CN115584088B - Rubber vulcanizate for roller and method for producing same - Google Patents
Rubber vulcanizate for roller and method for producing same Download PDFInfo
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- CN115584088B CN115584088B CN202210786525.7A CN202210786525A CN115584088B CN 115584088 B CN115584088 B CN 115584088B CN 202210786525 A CN202210786525 A CN 202210786525A CN 115584088 B CN115584088 B CN 115584088B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 173
- 239000005060 rubber Substances 0.000 title claims abstract description 173
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- 229920002678 cellulose Polymers 0.000 claims abstract description 63
- 239000001913 cellulose Substances 0.000 claims abstract description 63
- 239000002121 nanofiber Substances 0.000 claims abstract description 63
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 35
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 36
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 19
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims description 6
- 150000001451 organic peroxides Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 22
- 238000000576 coating method Methods 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- -1 polyethylene Polymers 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002978 peroxides Chemical group 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- HJUFTIJOISQSKQ-UHFFFAOYSA-N fenoxycarb Chemical compound C1=CC(OCCNC(=O)OCC)=CC=C1OC1=CC=CC=C1 HJUFTIJOISQSKQ-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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)
- Rolls And Other Rotary Bodies (AREA)
Abstract
The purpose of the present invention is to provide a hydrophilic rubber sulfide for rollers and a method for producing the same. The rubber sulfide for a roller of the present invention contains a nonpolar raw material rubber, a modified polyolefin resin, and cellulose nanofibers, and the cellulose nanofibers are blended in a proportion of 0.5 to 20 parts by mass inclusive relative to 100 parts by mass of the total amount of the nonpolar raw material rubber and the modified polyolefin resin.
Description
Technical Field
The present invention relates to a rubber vulcanizate for rolls and a method for producing the same.
Background
In a roller having a rubber layer on the surface, the rubber material of the rubber layer is hydrophobic in most cases. However, depending on the use of the roll, it may be desirable for its surface to be hydrophilic. As the rubber material having hydrophilicity, a rubber having a high polarity, i.e., a large surface energy, such as urethane rubber or nitrile rubber (NBR) can be used. Further, a rubber obtained by acid-modifying these rubbers or a rubber sulfide obtained by mixing a hydrophilic compounding agent is used.
There is also known a technique for imparting hydrophilicity to a hydrophobic rubber. Such a technique is disclosed in, for example, japanese patent application laid-open No. 2018-53160. This publication describes a rubber composition obtained by mixing a hydrophilizing plasticizer containing polyethylene glycol with a carboxyl-modified nitrile rubber to impart hydrophilicity.
However, the carboxyl group-modified nitrile rubber contained in the rubber composition of the above publication is a raw material rubber having high polarity, and therefore swells when it comes into contact with water. In addition, the modified nitrile rubber gradually dissolves and precipitates as the hydrophilizing plasticizer and the hydrophilicity decreases during use in contact with water.
Disclosure of Invention
The invention provides a rubber sulfide for a roller, which has hydrophilicity and inhibits swelling caused by contact with water, and a manufacturing method thereof.
The rubber vulcanizate for rolls of the present invention comprises a nonpolar raw material rubber, a modified polyolefin resin, and cellulose nanofibers. The cellulose nanofibers are blended in a proportion of 0.5 to 20 parts by mass based on 100 parts by mass of the total amount of the nonpolar raw material rubber and the modified polyolefin resin.
Drawings
Fig. 1 is a photograph in which the dispersed state of the cellulose nanofiber of example 1 was observed at a magnification of 50 times with a polarizing microscope.
Fig. 2 is a photograph of a dispersed state of cellulose nanofibers of comparative example 3 observed with a polarizing microscope at a magnification of 50 times.
Detailed Description
Hereinafter, a rubber vulcanizate and a method for producing the same according to embodiments of the present invention will be described.
The rubber vulcanizate of the embodiment comprises a nonpolar raw material rubber, a modified polyolefin resin, and cellulose nanofibers. The cellulose nanofibers are blended in a proportion of 0.5 to 20 parts by mass based on 100 parts by mass of the total amount of the nonpolar raw material rubber and the modified polyolefin resin.
The nonpolar raw material rubber may be, for example, one or a mixture of two or more selected from natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, and ethylene propylene rubber (EPDM). Among them, ethylene propylene rubber is preferable because it can further improve the durability of the rubber vulcanizate.
