JP6905472B2 - Chloroprene rubber composition, vulcanized molded article and its uses - Google Patents
Chloroprene rubber composition, vulcanized molded article and its uses Download PDFInfo
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- JP6905472B2 JP6905472B2 JP2017557467A JP2017557467A JP6905472B2 JP 6905472 B2 JP6905472 B2 JP 6905472B2 JP 2017557467 A JP2017557467 A JP 2017557467A JP 2017557467 A JP2017557467 A JP 2017557467A JP 6905472 B2 JP6905472 B2 JP 6905472B2
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- JP
- Japan
- Prior art keywords
- polyvinyl chloride
- mass
- chloroprene rubber
- rubber composition
- polychloroprene
- 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.)
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- 229920001084 poly(chloroprene) Polymers 0.000 title claims description 118
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- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- WQJONRMBVKFKOB-UHFFFAOYSA-N cyanatosulfanyl cyanate Chemical class N#COSOC#N WQJONRMBVKFKOB-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 1
- 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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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229960000789 guanidine hydrochloride Drugs 0.000 description 1
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- NGGXACLSAZXJGM-UHFFFAOYSA-N n-(diaminomethylidene)acetamide Chemical compound CC(=O)N=C(N)N NGGXACLSAZXJGM-UHFFFAOYSA-N 0.000 description 1
- XEBPBJPZBUSUEO-UHFFFAOYSA-N n-(diaminomethylidene)formamide Chemical compound NC(=N)NC=O XEBPBJPZBUSUEO-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- VUTVSWPVTJZPFU-UHFFFAOYSA-N propylsulfanylmethanethiol Chemical compound CCCSCS VUTVSWPVTJZPFU-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- GPNLWUFFWOYKLP-UHFFFAOYSA-N s-(1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound C1=CC=C2SC(SN)=NC2=C1 GPNLWUFFWOYKLP-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- AUZONCFQVSMFAP-UHFFFAOYSA-N tetraethylthiuram disulfide Natural products CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 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
- 229940099259 vaseline Drugs 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)
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 vulcanizing the chloroprene rubber composition, and various rubber products such as a mechanical belt, anti-vibration rubber, and a rubber tire 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 has an excellent balance of physical properties such as mechanical properties, weather resistance, and flame retardancy, and is easy to process, so it is widely used as a raw material for various automobile parts, belts, hoses, vibration-proof rubber, and other industrial rubber parts. ing. Polyvinyl chloride is also widely used as an industrial material that is inexpensive and has excellent 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 will 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 reality, the crystallinity of the chloroprene rubber is an obstacle and these compounds are not uniformly mixed. Therefore, a technique for blending chloroprene rubber and polyvinyl chloride has 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 means of adding a specific compound to a mixture of chloroprene rubber and polyvinyl chloride and kneading the mixture at a specific temperature multiple times is known (non-). See Patent Document 1).
Further, it is known that used agricultural polyvinyl chloride and natural rubber (or synthetic rubber) can be satisfactorily blended 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 compatible with each other. However, the obtained product does not have sufficient oil resistance, and further improvement in oil resistance has been required.
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, it is an object of the present invention to provide a chloroprene rubber composition having further improved oil heat resistance without impairing the mechanical properties evaluated in the tensile test of the dumbbell test piece. Another object of the present invention is to provide a vulcanized molded product of the chloroprene rubber composition, and various rubber products such as mechanical belts, anti-vibration rubbers, and vehicle tires using the vulcanized molded product.
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 the above problems, the present inventors have examined various types of chemicals for obtaining a co-crosslinked product of polyvinyl chloride and polychloroprene, as well as operating conditions and procedures, and have made mechanical properties. We succeeded in obtaining a chloroprene rubber composition having improved oil resistance without damaging 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 containing a co-crosslinked product of modified polyvinyl chloride and polychloroprene obtained by chemically reacting polyvinyl chloride with 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 polyfunctional nucleophile is preferably at least one selected from thiol compounds.
The modified polyvinyl chloride is preferably obtained by chemically reacting polyvinyl chloride with a polyfunctional nucleophilic reagent at 140 to 160 ° C., and is a co-crosslinked product of the 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% by mass in 100% by mass of the polyvinyl chloride. It is preferably%.
