CN101240088A - Elastomer composition, method for producing the same, and eraser using the same - Google Patents
Elastomer composition, method for producing the same, and eraser using the same Download PDFInfo
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- CN101240088A CN101240088A CNA2008100032736A CN200810003273A CN101240088A CN 101240088 A CN101240088 A CN 101240088A CN A2008100032736 A CNA2008100032736 A CN A2008100032736A CN 200810003273 A CN200810003273 A CN 200810003273A CN 101240088 A CN101240088 A CN 101240088A
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- eradicating instrument
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Abstract
Disclosed is an elastomer composition which is characterized in that crosslinked natural rubber particles are dispersed like islands in a matrix of a biomass plastic. Also disclosed is an eraser using such an elastomer composition as a base material. The elastomer composition and the eraser do not depend on fossil resources, while being recyclable. Consequently, the elastomer composition and the eraser are environmental friendly and suited to the recycling-oriented society.
Description
Technical field
The present invention relates to elastic composition, its manufacture method and use the eradicating instrument (word disappear) of said composition, more specifically, relate to do not rely on fossil resource, can circulate,, elastic composition, its manufacture method of adapting to circular form society useful and the eradicating instrument that uses said composition to environment.
Background technology
In the past, industrial economy developed by utilizing fossil resources such as oil, coal, had constructed mass production, a large amount of consumption, a large amount of depleted social system, and now, most of Life Basis depend on may exhausted fossil resource.
Present social system produces the abundant, convenient of economy, but on the other hand owing to waste, the carbonic acid gas of discharging above natural purifying ability, it is serious that environmental problems such as global warming, objectionable impurities become.
In order to solve such problem, strong request change in the past by limited resources mass production commodity and with its a large amount of consumption, the current social system of depleted folk prescription, to suppressing generation of waste, effectively utilizing the circular form social transformation of limited resources.In order to form this circular form society, Japan has determined " biomass Japan composite strategies " putting down into cabinet council in December, 14, is devoted to constructing again of industrial competitiveness.
Biomass (バ イ オ マ ス) be the bounties because of nature obtain can continue the organic resource of regenerated.Though carbonic acid gas is discharged in biomass burnings and since when growth by photosynthesis absorb, fixing Atmospheric Carbon Dioxide, so have the feature that does not make the carbonic acid gas increase basically.This is called " carbon neutralization (carbon neutral) ",, can significantly reduces the output of carbonic acid gas, therefore, need this technology of exploitation and product strongly by replacing to biomass from energy, the product of fossil resource.
In recent years, even in macromolecular material, also proposed One's name is legion consideration form the scheme of circular form society.
For example can enumerate, in Japanese kokai publication hei 10-274494 communique, put down in writing the rubber manufacturing that contains natural rubber and biodegradable plastic with composition (using vulcanizing agent, vulcanization accelerator in an embodiment) (patent documentation 1); In TOHKEMY 2000-95898 communique, put down in writing Biodegradable material and epoxidized polyisoprene and linking agent have as required been mixed the Biodegradable material composition (patent documentation 2) that obtains; In TOHKEMY 2000-319446 communique, put down in writing in natural rubber the biological degradability rubber combination (patent documentation 3) that adds Biodegradable resin and weighting agent and obtain; In TOHKEMY 2003-183488 communique, put down in writing the polylactic acid based resin composition (patent documentation 4) that contains crystalline polylactic acid and be selected from the rubber constituent in natural rubber, the polyisoprene; In TOHKEMY 2004-143315 communique, put down in writing little equably mixed with polymers material (patent documentation 5) that is dispersed with the disperse phase that comprises natural rubber etc. etc. in the external phase that constitutes by poly(lactic acid).
On the other hand, eradicating instrument can roughly be divided into following three classes: comprise vinyl chloride resin the vinylchlorid eradicating instrument, comprise the non-vinylchlorid eradicating instrument and the natural rubber eradicating instrument of styrene analog thermoplastic elastomer or olefin hydrocarbons thermoplasticity elastic body.