Polar groups are introduced into the molecular skeleton of the modified polyolefin resin. Examples of the polar group include a carboxyl group, an acid anhydride group, a hydroxyl group, and an epoxy group. Among them, polyolefin resins having carboxyl groups and acid anhydride groups introduced therein are preferred from the viewpoint of easy availability. The polar group may be introduced into a plurality of kinds. Such polar groups have the following effect: the affinity with cellulose nanofibers is improved, aggregation of cellulose nanofibers is suppressed, and the dispersibility of cellulose nanofibers is improved.
The polyolefin resin may be exemplified by: polyethylene, polypropylene, polybutene, ethylene-propylene copolymers, ethylene-butene copolymers, and the like. The modified polyolefin resins are obtained by modifying these polyolefin resins with an unsaturated carboxylic acid such as maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, etc. Among these, modified polyethylene, ethylene-propylene copolymer and ethylene-butene copolymer have low melting points and are preferable because they are improved in processability in the kneading step of the nonpolar raw material rubber.
The modified polyolefin resin may be mixed with two or more modified polyolefin resins.
In general, the compatibility of the nonpolar raw material rubber and the modified high molecular polymer is low. However, the inventors found that: the modified polyolefin is used to have a characteristic of being compatible with a nonpolar raw material rubber. The rubber vulcanizate comprising such a mixture can exhibit high durability in addition to hydrophilicity by virtue of the excellent water resistance of the nonpolar raw material rubber.
The blending ratio of the modified polyolefin resin is preferably 1 part by mass or more and 40 parts by mass or less relative to 100 parts by mass of the total amount of the nonpolar raw material rubber and the modified polyolefin resin. The blending ratio of the modified polyolefin resin is more preferably 5 parts by mass or more and 30 parts by mass or less, and still more preferably 5 parts by mass or more and 20 parts by mass or less. When the amount of the modified polyolefin resin is less than 1 part by mass, cellulose nanofibers described later may be easily aggregated. If the modified polyolefin resin exceeds 40 parts by mass, the elastic force of the rubber vulcanizate may be impaired. Further, since the production cost of the masterbatch gelation is high, it is also preferable to reduce the modified polyolefin resin as much as possible in economy, and it is preferable that the modified polyolefin resin is 40 parts by mass or less (60 parts by mass or more of the nonpolar raw material rubber).
Cellulose nanofibers have been attracting attention in recent years as reinforcing materials for rubber because of their light weight, high elastic modulus, and low environmental load. However, the inventors have found that the cellulose nanofibers have hydrophilicity, and that the hydrophilic properties can be imparted to the rubber vulcanizate by blending the cellulose nanofibers into the rubber vulcanizate. The cellulose nanofibers preferably have a diameter of 1nm to 1000nm, and a length of 10 to 1000 times the diameter, more preferably 1 to 1000nm, and further preferably 50 to 1000 times the diameter.
The cellulose nanofibers are blended in a range of 0.5 to 20 parts by mass based on 100 parts by mass of the total amount of the nonpolar raw material rubber and the modified polyolefin resin in the rubber sulfide. The cellulose nanofiber is preferably 1 to 10 parts by mass, more preferably 2 to 10 parts by mass. If the blending amount of the cellulose nanofibers is less than 0.5 parts by mass, the hydrophilicity cannot be sufficiently imparted to the rubber sulfide, and it is difficult to obtain the rubber sulfide having the desired properties. If the amount of the cellulose nanofibers to be blended exceeds 20 parts by mass, the cellulose nanofibers may be easily aggregated with each other, and aggregates may be generated in the rubber vulcanizate. If aggregates of cellulose nanofibers are generated in the rubber sulfide, the aggregates partially swell, and the dimensional stability and smoothness of the rubber sulfide are impaired. Further, since the material price of cellulose nanofibers is higher than that of general rubber components, an excessive increase in the amount of cellulose nanofibers is not preferable in terms of economy.
The rubber vulcanizate may contain general rubber compounding ingredients such as an anti-aging agent, a processing accelerator, a filler, and a plasticizer, as necessary.