The chloroprene rubber composition can be made into a vulcanized molded product by vulcanization molding.
Specific examples of products using the vulcanized molded product include mechanical belts, anti-vibration rubber, rubber tires, wiper blades, sponges, hoses, electric wire cable coatings, 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 which is a vulcanized molded product having further improved oil resistance as compared with the conventional one without impairing the mechanical properties evaluated in the tensile test and a vulcanized molded product using the same 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 chemically converts a polyfunctional nucleophile into polyvinyl chloride by mixing and heating a polyfunctional nucleophile 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。 Polyfunctional nucleophiles are used to promote co-crosslinking of polyvinyl chloride and polychloroprene. When the polyfunctional nucleophile is simply added to polyvinyl chloride and polychloroprene, the cross-linking of polyvinyl chloride proceeds and the co-crosslinking of polyvinyl chloride and polychloroprene does not proceed. Therefore, a polyfunctional nucleophilic reagent is chemically reacted with polyvinyl chloride in advance to introduce it into polyvinyl chloride as a cross-linking point, and polychloroprene is cross-linked at this cross-linking point to co-crosslink 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. The polyfunctional nucleophilic reagent includes a thiol compound, and specifically, the thiol compound includes isocyanurate, 2,5-dimercapto-1,3,4-thiadiazol, 1,2-bis [(2-2-). Mercaptoethyl) thio] -3-mercaptopropane, bis (mercaptomethyl) -3,6,9-trithia-1,11-undecandithiol, pentaerythritol tetrakis (β-mercaptopropionate), 1,1,3 Containing one or more selected from 3-tetrakis (mercaptomethylthio) propane, polyiso (thio) cyanate compounds are m-xylylene diisocyanate, bis (isocyanatomethyl) norbornan, bis (isocyanatomethyl). There are cyclohexane, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate.
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 obtained by polymerizing 3 to 10 of these polyfunctional nucleophiles.
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 amount of the polyfunctional nucleophile added is in the range of 0.1 to 1.5% by mass with respect to the total mass of polyvinyl chloride, the balance between the oil resistance and the mechanical strength of the obtained chloroprene rubber composition is improved. It is preferable to do so.
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。
As the polyvinyl chloride, commercially available polyvinyl chloride can be used, and the type and amount of additives such as the molecular weight, the molecular weight distribution, the chemical modification, and the plasticizer contained in the polyvinyl chloride can be determined. , There is no particular limitation as long as the effect of the present invention is not impaired. The softening temperature of polyvinyl chloride is preferably in the range of 80 to 160 ° C. When the softening temperature of polyvinyl chloride is less than 80 ° C., the modified polyvinyl chloride is thermally softened when the modified polyvinyl chloride and polychloroprene are co-crosslinked, and the desired chloroprene rubber composition cannot be obtained. There is.
When the softening temperature of polyvinyl chloride exceeds 160 ° C, the reaction temperature of the polyfunctional nucleophile and polyvinyl chloride inevitably exceeds 160 ° C. Therefore, the number of cross-linking points introduced into the obtained modified polyvinyl chloride may be reduced, and the desired 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。
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 device such as a known Banbury mixer, kneader mixer, or open roll, and a polyfunctional nucleophile is added thereto. By adding and continuing kneading for a predetermined time, the polyfunctional nucleophile and polyvinyl chloride chemically react 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 obtained 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 homopolymer of chloroprene or a copolymer of chloroprene and another monomer copolymerizable with chloroprene. Examples of the monomer copolymerizable with chloroprene include 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, styrene, acrylonitrile, methacrylonitrile, isoprene, butadiene, and acrylic acid. There are acids, methacrylic acids, esters thereof and the like, and they can be used within a range satisfying the object of the present invention. 