JP2012255099A - Crosslinked polymer composition and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinked polymer composition excellent in heat-aging resistance and the like.SOLUTION: The crosslinked polymer composition is obtained by blending, into a polymer: a zinc-based crosslinking aid in which zinc oxide particles or basic zinc carbonate particles are supported on the surface of a silicate particle; and an organic peroxide as a crosslinking agent, wherein the polymer is crosslinked by using the organic peroxide.

Description

  The present invention relates to a crosslinked polymer composition crosslinked using an organic peroxide as a crosslinking agent and a method for producing the same.

  In recent years, with an increase in the ambient temperature around the engine room of an automobile and an increase in the information processing speed of a computer, a demand for a polymer having excellent heat resistance is increasing.

  In order to increase heat resistance, organic peroxides are increasingly used as cross-linking agents instead of sulfur in cross-linked polymers (Patent Document 1).

  Moreover, in order to improve heat resistance, mixing metal oxides, such as a cerium oxide, is examined (patent document 2).

  In a fuel-based rubber hose used for transportation of fuel such as an automobile, a material polymer having high heat resistance is used (Patent Document 3).

JP 2003-103528 A JP 2000-212444 A JP 2008-195040 A

  An object of the present invention is to provide a crosslinked polymer composition excellent in heat aging resistance and the like and a method for producing the same.

  The crosslinked polymer composition of the present invention is prepared by blending a polymer with a zinc-based crosslinking aid in which zinc oxide fine particles or basic zinc carbonate fine particles are supported on the surface of silicate particles, and an organic peroxide as a crosslinking agent. It is characterized by being crosslinked with an organic peroxide.

  By using the crosslinking aid according to the present invention, the crosslinking density can be increased and a crosslinked polymer composition excellent in heat aging resistance and the like can be obtained.

  In this invention, it is preferable that the zinc type crosslinking adjuvant is mix | blended in the range of 0.5-10 mass parts with respect to 100 mass parts of polymers.

  Moreover, in this invention, it is preferable that the organic peroxide is mix | blended in the range of 0.5-10 mass parts with respect to 100 mass parts of polymers.

  The supported amount of zinc oxide fine particles or basic zinc carbonate fine particles in the zinc-based crosslinking aid in the present invention is preferably in the range of 6 to 75% by mass in terms of metallic zinc.

  In the present invention, examples of the silicate particles include anhydrous aluminum silicate mineral particles.

  The production method of the present invention is a method capable of producing the above-mentioned crosslinked polymer composition of the present invention, a step of blending a polymer with a zinc-based crosslinking aid and an organic peroxide, a zinc-based crosslinking aid and an organic It is characterized by comprising a step of heating a polymer containing a peroxide and crosslinking the polymer with an organic peroxide.

  According to the present invention, a crosslinked polymer composition having excellent heat aging resistance and the like can be obtained.

  According to the production method of the present invention, a crosslinked polymer composition excellent in heat aging resistance and the like can be efficiently produced.

  Hereinafter, the present invention will be described in more detail.

<Zinc-based crosslinking aid>
As the zinc-based crosslinking aid used in the present invention, those in which zinc oxide fine particles or basic zinc carbonate fine particles are supported on the surface of silicate particles are used. The surface of the silicate particles has an affinity for the zinc oxide fine particles and the basic zinc carbonate fine particles, and therefore, the zinc oxide fine particles or the basic zinc carbonate fine particles can be uniformly supported.

  The supported amount of zinc oxide fine particles or basic zinc carbonate fine particles is preferably in the range of 6 to 75% by mass in terms of metallic zinc. Here, the supported amount in terms of metal zinc is calculated from the following equation using the calculated Zn equivalent mass obtained by converting the supported zinc oxide fine particles or basic zinc carbonate fine particles to metal zinc. be able to.