(contact angle)
In the rubber vulcanizate of the embodiment, the contact angle with pure water in the aqueous state is preferably 100 degrees or less. That is, the rubber vulcanizate suitable for use in embodiments of the roller is used while in ordinary contact with water. Therefore, the rubber vulcanizate is in a state of being impregnated with water when in use. Therefore, in the measurement of the contact angle of the rubber sulfide according to the embodiment, the measurement sample is immersed in pure water in advance to be brought into a water-containing state, and the contact angle with pure water is measured in this water-containing state.
When the rubber sulfide of the embodiment is used as a rubber roll, the contact angle with pure water in the aqueous state is set to 100 degrees or less, and water or an aqueous coating material spreads uniformly in a wet state on the surface of the rubber roll, whereby a uniform thin film can be formed. On the other hand, if the contact angle exceeds 100 degrees, there is a concern that the water or the aqueous coating material unevenly spreads on the surface of the rubber roller.
(Mass change Rate of rubber vulcanizate)
In the rubber vulcanizate of the embodiment, the mass change rate obtained by the immersion test in pure water (according to JIS K6258) is preferably 20% or less, more preferably 10% or less, and still more preferably 5% or less. If the mass change rate exceeds 20%, swelling due to water absorption becomes large, and there is a risk of deterioration in the outer diameter accuracy when the rubber sulfide of the embodiment is used as a rubber roller.
The mass change rate of the rubber sulfides other than the cellulose nanofibers obtained by the immersion test in pure water is preferably 3% or less, more preferably 1% or less, and still more preferably 0.5% or less. If the mass change rate exceeds 3%, the water resistance of the rubber vulcanizate may be lowered, and if the rubber vulcanizate is used as a rubber roll for a long period of time, deterioration may be accelerated.
(hardness Change of rubber vulcanizate)
The rubber vulcanizate of the embodiment preferably has a hardness change of-3 to +3 before and after immersion in pure water (according to JIS K6258). If the hardness change is less than-3 or exceeds +3, there is a concern that the holding pressure between the rubber vulcanizate and the contacted member will change when the rubber vulcanizate is used as a rubber roll for a long period of time.
According to the rubber sulfide of the embodiment, the material of the rubber sulfide itself is hydrophilic, so that the aqueous coating material can be uniformly applied without thickness unevenness when used as a rubber roller. Further, the aqueous coating material may be applied to a film.
Further, since the rubber sulfide according to the embodiment is not hydrophilized by the surface treatment as in the prior art, even when abrasion occurs on the surface due to long-term use, the material itself does not change, and hydrophilicity can be maintained.
Further, since the cellulose nanofibers are fibrous, the cellulose nanofibers can be prevented from falling off from the rubber sulfides as compared with the spherical or irregularly shaped fillers.
Further, since the cellulose nanofibers contained in the rubber vulcanizate have extremely fine fiber diameters of, for example, 1nm to 1000nm, the smoothness of the surface of the rubber vulcanizate is not impaired even if the cellulose nanofibers absorb water.
In addition, the rubber vulcanizate of the embodiment does not need to be introduced into special equipment for production. Compared with the prior art, the hydrophilic coating can restrain the economic cost and endow hydrophilicity.
Further, the rubber sulfide of the embodiment imparts hydrophilicity to the cellulose nanofibers to the nonpolar raw material rubber, and therefore can suppress a change in hardness upon contact with water.
(method for producing rubber vulcanizate)
The method for producing a rubber vulcanizate according to the embodiment will be described.
The method for producing a rubber vulcanizate according to an embodiment comprises the following steps: (a) A step of mixing an aqueous dispersion of a modified polyolefin resin with an aqueous dispersion of cellulose nanofibers; (b) A step of removing water from the mixed solution obtained in the step (a) to obtain a resin masterbatch of the modified polyolefin resin and the cellulose nanofiber; and (c) kneading the resin masterbatch and the nonpolar raw material rubber obtained in the step (b) in a proportion of 0.5 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the total amount of the nonpolar raw material rubber and the modified polyolefin resin, to obtain an unvulcanized product of a rubber sulfide (rubber composition).
The steps (a) to (c) will be described in detail.
First, an aqueous dispersion of cellulose nanofibers is mixed with an aqueous dispersion of a modified polyolefin resin and uniformly dispersed. For example, an aqueous dispersion in which cellulose nanofibers are dispersed in water at a concentration of 0.2% by weight or more and 10% by weight or less may be used as the aqueous dispersion of cellulose nanofibers. Such a dispersion is commercially available. For example, a commercially available aqueous dispersion may be used as the aqueous dispersion of the modified polyolefin resin.