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 xanthate-modified type, and a sulfur-modified type according to the molecular weight modifier used. The mercaptan-modified type chloroprene rubber is obtained by using alkyl mercaptans such as n-dodecyl mercaptan, tert-dodecyl octyl mercaptan, and octyl mercaptan as a molecular weight regulator, and the xanthogen-modified type chloroprene rubber is an alkylxanthogen. It is obtained by using a compound as a molecular weight modifier. Further, the sulfur-modified type chloroprene rubber is obtained by plasticizing a polymer obtained by copolymerizing sulfur and a chloroprene-based monomer with thiuram disulfide and adjusting the viscosity to 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. Adjusting the kneading temperature within this range is preferable because the mechanical strength of the obtained chloroprene rubber composition is improved. As an apparatus for kneading the modified polyvinyl chloride and polychloroprene, a known kneading apparatus such as a Banbury mixer, a kneader mixer, or an 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 has a chloroprene rubber composition obtained by adjusting the composition ratio of polyvinyl chloride to 5 to 45 parts by mass and the composition ratio of polychloroprene to the range of 95 to 55 parts by mass. It is preferable because the product becomes a composition using chloroprene rubber as a matrix and the mechanical properties evaluated in 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 is further known as a vulcanizing agent, a vulcanization accelerator, a vulcanization aid, a primary anti-aging agent, a secondary anti-aging agent, a plasticizer, and a processing aid, as long as the effects of the present invention are not impaired. Agents 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。 Sulfurizers are simple metals such as sulfur, beryllium, magnesium, zinc, calcium, barium, germanium, titanium, tin, zirconium, antimony, vanadium, bismuth, molybdenum, tungsten, tellurium, selenium, iron, nickel, cobalt, and osmium. , And oxides and hydroxides of these metals can be used. Among these vulcanizing agents that can be added, sulfur, calcium oxide, zinc oxide, iron trioxide, titanium dioxide, lead oxide, trilead tetroxide, antimony dioxide, antimony trioxide, magnesium oxide, and hydrotalcite are added. It is preferable because it has a high sulfurizing effect. Moreover, you may use these vulcanizing agents in combination of 2 or more types. The blending amount of the vulcanizing agent can be added in the range of 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the 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。 The vulcanization accelerator is a compound added to accelerate the vulcanization of the chloroprene rubber composition, and thiourea-based, guanidine-based, thiuram-based, thiazole-based, peroxides, etc., which are generally used for vulcanization of chloroprene rubber, are used. be.
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, and N, N'-diphenyl thiourea.
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, and the like. 1-p-tolylbiguanide, di-o-triguanidine salt of dicatecholbolate, di-m-trilguanidine salt of dicatecholbolate, di-p-triguanidine salt of dicatecholbolate, guanidine hydrochloride, guanidine nitrate, carbonic acid Guanidine, guanidine phosphate, guanidine sulfamate, formyl guanidine, acetyl guanidine, chloracetyl guanidine, 1,2-n-diacetyl guanidine, 1,3-n-diacetyl guanidine, 1,3-n-dipropionyl guanidine, hipril There are guanidine, benzenesulfonylguanidine, etc.
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 the thiuram compound include tetramethylthium disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethyl thiuram tetrasulfide, tetramethyl thiuram monosulfide, tetrabenzyl thiuram disulfide, and tetrakis 2-ethylhexyl thiuram 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, and N-cyclohexyl-2-. Benzothiazolyl sulphenamide, N, N-dicyclohexyl-2-benzothiazolyl sulphenamide, 1- (N, N-diethylthiocarbamoisulfanyl) -1,3-benzothiazole and the like.
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 a dicumyl peroxide, a valerate peroxide, an alkyl peroxide, and a 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。 Other vulcanization accelerators include vulcanizations such as a mixture of 3-methylthiazolidinethio-2-thiadiazole and phenylenedimaleimide, dimethylammonium hydrogenisophthalate or a 1,2-dimercapto-1,3,4-thiadiazole derivative. 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。 As these vulcanization accelerators, two or more of those listed above may be used in combination. The amount of these vulcanization accelerators added 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。
The vulcanization aid is a compound added to increase the efficiency of the vulcanization accelerator, and includes fatty acids such as stearic acid and zinc stearate and metal salts thereof. When a peroxide is used, it is preferable to use at least one compound selected from a bifunctional ester compound or a trifunctional ester compound in combination. Specifically, trimethylolpropane, ethylene glycol dimethacrylate, triallyl isocyanate, and phenylenedimaleimide are used.