  Metal zinc equivalent loading (mass%) = [(Zn equivalent mass) / (mass of zinc-based crosslinking aid)] × 100

  If the supported amount is less than the above range, the crosslinking density cannot be sufficiently increased, and good heat aging resistance or the like may not be obtained. Moreover, even if there is too much carrying amount than said range, the effect accompanying it may not be acquired but it may become economically disadvantageous.

BET specific surface area of the silicate particles carrying the zinc oxide fine particles is preferably in the range of 10~55m ² / g, more preferably in the range of 15 to 50 m ² / g, more preferably 20～45M ² / G.

It is preferable that the BET specific surface area of the silicate particle | grains which carry | supported the basic zinc carbonate fine particle is the range of 25-90 m < ² > / g, More preferably, it is 30-85 m < ² > / g, More preferably, it is 35-80 m < ² >. / G.

  Basic zinc carbonate fine particles are finer than zinc oxide fine particles, and can be fine particles having a high BET specific surface area. Therefore, as described above, when the basic zinc carbonate fine particles are supported, the BET specific surface area is higher than when the zinc oxide fine particles are supported.

The BET specific surface area can be determined by a nitrogen adsorption method using a BET specific surface area measuring device. The BET specific surface area (BET _Zn ) of the zinc oxide fine particles and basic zinc carbonate fine particles supported on the silicate particles can be calculated by the following formula.

_{BET Zn = {(BET Zn-} Si × W Zn) + W Si (BET Zn-Si -BET Si)} / W Zn
BET _Zn—Si : BET specific surface area of zinc-based crosslinking aid BET _Si : BET specific surface area of silicate particles W _Zn : Mass% of zinc oxide or basic zinc carbonate contained in zinc-based crosslinking aid
W _Si : Mass% of silicate particles contained in zinc-based crosslinking aid

In the case of zinc oxide fine particles, the BET specific surface area (BET _Zn ) of the zinc oxide fine particles and the basic zinc carbonate fine particles supported on the surface of the silicate particles is preferably in the range of 15 to 100 m ² / g. In the case of zinc carbonate fine particles, the range is preferably from 15 to 100 m ² / g.

  Regarding the zinc-based crosslinking aid, if the BET specific surface area is too low, sufficient crosslinking may not be obtained, and the heat aging resistance and the like may not be sufficiently improved. Moreover, when the BET specific surface area becomes too high, free zinc oxide fine particles or basic zinc carbonate fine particles that are not supported are mixed, which become aggregated particles, and a uniform cross-linked structure may not be formed. Moreover, since the carrying amount of zinc oxide or basic zinc carbonate is relatively increased, it may be difficult to obtain an economic merit.

  As the silicate particles in the present invention, aluminum silicate mineral particles are preferably used. Examples of the silicate particles other than the aluminum silicate mineral particles include talc, mica, feldspar, bentonite, magnesium silicate, silica, calcium silicate (wollastonite), and diatomaceous earth.

  Examples of the aluminum silicate salt mineral particles in the present invention include at least one selected from kaolinite, halloysite, pyrophyllite, and sericite.

  In the present invention, the aluminum silicate mineral particles are preferably anhydrous aluminum silicate mineral particles. Examples of anhydrous aluminum silicate salt particles include those obtained by firing at least one selected from kaolinite, halloysite, pyrophyllite, and sericite. For example, those obtained by firing these clay minerals composed of fine particles having a particle size of 2 μm or less having a content of 80% or more at a temperature of 500 to 900 ° C. can be mentioned.

  The zinc-based crosslinking aid of the present invention, for example, in the presence of silicate particles, by mixing an acidic aqueous solution and an alkaline aqueous solution of zinc salt to precipitate zinc oxide fine particles or basic zinc carbonate, It can be produced by supporting zinc oxide fine particles or basic zinc carbonate on the surface.

  Specific examples of a method for depositing zinc oxide fine particles or basic zinc carbonate fine particles by mixing an acidic aqueous solution and an alkaline aqueous solution of zinc salt in the presence of silicate particles include the following methods.

