３に示すとおり引張り試験で評価される機械的特性を損なわずに、耐油熱性をさらに向上させたクロロプレンゴム組成物の加硫物を得ることができた。 As shown in Table 3, the chloroprene rubber composition of the present invention was able to obtain a vulcanized product of the chloroprene rubber composition having further improved oil heat resistance without impairing the mechanical properties evaluated by the tensile test.
本出願は、２０１５年５月０４日に中国特許局に提出し、出願番号が２０１５１０２２１８４９．６であり、発明名称が「クロロプレンゴム組成物、加硫成形体及びその用途」との中国特許出願を基礎とする優先権を主張し、その開示の総てをここに取り込む。 This application was filed with the Chinese Patent Office on May 04, 2015, and the application number was 2015102211849.6, and the title of the invention was “Chloroprene rubber composition, vulcanized molded product and use thereof”. Claims the underlying priority and incorporates all of its disclosure here.
Claims (12)
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| CN201510221849.6 | 2015-05-04 | ||
| CN201510221849.6A CN106188707A (en) | 2015-05-04 | 2015-05-04 | Chloroprene rubber composition, sulfidization molding body and application thereof |
| PCT/CN2016/080989 WO2016177327A1 (en) | 2015-05-04 | 2016-05-04 | Chloroprene rubber composition, vulcanized moulded body and use thereof |
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| JP (1) | JP6905472B2 (en) |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6333438A (en) * | 1986-07-28 | 1988-02-13 | Nippon Zeon Co Ltd | Thermoplastic rubber composition |
| JPH07502555A (en) * | 1991-12-23 | 1995-03-16 | ノルスク・ヒドロ・アクシェセルスカープ | Method of manufacturing heat-stable and chemical-resistant plastics |
| WO2014157602A1 (en) * | 2013-03-28 | 2014-10-02 | 電気化学工業株式会社 | Blended rubber, blended rubber composition and vulcanizate |
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| CA1124445A (en) * | 1977-10-17 | 1982-05-25 | Hercules Incorporated | 2,5-dimercapto-1,3,4-thiadiazole as a cross-linker for saturated, halogen containing polymers |
| JPS5856537B2 (en) * | 1979-04-13 | 1983-12-15 | 東洋リノリユ−ム株式会社 | Crosslinkable composition of polyvinyl chloride resin |
| NO175597C (en) * | 1992-09-14 | 1994-11-02 | Norsk Hydro As | Crosslinked silane-containing PVC copolymer and a process for its preparation |
| CN102775658A (en) * | 2012-08-01 | 2012-11-14 | 天津铭天高分子材料有限公司 | Chloroprene rubber/polyvinyl chloride co-precipitation rubber and preparation method thereof |
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2015
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6333438A (en) * | 1986-07-28 | 1988-02-13 | Nippon Zeon Co Ltd | Thermoplastic rubber composition |
| JPH07502555A (en) * | 1991-12-23 | 1995-03-16 | ノルスク・ヒドロ・アクシェセルスカープ | Method of manufacturing heat-stable and chemical-resistant plastics |
| WO2014157602A1 (en) * | 2013-03-28 | 2014-10-02 | 電気化学工業株式会社 | Blended rubber, blended rubber composition and vulcanizate |
Non-Patent Citations (1)
| Title |
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| 中村儀郎、外１名: "ポリ塩化ビニルの改質に関する研究", 高分子化学, vol. 22巻、246号, JPN7020001076, 11 March 1965 (1965-03-11), JP, pages 646 - 651, ISSN: 0004478545 * |
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| WO2016177327A1 (en) | 2016-11-10 |
| CN107531952B (en) | 2020-07-10 |
| TW201702304A (en) | 2017-01-16 |
| JP6905472B2 (en) | 2021-07-21 |
| CN107531952A (en) | 2018-01-02 |
| CN106188707A (en) | 2016-12-07 |
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