Then, the mixed dispersion is dried to remove moisture, thereby obtaining a masterbatch of cellulose nanofibers and a modified polyolefin resin.
Thereafter, the obtained masterbatch was kneaded with a nonpolar raw material rubber to obtain a rubber composition. In this mixing, the cellulose nanofibers are present in an amount of 0.5 to 20 parts by mass based on 100 parts by mass of the total amount of the nonpolar raw material rubber and the modified polyolefin resin. In addition to the masterbatch and the nonpolar raw material rubber, a general rubber compounding agent such as a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, a processing aid, a filler, or a plasticizer may be appropriately compounded during kneading.
The vulcanizing agent is preferably a peroxide crosslinking agent. By using the peroxide crosslinking agent, not only the crosslinking of the nonpolar rubber material but also the crosslinking of the modified polyolefin resin is performed, and therefore the rubber vulcanizate can have higher physical properties.
The method of kneading is not particularly limited, and for example, a known technique such as a kneader, a Banbury mixer (Banbury mixer), or an open mill may be used. The temperature during kneading is preferably a temperature equal to or higher than the melting point of the modified polyolefin resin.
The rubber composition obtained by kneading may be molded on the surface of a roll. As the roller, a known support having rigidity such as iron, aluminum, or stainless steel, or carbon fiber reinforced plastic can be used. The support may be cylindrical or may be cylindrical. The shaft may be pressed against both ends of the cylindrical support. The surface of the support is sandblasted, cleaned, and an adhesive is applied. Then, the rubber composition obtained by kneading is coated on the surface of the support. For example, a known method such as a method of winding a rubber composition in a sheet form separately on the surface of a support or a method of coating a rubber composition in a cylindrical form on the surface of a support using an extruder can be used as the coating method. Then, the surface is vulcanized by heating, and then polished using a rotary grinding wheel or the like, whereby a roller coated with a rubber sulfide adjusted to a predetermined outer diameter size can be produced.
The dispersibility of cellulose nanofibers is poor relative to the dispersibility of the nonpolar raw material rubber. However, as in the method for producing a rubber sulfide according to the embodiment, a masterbatch of cellulose nanofibers and a modified polyolefin resin is prepared in advance, and then a nonpolar raw material rubber is kneaded into the masterbatch, whereby a rubber sulfide in which cellulose nanofibers are well dispersed can be obtained.
Examples (example)
Hereinafter, examples will be described in detail.
Example 1
(preparation of a masterbatch of cellulose nanofibers and modified polyolefin resin)
1250g of an aqueous dispersion of cellulose nanofibers (manufactured by AUROVISCO, oji holders, inc. having a solid content of 2.0%) and 400g of an aqueous dispersion of modified polyethylene (trade name: arrowbase SB-1200, manufactured by UNITKA, inc. having a total solid content of 25%) were mixed using a homogenizer, and uniformly dispersed. The resulting mixture of the aqueous dispersion of cellulose nanofibers and the aqueous dispersion of modified polyethylene was dried in a constant temperature bath at 60℃for 72 hours to obtain a masterbatch containing 25 parts by mass of cellulose nanofibers.
(production of rubber composition)
80 parts by mass of ethylene propylene rubber (JSR EP342 (manufactured by JSR corporation)), 25 parts by mass of the masterbatch, 5 parts by mass of zinc oxide (zinc oxide 2 types, manufactured by orthochemical industries, inc.), 1 part by mass of stearic acid (LUNAC S-70V, manufactured by Huawang corporation) as a processing aid, 5.4 parts by mass of an organic peroxide (dicumyl peroxide) (Percumyl D-40 (manufactured by daily oil corporation)) as a vulcanizing agent, and 2 parts by mass of a co-crosslinking agent (triallyl isocyanurate) (TAIC (manufactured by TAIC Mitsubishi Chemical)) as a heat-resistant modifier were kneaded by an open mill to prepare a rubber composition. The rubber composition contained 20 parts by mass of modified polyethylene and 5 parts by mass of Cellulose Nanofibers (CNF) per 100 parts by mass of the total amount of ethylene propylene rubber and modified polyethylene.