  (1) Silicate particles are dispersed in an acidic aqueous solution of zinc salt, and an alkaline aqueous solution is added to the dispersion.

  (2) Silicate particles are dispersed in an alkaline aqueous solution, and an acidic aqueous solution of zinc salt is added to the dispersion.

  (3) Silicate particles are dispersed in water, and an acidic aqueous solution and an alkaline aqueous solution of zinc salt are simultaneously added to the dispersion.

  Of the above methods (1) to (3), the method (1) is particularly preferably employed.

  The acidic aqueous solution of zinc salt can be prepared, for example, by adding zinc oxide, zinc hydroxide, basic zinc carbonate, zinc sulfate, zinc nitrate or the like to the acidic aqueous solution. As zinc oxide, zinc white used as various industrial raw materials may be used. Examples of the acidic aqueous solution include aqueous solutions of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, and the like. Moreover, you may prepare by adding water-soluble zinc compounds, such as a zinc chloride, in acidic aqueous solution.

  Examples of the alkaline aqueous solution include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, and the like. In general, when sodium hydroxide, potassium hydroxide or the like is used as an alkaline aqueous solution, zinc oxide fine particles can be deposited and supported. Further, when carbonic acid is used as the acidic aqueous solution or when sodium carbonate or the like is used as the alkaline aqueous solution, basic zinc carbonate can be deposited and supported.

  In addition, as described above, the silicate particles supporting basic zinc carbonate are prepared by a method of treating silicate particles supporting zinc oxide fine particles with an aqueous ammonium salt solution or water suspension of silicate particles supporting zinc oxide fine particles. It can be produced by converting the supported zinc oxide fine particles into basic zinc carbonate fine particles by treating with a method such as carbonation by introducing carbon dioxide into the suspension. These treatment methods may be carried out singly or in combination.

  Examples of the aqueous ammonium salt solution include aqueous solutions of ammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, and the like. These may be used alone or in combination of two or more.

  As described above, it can be supported as finer particles by treating with an aqueous ammonium salt solution and converting the zinc oxide fine particles into basic zinc carbonate fine particles.

  After zinc oxide fine particles or basic zinc carbonate fine particles are deposited and supported on the surface of aluminum silicate salt mineral particles, they are generally washed thoroughly, dehydrated and dried, and then pulverized.

  The zinc-based crosslinking aid is at least selected from organic acids, fatty acids, fatty acid metal salts, fatty acid esters, resin acids, resin acid metal salts, resin acid esters, silicic acid, silicates (Na salts, etc.), and silane coupling agents. One type of surface treatment may be performed. Any structure that covers all or part of the surface may be used, and it is not always necessary to continuously cover the entire surface.

  As the surface treatment method, when the zinc-based crosslinking aid is an aqueous slurry, the surface treatment agent can be treated in a wet state by dissolving the surface treatment agent as it is or in an appropriate temperature and solvent. Further, if the zinc-based crosslinking aid is in a powder form, the surface treatment agent can be processed in a dry state by dissolving the surface treatment agent as it is or with an appropriate temperature and solvent.

<Polymer>
The polymer used in the present invention is not particularly limited as long as it can be crosslinked by an organic peroxide. For example, at least one selected from natural rubber, synthetic rubber, and plastic is selected.

  As the synthetic rubber, a crosslinkable rubber is used. Specific examples of the synthetic rubber include, for example, cis-1,4-polyisoprene, emulsion polymerized styrene butadiene copolymer, solution polymerized styrene butadiene copolymer, low cis-1,4-polybutadiene, and high cis-1. , 4-polybutadiene, ethylene-propylene-diene copolymer, ethylene-polyprene rubber, silicone rubber (HTV, RTV, LIM), acrylic rubber, modified acrylic rubber, fluoro rubber, chloroprene, halogenated butyl rubber, acrylonitrile-butadiene rubber, hydrogen And acrylonitrile-butadiene rubber and the like.