The amount of these vulcanization accelerating aids added 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, breaking elongation, and compressive permanent strain when the obtained chloroprene rubber composition vulcanized molded product and its anti-vibration rubber are heated. There are phenol-based anti-aging agents, amine-based anti-aging agents, acrylate-based anti-aging agents, carbamic acid metal salts, and waxes. These primary anti-aging agents can be used alone or in combination. Among these compounds, amine-based antiaging agents 4,4'-bis (α, α-dimethylbenzyl) diphenylamine and octylated diphenylamine 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 blending 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 in this range, deterioration of mechanical properties such as elongation at break of the obtained vulcanized molded product 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 used to suppress the decrease in durometer hardness, breaking elongation, and compression set when the obtained chloroprene rubber composition vulcanized molded product and its vibration-proof rubber are heated, and to improve heat resistance. 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, the phosphorus-based anti-aging agents tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, and the sulfur-based anti-aging agents dilauryl thiodiopropionate, dimystyl- 3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole and 1-benzyl-2-ethylimidazole, which are imidazole-based antiaging 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 blending amount of the secondary 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 secondary anti-aging agent within this range, deterioration of mechanical properties such as elongation at break of the obtained vulcanized molded product can be 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 added to plasticize the obtained chloroprene rubber composition, and is a vegetable oil such as rapeseed oil, vegetable oil such as flaxseed oil, castor oil, and palm oil, a phthalate plasticizer, and 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-based plasticizers such as Vaseline and petroleum asphalt. One type or a plurality of types can be used in combination according to the properties required for the chloroprene rubber composition. The blending amount of the plasticizer can be 5 to 50 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 added to improve the processing characteristics, such as making the chloroprene rubber composition easier to peel off from a roll, a molding die, a screw of an extruder, or the like. Specifically, there are fatty acids such as stearic acid, paraffin-based processing aids such as polyethylene, fatty acid amides, etc., with respect to 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 to 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. Two or more of these fillers and reinforcing agents may be used in combination according to the purpose of use. The amount of these fillers and reinforcing agents added 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 product>
The vulcanized molded product is obtained by vulcanizing the chloroprene rubber composition obtained by the above method. The vulcanized molded product may be one obtained by molding the chloroprene rubber composition into various desired shapes and then vulcanizing it, or one in which the chloroprene rubber composition is vulcanized in advance and then molded into various shapes. May be good. As a method for molding the chloroprene rubber composition or vulcanized rubber, there are conventional press molding, extrusion molding, calendar molding and the like. For these, the method used in the ordinary 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 vulcanization method of the chloroprene rubber composition is not particularly selected, but it 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. It is a means for vulcanization. Further, during press vulcanization or injection molding, the mold temperature may be raised to the vulcanization temperature while the chloroprene rubber composition is held inside the molding mold for vulcanization. The vulcanization temperature can be appropriately set depending on the composition of the chloroprene rubber composition and the type of 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 product is used as a mechanical belt, anti-vibration rubber, rubber tire, wiper blade, sponge, hose, wire cable coating, and 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, the present invention will be described in more detail with reference to Reference Examples and Examples, but the present invention is not limited to these. The following reference examples, internal mixers used in the examples, devices such as double rolls, polyvinyl chloride, polychloroprene, and various chemicals shall all be 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。
<Preparation of modified polyvinyl chloride A>
Using an internal mixer (device name: Labplast Mill 75C 100 type, manufactured by Toyo Seiki Seisakusho Co., Ltd.), 20 parts by mass of polyvinyl chloride (manufactured by Shanghai Chlor-Alkali Chemical Co., Ltd.), thiocianulic acid (Yellow Rock Tokai Kako) 0.3 parts by mass of (manufactured by Kyowa Chemical Industry Co., Ltd.) and 4 parts by mass of magnesium oxide (manufactured by Kyowa Chemical Industry Co., Ltd.) 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。
<Preparation of modified polyvinyl chlorides B to E>
All conditions were adjusted to the conditions of modified polyvinyl chloride A, except that the temperatures for kneading the polyvinyl chloride and each additive were 140 ° C, 150 ° C, 160 ° C, and 170 ° C, respectively, and the modified polyvinyl chloride was used. 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。
<Preparation of modified polyvinyl chloride F and G>
All the conditions were adjusted to the conditions of modified polyvinyl chloride C, except that the time for kneading the polyvinyl chloride and each additive was 8 minutes and 16 minutes, respectively, to obtain modified polyvinyl chlorides F and G. rice field.