Comparative example 1
In 98.8 parts by mass of ethylene propylene rubber (JSR EP342 (JSR corporation)) as a nonpolar raw material rubber and 1.5 parts by mass of a masterbatch prepared in the same manner as in example 1, zinc oxide, stearic acid, an organic peroxide, and a co-crosslinking agent were kneaded using an open mill in the same manner as in example 1 to prepare a rubber composition. The rubber composition contained 1.2 parts by mass of modified polyethylene and 0.3 parts by mass of Cellulose Nanofibers (CNF) per 100 parts by mass of the total amount of ethylene propylene rubber and modified polyethylene.
Comparative example 2
In 80 parts by mass of a carboxyl group-containing nitrile rubber (Nipol DN1072 (manufactured by ZEON corporation) as a polar raw material rubber) and 25 parts by mass of a masterbatch of example 1, zinc oxide, stearic acid, an organic peroxide, and a co-crosslinking agent were kneaded using an open mill in the same manner as in example 1 to prepare a rubber composition. The rubber composition contained 20 parts by mass of modified polyethylene and 5 parts by mass of Cellulose Nanofibers (CNF) per 100 parts by mass of the total amount of the carboxyl group-containing nitrile rubber and the modified polyethylene.
Comparative example 3
1250g of an aqueous dispersion (AUROVISCO, manufactured by Oji holders, inc. having a solid content of 2.0%) of cellulose nanofibers was mixed with 217g of a latex (trade name: nipol LX511A, manufactured by ZEON, japan, inc. having a solid content of 46%) of a carboxyl group-containing nitrile rubber using a homogenizer, and the mixture was uniformly dispersed. The aqueous dispersion of the cellulose nanofibers thus obtained was dried in a constant temperature bath at 80℃for 72 hours to obtain a masterbatch containing 25 parts by mass of cellulose nanofibers, as a mixed solution of a latex of a carboxyl group-containing nitrile rubber (X-NBR).
In 80 parts by mass of ethylene propylene rubber (JSR EP342 (JSR corporation)) as a nonpolar raw material rubber and 25 parts by mass of the masterbatch, zinc oxide, stearic acid, an organic peroxide, and a co-crosslinking agent were kneaded using an open mill in the same manner as in example 1 to prepare a rubber composition. The rubber composition contained 20 parts by mass of a carboxyl group-containing nitrile rubber and 5 parts by mass of Cellulose Nanofibers (CNF) per 100 parts by mass of the total amount of ethylene propylene rubber and the carboxyl group-containing nitrile rubber.
The rubber compositions obtained in example 1 and comparative examples 1 to 3 were prepared into rubber vulcanizates by the following methods, and evaluated.
(evaluation of contact Angle)
The rubber composition was heated and vulcanized by press molding to prepare a rubber vulcanizate having a thickness of 2mm, and the rubber vulcanizate was punched out to 10 mm. Times.50 mm. Thereafter, the surface of the punched sheet was polished with a surface grinder to prepare a sample for measuring the contact angle.
The sample was immersed in pure water and left to stand at room temperature of 25℃for 7 days. The sample was taken out of the pure water, and after removing the superfluous water droplets on the surface, the contact angle was measured using pure water. Contact angle measurement the contact angle after 10 seconds of addition was measured with a contact angle meter CA-X (Co., ltd.) at a drop size of 1.8. Mu.L.
(immersion test)
Using the rubber compositions obtained in example 1 and comparative examples 1 to 3, rubber sulfides having a thickness of 2mm similar to those used in the measurement of the contact angle were produced.
Further, rubber compositions obtained by removing cellulose nanofibers from the rubber compositions obtained in example 1 and comparative examples 1 to 3 were prepared, and rubber sulfides having a thickness of 2mm were produced in the same manner. Each of the obtained rubber sulfides was punched out to 20mm×50mm to prepare a sample.
Each sample was tested in accordance with JIS K6258. The test was carried out by immersing each sample in pure water at 40℃for 28 days.
The evaluation was performed by the mass change rate and the hardness change, and the appearance was also observed.
The mass change rate was measured before immersing the sample in pure water and the mass after the water resistance test, and calculated by the following formula (1).
Δm 100 ＝(m 2 －m 1 )/m 1 ×100……(1)
Here Δm 100 : mass change rate (%), m 1 : mass (mg) before impregnation, m 2 : mass (mg) after impregnation.