  Among the rubber components described above, natural rubber, ethylene propylene rubber, ethylene-propylene-diene copolymer, silicone rubber, low cis-1,4-polybutadiene, and high cis-1,4-polybutadiene are particularly preferably used. It is done.

  As the rubber component, one kind of natural rubber or synthetic rubber described above may be used, or two or more kinds thereof may be mixed and used. The mixing ratio can be appropriately set according to required characteristics.

  Any plastic can be used as long as it is crosslinkable, and examples thereof include polyethylene (PE) and ethylene vinyl acetate copolymer (EVA).

  Thermoplastic elastomers can also be used. Examples of thermoplastic elastomers include polystyrene-based thermoplastic elastomers, polypropylene-based thermoplastic elastomers, polydiene-based thermoplastic elastomers, chlorine-based thermoplastic elastomers, and engineering plastic-based elastomers. Can do.

<Organic peroxide>
Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne- 3, or 1,3-bis (t-butylperoxypropyl) benzene, di-t-butylperoxy-diisopropylbenzene, t-butylperoxybenzene, 2,4-dichlorobenzoyl peroxide, 1,1-di -T-butylperoxy-3,3,5-trimethylsiloxane, n-butyl-4,4 Di -t- butyl peroxy valerate, and the like.

<Other additives>
In the present invention, as the crosslinking aid, in addition to the zinc-based crosslinking aid, other crosslinking aids may be used in combination. For example, zinc oxide, activated zinc white, basic zinc carbonate, fine particle zinc oxide, cerium oxide, polyfunctional acrylic monomer (TAIC), bismaleimide and the like can be mentioned.

  Moreover, you may contain a well-known additive as needed. As such, for example, wet silica, dry silica, alkali silica, highly dispersible silica (HDS), clay, talc, aluminum hydroxide, magnesium hydroxide, feldspar, basic magnesium carbonate, carbon black, etc. are used in combination as appropriate. Can be used. Furthermore, process oils, antioxidants, anti-aging agents, activators, additives such as stearic acid, zinc oxide, wax, and vulcanizing agents such as sulfur and vulcanization accelerators may be added as desired. it can.

<Crosslinked polymer composition>
The cross-linked polymer composition of the present invention is obtained by blending a zinc-based cross-linking aid and an organic peroxide into a polymer and cross-linking with the organic peroxide.

  The compounding amount of the zinc-based crosslinking aid is preferably in the range of 0.5 to 10 parts by mass, more preferably in the range of 1 to 5 parts by mass with respect to 100 parts by mass of the polymer. . If the blending amount of the zinc-based crosslinking aid is small, the heat aging resistance may not be sufficiently improved. Moreover, when there are too many zinc type crosslinking adjuvants, while being unable to acquire the effect proportional to the compounding quantity, there exists a possibility that the mechanical characteristic etc. of a polymer may fall.

  The compounding amount of the organic peroxide is preferably in the range of 0.5 to 10 parts by mass, more preferably in the range of 0.75 to 5 parts by mass with respect to 100 parts by mass of the polymer. If the amount of the organic peroxide is small, a sufficient crosslinked structure may not be formed in the polymer composition. Moreover, when there are too many compounding quantities of an organic peroxide, there exists a possibility that the mechanical characteristic etc. of a polymer may fall.

  The ratio of the zinc-based crosslinking aid to the organic peroxide is preferably in the range of 5 to 2000 parts by mass and more preferably in the range of 20 to 1333 parts by mass with respect to 100 parts by mass of the organic peroxide. preferable. If the blending amount of the zinc-based crosslinking aid with respect to the organic peroxide is too small, the heat aging resistance and the like may not be sufficiently improved. Further, if the ratio of the zinc-based crosslinking aid to the organic peroxide is too large, the effect of the present invention that the heat aging resistance and the like can be improved in proportion to the blending amount may not be sufficiently obtained. In addition, the mechanical characteristics and the like may be deteriorated.