Wherein, it is many that vinylchlorid eradicating instrument, non-vinylchlorid eradicating instrument account for 9 one-tenth of eradicating instrument market, the macromolecular material, softening agent, the tenderizer that constitute these eradicating instruments all are the materials from fossil resources such as oil, continue to utilize the aim of these eradicating instruments and above-mentioned formation circular form society to run counter to.
Relative therewith, for example, such as TOHKEMY 2000-43492 communique, " rubber industry brief guide " (industry of go system is list just) (new edition, 25.2,817 pages of Japan rubber association tabulatings, clear and rubber association of Corporation distribution on November 15th, 48) record, the natural rubber eradicating instrument effectively uses the Asia biomass of being made by natural rubber, vegetables oil such as (ointment), with the aim consistent (patent documentation 6, non-patent literature 1) that forms circular form society.
Patent documentation 1: Japanese kokai publication hei 10-274494 communique
Patent documentation 2: TOHKEMY 2000-95898 communique
Patent documentation 3: TOHKEMY 2000-319446 communique
Patent documentation 4: TOHKEMY 2003-183488 communique
Patent documentation 5: TOHKEMY 2004-143315 communique
Patent documentation 6: TOHKEMY 2000-43492 communique (with reference to embodiment 1,2)
Non-patent literature 1: 25.2,817 pages of " rubber industry brief guide " (new edition) Japan rubber association tabulatings, clear and rubber association of Corporation distribution on November 15th, 48
Summary of the invention
Yet in above-mentioned technology in the past, because it is not enough rubber not to be imposed tensile strength, the elasticity of sulfuration, crosslinked material, so purposes is limited sometimes, for example, does not present caoutchouc elasticity and is not suitable as the eradicating instrument material.On the other hand, impose sulfuration, crosslinked material because tensile strength, elasticity is excessive and purposes is limited sometimes, for example, therefore hardening and can't obtain caoutchouc elasticity is not suitable as the eradicating instrument material.Therefore and then owing to need sulfuration, crosslinked operation, not only manufacturing process becomes complicated, and is also having problems aspect the security of the sulfuration reagent such as zinc oxide of the sulphur of vulcanizing agent, vulcanization accelerator, auxiliary agent.
On the other hand, the natural rubber eradicating instrument as mentioned above, though be fit to form the circular form social requirement, but for example compare the word poor performance that disappears with the vinylchlorid eradicating instrument, compare manufacturing process's complexity owing to comprising vulcanization process and with vinylchlorid eradicating instrument or non-vinylchlorid eradicating instrument, and, as mentioned above, also have problems at the aspects such as security of sulfuration reagent such as sulphur or vulcanization accelerator.And then, uneconomical owing to be difficult to utilize again the sapwood that in manufacturing process, produces, aspect productivity, also have problems.
The present invention is the invention that solves the problem points of above-mentioned conventional art in view of described practical situation, provides to have by elastic compositions rerum natura, be dispersed with crosslinked natural rubber particle in the matrix that comprises biomass plastics (バ イ オ マ ス プ ラ ス チ Star Network) such as sulfuration in the past, crosslinked unavailable tensile strength, elasticity island; With biomass plastics, natural rubber and a rubber crosslinker more than the melt temperature of biomass plastics and carry out more than the crosslinking temperature at a rubber crosslinker mixing, thereby make crosslinked natural rubber particle island be dispersed in the manufacture method of the elastic composition in the matrix that comprises the biomass plastics; And the eradicating instrument that uses said composition.
The present invention carries out in order to achieve the above object, and the 1st content of the present invention is: a kind of elastic composition, it is characterized in that, and in the matrix that comprises the biomass plastics, be dispersed with crosslinked natural rubber particle island.
The 2nd content of the present invention is: the 1st described elastic composition, it is characterized in that the biomass plastics are to be selected from least a in poly(lactic acid), polybutylene succinate, polymeric amide 11, poly--the 3-hydroxybutyric acid, rhodia, esterification starch, chitosan-Mierocrystalline cellulose starch, the starch-modified polyvinyl alcohol.
The 3rd content of the present invention is: the 1st described elastic composition is characterized in that the biomass plastics are biological degradability biomass plastics.