The hardness (type a) before immersing the sample in pure water (according to JIS K6253) and the hardness (type a) after the water resistance test were measured and calculated by the following formula (2).
S H ＝H 1 －H 0 ……(2)
Here, S H : hardness change, H 0 : hardness before impregnation (type A), H 1 : hardness after impregnation (type a).
In the hardness change, when the hardness change after the initial and 28 days was-3 or more and +3 or less, it was determined that the water resistance was sufficiently excellent. On the other hand, when it is smaller than-3 or exceeds +3, it is determined that the water resistance is poor.
The results of the above evaluation are shown below.
TABLE 1
The contact angle of the rubber sulfide of example 1 in the aqueous state was 90 degrees, and the water film was thin and uniformly diffused on the surface of the rubber sulfide, and had good hydrophilicity. The mass change rate and hardness change are good.
The mass change rate and hardness change in the impregnation test of the rubber vulcanizate of comparative example 1 were as good as those of example 1. However, the water film on the surface of the rubber vulcanizate is not uniform. The reason for this is considered to be that the content of cellulose nanofibers contained in the rubber vulcanizate is less than 0.3 parts by mass of the lower limit of the range of the present invention (0.5 parts by mass or more and 20 parts by mass or less) relative to 100 parts by mass of the total amount of the ethylene propylene rubber and the modified polyethylene, and thus the hydrophilicity is insufficient as a result.
The rubber sulfide of comparative example 2 contained 5 parts by mass of cellulose nanofibers in the same manner as the rubber sulfide of example 1. However, in the evaluation of the impregnation test of the rubber vulcanizate, the mass change rate of the CNF-free rubber was larger than that of the rubber vulcanizate of example 1, and the hardness change was larger than that of the rubber vulcanizate of example 1. The reason for this is considered to be that the carboxyl group-containing nitrile rubber of the polar rubber is used instead of the nonpolar rubber as the raw material rubber, and therefore the water resistance of the rubber vulcanizate is poor.
In the mixing of the ethylene propylene rubber and the masterbatch, the rubber vulcanizate of comparative example 3 had low masterbatch compatibility and was difficult to mix. The mixture of the nonpolar raw rubber and the masterbatch of example 1 and comparative example 3 was pressed into a film having a thickness of 50. Mu.m, and the dispersion was recorded with a photograph at a magnification of 50 times by using a polarizing microscope (ECLIPSE LV N POL manufactured by Nikon). As shown in fig. 1, no aggregates of cellulose nanofibers were observed in the mixture of example 1. On the other hand, as shown in fig. 2, aggregates of cellulose nanofibers were observed in the mixture of comparative example 3. From these results, it is understood that the mixture of comparative example 3 has poor dispersibility of cellulose nanofibers compared to the mixture of example 1. The reason for this is considered to be that the carboxyl group-containing nitrile rubber is used in the preparation of the masterbatch instead of the modified polyolefin.
A rubber roller covered with a rubber sulfide on the surface was produced using the rubber composition of example 1. The resulting rubber roll was used as a coating roll for coating an aqueous coating material on the film surface. As a result, the aqueous coating material can be uniformly applied at a uniform thickness. Furthermore, the use is stable for more than 6 months.
A rubber roller covered with a rubber sulfide on the surface was produced using the rubber composition of comparative example 1. The same as described above was used as the coating roll. As a result, the coating thickness of the aqueous coating material is not uniform, and the aqueous coating material cannot be used as a coating roll.
A rubber roller covered with a rubber sulfide on the surface was produced using the rubber composition of comparative example 2. The same as described above was used as the coating roll. As a result, coating was initially possible with a uniform coating thickness, but uneven coating thickness was gradually generated, and it was not possible to use for 6 months. When the rubber roll after use was investigated, the hardness of the rubber roll was reduced by 5 percentage points.
Although several embodiments have been described, these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments may be implemented in various other forms, and various omissions, substitutions, and changes may be made without departing from the spirit of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and their equivalents.
Claims (5)
1. A rubber vulcanizate for roller comprising a nonpolar raw material rubber, a modified polyolefin resin, and cellulose nanofibers, crosslinked by an organic peroxide,
the modified polyolefin resin is blended in an amount of 1 to 40 parts by mass based on 100 parts by mass of the total weight of the nonpolar raw material rubber and the modified polyolefin resin,
the cellulose nanofibers are blended in a proportion of 0.5 to 5 parts by mass based on 100 parts by mass of the total amount of the nonpolar raw material rubber and the modified polyolefin resin,
the nonpolar raw material rubber and the modified polyolefin resin are crosslinked with each other.