＜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。
<Preparation of modified polyvinyl chloride H>
All conditions were modified polyvinyl chloride except that 0.3 parts by mass of thiocyanuric acid was changed to 0.3 parts by mass of 2,5-dimercapto-1,3,4-thiadiazole (manufactured by Adamas Reagent, Ltd.). The modified polyvinyl chloride H was obtained under the conditions in which C was prepared.
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 body A>
Using an internal mixer, mix 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.), knead at 130 ° C. for 4 minutes, and co-crosslink A. 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 for replacing the modified polyvinyl chloride A with the modified polyvinyl chlorides B to H, all the conditions were adjusted to the conditions for producing the co-crosslinked products A to obtain co-crosslinked products 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>
Except that the temperatures at which the modified polyvinyl chloride and polychloroprene were kneaded were set to 120 ° C. and 140 ° C., respectively, all the conditions were adjusted to the conditions under which the co-crosslinked product C was prepared to obtain co-crosslinked products 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>
Except that the blending amounts of the modified polyvinyl chloride C and polychloroprene were 5:95 and 45:55, respectively, all the conditions were adjusted to the conditions for producing the co-crosslinked product C, and the co-crosslinked products K and L were obtained. rice field.
＜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>
Except that the temperature at which the modified polyvinyl chloride and polychloroprene were kneaded was 105 ° C. and 155 ° C., respectively, all the conditions were adjusted to the conditions under which the co-crosslinked product C was prepared to obtain co-crosslinked products M and N. ..
＜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>
After kneading 20 parts by mass of the polyvinyl chloride and 80 parts by mass of the polychloroprene for 14 minutes using the internal mixer, 0.3 parts by mass of the thiocyanic acid and 4 parts by mass of the magnesium oxide were added, and further. 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 body P>
All the conditions were changed to 0.3 parts by mass of 2,5-dimercapto-1,3,4-thiadiazole (manufactured by Adamas Reagent, Ltd.), except that 0.5 parts by mass of thiocianulic acid was changed to co-crosslinked O. The co-crosslinked product P was obtained according to 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 body Q>
All the conditions except that 0.5 part by mass of thiocyanic acid was not added were adjusted to the conditions for producing the co-crosslinked product O to obtain the co-crosslinked product Q.
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 co-crosslinked product A obtained by the above method, 5 parts by mass of zinc oxide (manufactured by Mitsui Metal Industry Co., Ltd.), and 0.5 parts by weight of ethylenethiourea (product name: Accelerator 22S, manufactured by Kawaguchi Chemical Industry Co., Ltd.) Example 1 by adding 0.5 parts by mass and 0.5 parts by mass of stearic acid (manufactured by China Pharmaceutical Group Chemical Testing 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 method was press-vulcanized under the conditions of 160 ° C. × 20 minutes and a pressure of 0.8 MPa to prepare a vulcanized molded article sheet having a thickness of 2.0 mm. A test piece was cut out from this vulcanized molded product sheet, and immediately after the test piece was prepared, a mechanical strength test (tensile strength, breaking elongation, 100% tensile elastic modulus measurement) was performed in accordance with JIS K6251. Specifically, a test piece is cut out from a vulcanized molded product sheet using a dumbbell No. 3 type, and an atmospheric temperature is set to 23 ° C. using a fully automatic rubber tensile tester (device name: AGS-H, manufactured by Shimadzu Corporation). , The measurement was carried out under the condition of a tensile speed of 500 mm / min.