  After blending the polymer with a zinc-based crosslinking aid and an organic peroxide, the polymer composition is heated in order to crosslink the polymer with the organic peroxide. Although heating temperature is suitably adjusted with the organic peroxide etc. to be used, generally it is preferable that it is the range of 120-200 degreeC, More preferably, it is the range of 150-180 degreeC. The heating time is determined with reference to tc (90) measured with a curast meter at each temperature.

  The method for blending the polymer with the zinc-based crosslinking aid and the organic peroxide is not particularly limited, and conventionally known kneading apparatuses, specifically, Banbury mixer (registered trademark), intermix (registered trademark). , Kneader, roll or the like.

  Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples.

(Synthesis Example 1)
91.5 g of zinc oxide was added to 847 ml of a baked clay water suspension having a concentration of 5.5% by mass and sufficiently stirred. Subsequently, 330 g of a 10% by mass sodium carbonate aqueous solution and 340 g of a 10% by mass zinc chloride aqueous solution were added and further stirred. Carbon dioxide gas with a concentration of 30% by mass was blown into this until the pH became 7 or less, and basic zinc carbonate was precipitated on the surface of the baked clay to synthesize a zinc-based crosslinking aid. Thereafter, the mixture was pulverized through dehydration, drying, and pulverization steps to obtain a crosslinking aid A.

The BET specific surface area of the crosslinking aid A was 50 m ² / g. In the crosslinking aid A, 45% by mass of basic zinc carbonate as metal zinc was supported on the calcined clay. Therefore, the supported basic zinc carbonate had a BET specific surface area of 60 m ² / g.

(Synthesis Example 2)
To 847 ml of the baked clay water suspension having a concentration of 7.3% by mass, 25.5 g of zinc oxide was added and sufficiently stirred. Subsequently, 330 g of a 10% by mass sodium carbonate aqueous solution and 340 g of a 10% by mass zinc chloride aqueous solution were added and further stirred. Carbon dioxide gas with a concentration of 30% by mass was blown into this until the pH became 7 or less, and basic zinc carbonate was precipitated on the surface of the baked clay to synthesize a zinc-based crosslinking aid. Thereafter, the mixture was pulverized through dehydration, drying, and pulverization steps to obtain a crosslinking aid B.

The BET specific surface area of the crosslinking aid B was 38 m ² / g. In the crosslinking aid B, 30% by mass of basic zinc carbonate as metal zinc was supported on the calcined clay. Therefore, the supported basic zinc carbonate had a BET specific surface area of 59 m ² / g.

[Formulation in EPDM]
(Examples 1-4 and Comparative Examples 1-5)
To 100 parts by weight of EPDM, 1 part by weight of stearic acid, 50 parts by weight of carbon black (FEF), 10 parts by weight of process oil, 2.7 parts by weight of DCP (dicumyl peroxide) as a crosslinking agent, crosslinking aids A and B, C, D, or E was blended so as to have the addition amount shown in Table 1 to prepare a polymer composition.

  In addition, the following were used as EPDM, stearic acid, process oil, and DCP.

EPDM: ethylene propylene diene rubber (ethylene content 61%), manufactured by JSR, EP21
・ Stearic acid: LUNAC S-50, manufactured by Kao Corporation ・ Process oil: PW-380, manufactured by Idemitsu Kosan Co., Ltd. ・ DCP: Park Mill D, manufactured by NOF Corporation

    The crosslinking aids A to F are as follows.

Crosslinking aid A: Zinc-based crosslinking aid prepared in Synthesis Example 1 Crosslinking aid B: Zinc-based crosslinking aid prepared in Synthesis Example 2 Crosslinking aid C: Zinc oxide (2 types of zinc oxide, manufactured by Shodo Chemical Co., Ltd.) )
Crosslinking aid D: activated zinc white (active zinc white AZO, manufactured by Shodo Chemical Co., Ltd.)
Crosslinking aid E: Fine particle zinc oxide (Inoue Lime, Meta Z102)
Crosslinking aid F: Crosslinking aid A 100 parts by mass of vinyl trimethoxysilane surface-treated by 0.5 parts by mass.