The 4th content of the present invention is: the manufacture method of elastic composition, it is characterized in that, by with biomass plastics, natural rubber and a rubber crosslinker more than the melt temperature of biomass plastics and carry out mixingly more than the crosslinking temperature at a rubber crosslinker, above-mentioned cross-linked rubber particle is dispersed in the above-mentioned matrix that comprises the biomass plastics.
The 5th content of the present invention is: the manufacture method of the 4th described elastic composition, it is characterized in that the biomass plastics are to be selected from least a in poly(lactic acid), polybutylene succinate, polymeric amide 11, poly--the 3-hydroxybutyric acid, rhodia, esterification starch, chitosan-Mierocrystalline cellulose starch, the starch-modified polyvinyl alcohol.
The 6th content of the present invention is: the manufacture method of the 4th described elastic composition is characterized in that the biomass plastics are biological degradability biomass plastics.
The 7th content of the present invention is: a kind of eradicating instrument, it is characterized in that it comprises elastic composition, and described elastic composition is the elastic composition that is dispersed with crosslinked natural rubber particle in the matrix that comprises the biomass plastics island.
The 8th content of the present invention is: the 7th described eradicating instrument, it is characterized in that the biomass plastics are to be selected from least a in poly(lactic acid), polybutylene succinate, polymeric amide 11, poly--the 3-hydroxybutyric acid, rhodia, esterification starch, chitosan-Mierocrystalline cellulose starch, the starch-modified polyvinyl alcohol.
The 9th content of the present invention is: the 7th described eradicating instrument is characterized in that the biomass plastics are biological degradability biomass plastics.
The 10th content of the present invention is: each described eradicating instrument in the 7th～9, it is characterized in that elastic composition is the biomass plastics of the natural rubber that contains 50～99 weight %, 50～1 weight % and is the elastomerics eradicating instrument composition of a rubber crosslinker of 0.1～5 weight part with respect to natural rubber 100 weight parts.
The 11st content of the present invention is: each described eradicating instrument in the 7th～10, it is characterized in that, and further contain tenderizer.
The 12nd content of the present invention is: the 11st described eradicating instrument is characterized in that tenderizer derives from biomass.
The 13rd content of the present invention is: the 11st or 12 described eradicating instrument is characterized in that tenderizer is selected from vegetable and animals oils, derives from the softening agent of vegetable and animals oils.
The 14th content of the present invention is: each described eradicating instrument in the 11st～13 is characterized in that with respect to total 100 weight parts of natural rubber and biomass plastics, tenderizer is 1～200 weight part.
The 15th content of the present invention is: each described eradicating instrument in the 7th～14, it is characterized in that, and further contain weighting agent.
The 16th content of the present invention is: the 15th described eradicating instrument is characterized in that weighting agent derives from biomass.
The 17th content of the present invention is: the 15th or 16 described eradicating instrument is characterized in that weighting agent is selected from shell powder, eggshell powder.
The 18th content of the present invention is: each described eradicating instrument in the 15th～17 is characterized in that with respect to total 100 weight parts of natural rubber and biomass plastics, weighting agent is 10～1000 weight parts.
The 19th content of the present invention is: a kind of eradicating instrument is characterized in that contain elastomerics and vinyl chloride resin, described elastomerics is the elastomerics that is dispersed with crosslinked natural rubber particle in the matrix that comprises the biomass plastics island.
The 20th content of the present invention is: the 19th described eradicating instrument, it is characterized in that the biomass plastics are to be selected from least a in poly(lactic acid), polybutylene succinate, polymeric amide 11, poly--the 3-hydroxybutyric acid, rhodia, esterification starch, chitosan-Mierocrystalline cellulose starch, the starch-modified polyvinyl alcohol.
The 21st content of the present invention is: the 19th described eradicating instrument is characterized in that the biomass plastics are biological degradability biomass plastics.
The 22nd content of the present invention is: each described eradicating instrument in the 19th～21, it is characterized in that elastomerics is the biomass plastics of the natural rubber that contains 50～99 weight %, 50～1 weight % and is the elastomerics eradicating instrument composition of a rubber crosslinker of 0.1～5 weight part with respect to natural rubber 100 weight parts.