In addition, the cut out test piece was designated as ASTM No. After immersing in 3 oils at 100 ° C. for 70 hours, a dipping test was conducted in accordance with JIS K6258, and an oil resistance test (volume change rate, weight change rate) was performed. The mechanical strength of the vulcanized molded product obtained by using the chloroprene rubber composition was acceptable if it had a tensile strength of 7.5 MPa or more, a breaking elongation of 220% or more, and a 100% tensile elastic modulus of 0.2 MPa. The oil resistance was judged to be acceptable if the volume change rate was 80% or less and the weight change rate was 100% or less. The results obtained 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>
All the conditions were adjusted to the conditions of Example 1 except that the co-crosslinked bodies A were replaced with the co-crosslinked bodies B to Q, respectively, and the chloroprene rubber compositions of Examples 2 to 12 and Comparative Examples 1 to 5 were prepared. , The evaluation was performed under the same conditions as in Example 1. The evaluation results are shown in Table 3. In Comparative Example 1, since 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 of the modified polyvinyl chloride rubber composition became a powdery chloroprene rubber composition. Therefore, 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 in 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 submitted to the Chinese Patent Office on May 04, 2015, and a Chinese patent application with the application number 201510221849.6 and the invention name "chloroprene rubber composition, vulcanized molded article and its use" was filed. Claim the underlying priority and incorporate all of its disclosures here.
Claims (7)
前記ポリ塩化ビニルと前記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質量部以下の加硫剤とを含み、
前記多官能性求核試薬が、チオール化合物から選ばれる少なくとも一種であり、
前記共架橋体が、前記改質ポリ塩化ビニル５〜２０質量部と前記ポリクロロプレン９５〜８０質量部との共架橋体である、クロロプレンゴム組成物。 A co-crosslinked product of modified polyvinyl chloride and polychloroprene obtained by chemically reacting polyvinyl chloride with a polyfunctional nucleophile,
A vulcanizing agent of 0.1 part by mass or more and 10 parts by mass or less is contained with respect to 100 parts by mass of the total of the polyvinyl chloride and the polychloroprene.
The polyfunctional nucleophile is at least one selected from thiol compounds.
A chloroprene rubber composition in which the co-crosslinked product is a co-crosslinked product of 5 to 20 parts by mass of the modified polyvinyl chloride and 95 to 80 parts by mass of the polychloroprene.
ポリ塩化ビニルと多官能性求核試薬を１４０〜１６０℃で化学反応させて前記改質ポリ塩化ビニルを得る工程と、
前記改質ポリ塩化ビニル５〜２０質量部と前記ポリクロロプレン９５〜８０質量部とを共架橋させて前記共架橋体を得る工程と、
前記ポリ塩化ビニルと前記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質量部以下の前記加硫剤を、前記共架橋体に添加する工程と、を備え、
前記多官能性求核試薬が、チオール化合物から選ばれる少なくとも一種である、製造方法。 A method for producing a chloroprene rubber composition containing a co-crosslinked product of modified polyvinyl chloride and polychloroprene and a vulcanizing agent.
A step of chemically reacting polyvinyl chloride with a polyfunctional nucleophile at 140 to 160 ° C. to obtain the modified polyvinyl chloride, and
A step of co-crosslinking 5 to 20 parts by mass of the modified polyvinyl chloride and 95 to 80 parts by mass of the polychloroprene to obtain the co-crosslinked product.
A step of adding the vulcanizing agent of 0.1 part by mass or more and 10 parts by mass or less to the co-crosslinked product with respect to 100 parts by mass of the total of the polyvinyl chloride and the polychloroprene is provided.
A production method, wherein the polyfunctional nucleophile is at least one selected from thiol compounds.
前記多官能性求核試薬の添加量が、前記ポリ塩化ビニルの全質量に対して０．１〜１．５質量％である、請求項２又は３に記載の製造方法。 The softening temperature of the polyvinyl chloride is 80 to 160 ° C.
The production method according to claim 2 or 3, wherein the amount of the polyfunctional nucleophile added is 0.1 to 1.5% by mass with respect to the total mass of the polyvinyl chloride.
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| CN201510221849.6A CN106188707A (en) | 2015-05-04 | 2015-05-04 | Chloroprene rubber composition, sulfidization molding body and application thereof |
| CN201510221849.6 | 2015-05-04 | ||
| PCT/CN2016/080989 WO2016177327A1 (en) | 2015-05-04 | 2016-05-04 | Chloroprene rubber composition, vulcanized moulded body and use thereof |
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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 |
| JPS6333438A (en) * | 1986-07-28 | 1988-02-13 | Nippon Zeon Co Ltd | Thermoplastic rubber composition |
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