  In this example and this comparative example, and in the following examples and comparative examples, the polymer and additive were kneaded and blended using an 8-inch roll.

  About the obtained polymer composition, the optimal vulcanization time tc (90) was calculated | required using the curast meter, based on the obtained data, it heated for a predetermined time, was made to bridge | crosslink, and the test sheet of thickness 2mm was obtained. Produced.

  EPDM was heated at 160 ° C. for 30 minutes.

[Evaluation of heat aging resistance]
About the obtained rubber sheet, the heat aging resistance was evaluated by the following method. Specifically, the tensile strength and elongation change rate before and after the test were obtained.

  For tensile strength and elongation, tensile strength and elongation at 23 ° C. were measured using a shopper tensile tester according to the method defined in JIS K 6251. The heating conditions were 150 ° C. × 72 hours, the tensile strength and elongation before and after the heating test were measured, and the TB change rate and EB change rate were determined as follows.

    TB change rate (%) = [(tensile strength after heating test) − (tensile strength before heating test) / (tensile strength before heating test)] × 100

    EB change rate (%) = [(Elongation after heating test) − (Elongation before heating test) / (Elongation before heating test)] × 100

[Evaluation of conductivity]
For Examples 1 to 3 and Comparative Examples 1 to 5, rubber sheets having a thickness of 2 mm and a diameter of 6 cm were prepared, and the rubber sheets were immersed in 200 ml of ion exchange water at 80 ° C. for 30 days. The conductivity of ion-exchanged water after the immersion was measured and shown in Table 1.

  As shown in Table 1, the crosslinked polymer compositions of Examples 1 to 4 according to the present invention have a smaller TB change rate and EB change rate than the crosslinked polymer compositions of Comparative Examples 1 to 5. Therefore, the heat aging resistance is greatly improved.

  According to the present invention, it is considered that the heat aging resistance can be improved because the crosslink density can be increased by using a zinc-based crosslinking aid. The crosslinked polymer of the present invention includes a sealing material (for example, O-ring, D-ring, X-ring, gasket), packing, electric wire, rubber plate, rubber sheet, anti-vibration rubber, belt (power transmission belt, etc.), hose (radiator hose, etc.), It can be suitably used for sponges and the like.

  In addition, the cross-linked polymer compositions of Examples 1 to 3 according to the present invention have a lower electrical conductivity than the cross-linked polymer compositions of Comparative Examples 2 to 5. This seems to be because the elution amount of Zn could be reduced by using the zinc-based crosslinking aid of the present invention as the crosslinking aid according to the present invention. Therefore, the crosslinked polymer composition of the present invention can be suitably used, for example, for packing for fuel cells.

[Combination with NR rubber]
(Example 5 and Comparative Examples 6-9)
As the polymer, NR rubber (natural rubber) was used to prepare a crosslinked polymer composition.

  With respect to 100 parts by mass of NR, 1 part by mass of stearic acid and 50 parts by mass of carbon black (FEF) were blended, and a crosslinking agent, a crosslinking aid and a vulcanization accelerator were blended as shown in Table 2.

  In Comparative Examples 8 and 9, sulfur is used as the crosslinking agent instead of the organic peroxide.

  The following were used as NR rubber, vulcanization accelerator D, and vulcanization accelerator DM.

NR rubber: natural rubber, SML # 3
・ Vulcanization accelerator D: Product name Noxeller D, manufactured by Ouchi Shinsei Chemical Co., Ltd. ・ Vulcanization accelerator DM: Product name Noxeller DM, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

  In the same manner as in Example 1, the mixture was kneaded using an 8-inch roll and then crosslinked. The heating conditions for crosslinking by DCP were 160 ° C. × 60 minutes in Comparative Example 6 in which no crosslinking assistant was blended, and 160 ° C. × 30 minutes in Example 5 and Comparative Example 7.