2. The rubber vulcanizate for roll according to claim 1, wherein,
the nonpolar raw material rubber is ethylene propylene rubber.
3. The rubber vulcanizate for roll according to claim 1 or 2, wherein,
the contact angle of the rubber sulfide for roller with pure water in the state of water is 100 degrees or less.
4. The rubber vulcanizate for roll according to claim 1 or 2, wherein,
the mass change rate of the rubber sulfide for rolls in the immersion test in pure water is 20% or less, and the mass change rate of the rubber sulfide for rolls other than the cellulose nanofibers in the immersion test in pure water is 3% or less.
5. A process for producing a rubber vulcanizate for rolls according to claim 1, comprising:
(a) A step of mixing an aqueous dispersion of a modified polyolefin resin with an aqueous dispersion of cellulose nanofibers;
(b) A step of removing water from the mixed solution obtained in the step (a) to obtain a masterbatch of the modified polyolefin resin and the cellulose nanofiber;
(c) A step of kneading the masterbatch, the nonpolar raw material rubber, and the organic peroxide obtained in the step (b) so that 100 parts by mass of the modified polyolefin resin relative to the total weight of the nonpolar raw material rubber and the modified polyolefin resin is 1 part by mass or more and 40 parts by mass or less, and 100 parts by mass of the cellulose nanofiber relative to the total weight of the nonpolar raw material rubber and the modified polyolefin resin is 0.5 part by mass or more and 5 parts by mass or less, thereby obtaining a rubber composition; and
(d) And (c) heating the rubber composition obtained in the step (c) to obtain a rubber vulcanizate for rolls.
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| JPS6333446A (en) * | 1986-07-25 | 1988-02-13 | Nippon Denso Co Ltd | Polyolefin composition |
| CN101631829A (en) * | 2007-09-10 | 2010-01-20 | 住友橡胶工业株式会社 | Vulcanized rubber composition, pneumatic tire, and their production methods |
| JP2019172752A (en) * | 2018-03-27 | 2019-10-10 | 三菱製紙株式会社 | Process for producing microfibrillated cellulose-containing polypropylene resin composite |
| CN110770469A (en) * | 2017-06-19 | 2020-02-07 | 阪东化学株式会社 | Transmission belt |
| CN110857351A (en) * | 2018-08-24 | 2020-03-03 | 松下电器产业株式会社 | Cellulose composite resin and method for producing same |
| EP3623416A1 (en) * | 2018-09-12 | 2020-03-18 | Sumitomo Rubber Industries, Ltd. | Tire rubber composition and tire |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6889358B2 (en) | 2018-02-02 | 2021-06-18 | 株式会社スギノマシン | Cellulose nanofiber-containing resin composition |
| JP6650476B2 (en) | 2018-02-27 | 2020-02-19 | 横浜ゴム株式会社 | Rubber composition for tire |
| JP2020125420A (en) | 2019-02-06 | 2020-08-20 | 三井化学株式会社 | Thermoplastic elastomer composition and its use |
| JP7353600B2 (en) | 2020-02-04 | 2023-10-02 | 国立大学法人信州大学 | Composition and method for producing the composition |
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| JPS6333446A (en) * | 1986-07-25 | 1988-02-13 | Nippon Denso Co Ltd | Polyolefin composition |
| CN101631829A (en) * | 2007-09-10 | 2010-01-20 | 住友橡胶工业株式会社 | Vulcanized rubber composition, pneumatic tire, and their production methods |
| CN110770469A (en) * | 2017-06-19 | 2020-02-07 | 阪东化学株式会社 | Transmission belt |
| JP2019172752A (en) * | 2018-03-27 | 2019-10-10 | 三菱製紙株式会社 | Process for producing microfibrillated cellulose-containing polypropylene resin composite |
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| EP3623416A1 (en) * | 2018-09-12 | 2020-03-18 | Sumitomo Rubber Industries, Ltd. | Tire rubber composition and tire |
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| CN115584088A (en) | 2023-01-10 |
| JP7235257B2 (en) | 2023-03-08 |
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