  In the case of crosslinking using sulfur, heating was performed at 150 ° C. × 10 minutes.

[Evaluation of heat aging resistance]
The TB change rate and the EB change rate were measured in the same manner as described above except that the heating conditions in the heating test were 120 ° C. × 72 hours, and the results are shown in Table 2.

  As shown in Table 2, Example 5 according to the present invention has a smaller TB change rate than Comparative Examples 6 and 7, and it can be seen that the heat aging resistance is greatly improved.

  In Comparative Example 8 and Comparative Example 9, crosslinking with sulfur is performed, Comparative Example 9 uses the zinc-based crosslinking aid of the present invention, and Comparative Example 8 uses zinc oxide, which is a conventional crosslinking aid. ing. As is clear from the comparison between Comparative Example 8 and Comparative Example 9, it can be seen that the effect of the present invention cannot be obtained by crosslinking with sulfur. The crosslinked polymer of the present invention is a sealing material (for example, O-ring, D-ring, X-ring, gasket), packing, electric wire, rubber plate, rubber sheet, anti-vibration rubber, belt (power transmission belt, etc.), hose (air hose, gas hose, etc.) ), Sponge, and the like.

[Combination with NBR rubber]
(Example 6 and Comparative Examples 10-11)
Here, it mix | blended with the NBR rubber | gum. To 100 parts by weight of NBR, 1 part by weight of stearic acid, 50 parts by weight of carbon black (FEF), 1 part by weight of Nocrak CD, 1 part by weight of Nocrack MBZ, 5 parts by weight of plasticizer (TOTM), 3.2 parts by weight of DCP, A crosslinking aid was blended as shown in Table 3 to prepare a crosslinked polymer composition.

  The NBR rubber, no crack CD, no crack MBZ, and plasticizer are as follows.

NBR rubber: Medium-high nitrile rubber (acrylonitrile content of 31% or more and less than 36%), manufactured by Nippon Zeon Co., Ltd., Nipol 1042
・ Anti-aging agent CD: Trade name NOCRACK CD, manufactured by Ouchi Shinsei Chemical Industries ・ Aging inhibitor MBZ: Trade name NOCRACK MBZ, manufactured by Ouchi Shinsei Chemical Industries ・ Plasticizer TOTM: Trade name Trimerix T-08, manufactured by Kao

  Kneading was performed using an 8-inch roll in the same manner as described above, and the heating conditions for crosslinking were 160 ° C. × 20 minutes.

[Evaluation of heat aging resistance]
The TB change rate and EB change rate were measured in the same manner as in the above (EPDM blend), and are shown in Table 3.

  As shown in Table 3, even when blended with NBR rubber, Example 6 using the zinc-based crosslinking aid of the present invention has significantly improved heat aging resistance as compared with Comparative Example 10 and Comparative Example 11. Yes. The crosslinked polymer of the present invention can be used in applications that require oil resistance, such as sealing materials (for example, O-rings, D-rings, X-rings, gaskets), packing, electric wires, rubber plates, rubber sheets, anti-vibration rubbers, belts (power transmission) Belts, etc.), hoses (fuel hoses etc.), sponges, etc.

[Formulation in silicone rubber]
(Examples 7 to 10 and Comparative Examples 12 to 15)
RC-4 (5OP) 0.75 mass part was mix | blended with respect to 100 mass parts of silicone rubbers, and also the crosslinking adjuvant was mix | blended as shown in Table 4.

  Silicone rubber and RC-4 (5OP) are as follows.

・ Silicone rubber: Trade name SH831U, Millable silicone rubber, manufactured by Toray Dow Corning ・ Crosslinking agent: Trade name RC-4 (5OP), manufactured by Toray Dow Corning

  Kneading was performed using an 8-inch roll, and after the kneading, crosslinking was performed by setting the heating conditions for primary crosslinking to 170 ° C. for 15 minutes and the heating conditions for secondary crosslinking to 200 ° C. for 4 hours.

  For silicone rubber, the difference in crosslink density hardly appears in the heat aging test, so the compression set under heating conditions was measured.

[Evaluation of compression set]
According to the method specified in JIS K 6262, it was tested using a compression apparatus. The compression ratio was 25%, the test temperature (constant temperature) was 150 ° C., and the test time was 72 hours. After putting in a thermostat of 150 ° C. for 72 hours, the test piece was taken out and allowed to stand at room temperature for 30 minutes, and then the compression set was measured.

  Table 4 shows the measurement results.

  As is clear from the results shown in Table 4, Examples 7 to 10 using the zinc-based crosslinking aid according to the present invention have a smaller compression set than Comparative Examples 12 to 15. Therefore, it can be seen that the heat aging resistance is remarkably improved. Further, in Example 10, roll processability was improved by subjecting vinyltrimethoxysilane to a surface treatment.

  In the fields of E & E, OA equipment, heavy electricity, and electric wires, the crosslinked polymer of the present invention is packing, gasket, tape, tube, sheets, heater heating element, defroster wire, TV parts, sensors, connectors, keyboard switches, Rolls, heat generating sheets, cables, anode caps, defrosters, hot air brushes, turn belts, O-rings, valves, harness end insulation, packing for jar pots, automobiles, in the transportation field, diaphragms, rolling, plug boots, waterproof connectors, radiators Hose, turbocharge hose, intercooler hose, oil seal, ignition hood, packing, gacket, heat shrink tube, joint hose, cable joint connector, plug cover, terminal plate, high voltage generator Products, EGR hoses, oil seals for rear flange shafts, in the industrial machinery field, hoses, rolls, anti-vibration rubber, valves, packing, tubes, jigs, heat-resistant mechanical parts, in the medical / food field, packing, lumicar, Nipples, various catheters, tubes for blood transfusion, shunts, storage containers, cardiopulmonary, artificial skin, gaskets, stoppers, O-rings, milking machine tubes, plugs for household cooking utensils, food production equipment parts, conveyor belts, pipettor spots In other fields, it is suitably used in underwater glasses, snorkels, mouthpieces, goggles bands, architectural gaskets and the like.

  Moreover, since improvement in water vapor resistance can also be expected, it can be suitably used for food packing (jars, rice cookers, pots), gaskets, sealing materials used for O-rings, and packing.

Claims (6)

  Zinc-based cross-linking aid with zinc oxide fine particles or basic zinc carbonate fine particles supported on the surface of silicate particles and organic peroxide as cross-linking agent were blended into the polymer and cross-linked with organic peroxide A crosslinked polymer composition characterized by the above.   The crosslinked polymer composition according to claim 1, wherein 0.5 to 10 parts by mass of a zinc-based crosslinking aid is blended with 100 parts by mass of the polymer.   The crosslinked polymer composition according to claim 1 or 2, wherein 0.5 to 10 parts by mass of an organic peroxide is blended with 100 parts by mass of the polymer.   The amount of supported zinc oxide fine particles or basic zinc carbonate fine particles in the zinc-based crosslinking aid is in the range of 6 to 75% by mass in terms of metal zinc, according to any one of claims 1 to 3. A crosslinked polymer composition as described.   The crosslinked polymer composition according to any one of claims 1 to 4, wherein the silicate particles are anhydrous aluminum silicate salt mineral particles. A method for producing the crosslinked polymer composition according to any one of claims 1 to 5,
Blending a polymer with a zinc-based crosslinking aid and an organic peroxide;
And heating the polymer containing the zinc-based crosslinking aid and the organic peroxide to crosslink the polymer with the organic peroxide.