The 23rd content of the present invention is: the 22nd described eradicating instrument, it is characterized in that, and further contain tenderizer.
The 24th content of the present invention is: the 23rd described eradicating instrument is characterized in that tenderizer derives from biomass.
The 25th content of the present invention is: the 23rd or 24 described eradicating instrument is characterized in that tenderizer is selected from vegetable and animals oils, derives from its softening agent.
The 26th content of the present invention is: each described eradicating instrument in the 23rd～25 is characterized in that with respect to total 100 weight parts of natural rubber and biomass plastics, tenderizer is 1～200 weight part.
The 27th content of the present invention is: each described eradicating instrument in 22～26, it is characterized in that, and further contain weighting agent.
The 28th content of the present invention is: the 27th described eradicating instrument is characterized in that weighting agent derives from biomass.
The 29th content of the present invention is: the 27th or 28 described eradicating instrument is characterized in that weighting agent is selected from shell powder, eggshell powder.
The 30th content of the present invention is: each described eradicating instrument in the 27th～29 is characterized in that with respect to total 100 weight parts of natural rubber and biomass plastics, weighting agent is 10～1000 weight parts.
The 31st content of the present invention is: each described eradicating instrument in the 19th～30 is characterized in that vinyl chloride resin is the vinyl chloride resin eradicating instrument composition that contains vinyl chloride resin 100 weight parts, softening agent 60～180 weight parts.
The 32nd content of the present invention is: the manufacture method of eradicating instrument, it is characterized in that, and will comprise the eradicating instrument and the eradicating instrument melting mixing that comprises vinyl chloride resin eradicating instrument composition of elastomerics eradicating instrument composition, carry out moulding.
The 33rd content of the present invention is: the manufacture method of the 32nd described eradicating instrument, it is characterized in that, elastomerics eradicating instrument composition contain 50～99 weight % natural rubber, 50～1 weight % the biomass plastics and be a rubber crosslinker of 0.1～5 weight part with respect to natural rubber 100 weight parts.
The 34th content of the present invention is: the manufacture method of the 32nd or 33 described eradicating instrument is characterized in that vinyl chloride resin eradicating instrument composition contains vinyl chloride resin 100 weight parts, softening agent 60～180 weight parts.
The 35th content of the present invention is: the manufacture method of each described eradicating instrument in the 32nd～34, it is characterized in that, the eradicating instrument that comprises elastomerics eradicating instrument composition is 30～90 weight %, and the eradicating instrument that comprises vinyl chloride resin eradicating instrument composition is 70～10 weight %.
Elastic composition of the present invention does not rely on fossil resource, all come the natural rubber and the biomass plastics of authigenic material as the material of raw material use, therefore, also can not increase Atmospheric Carbon Dioxide even discard, be the elastic composition useful to environment.And, be provided at decomposition physical environment under, the conform elastic composition of type more by using the biological degradability material as the biomass plastics.
In addition, elastic composition of the present invention is owing to be thermoplastic elastomer, so therefore the sapwood recirculation easily that produces during moulding, can realize that cost reduces, and suitable resource recycling society.
And then, the manufacture method of elastic composition of the present invention, because the crosslinked of mixing and natural rubber of natural rubber and biomass plastics carry out simultaneously, so operation is simplified the productivity height.In addition, natural rubber is crosslinked owing to not using vulcanizing agent, vulcanization accelerators such as sulphur, zinc oxide, so security is also high.
Elastic composition of the present invention with in the past pass through sulfuration, the crosslinked material that obtains is different, for example is suitable as the base material of eradicating instrument.
The eradicating instrument that comprises elastic composition of the present invention, different with the vinylchlorid eradicating instrument in the past that depends on fossil resource, non-vinylchlorid eradicating instrument, the sapwood that environment is produced during useful and moulding is recycled easily, realizes that owing to reducing waste of material cost reduces.
In addition, essential mixing operation of natural rubber eradicating instrument in the past and other crosslinked operation, relative therewith, crosslinked owing in mixing, carrying out in the present invention, so operation is simplified the productivity height.
In addition, natural rubber eradicating instrument in the past uses vulcanizing agent, vulcanization accelerators such as sulphur, zinc sulphide, and is relative therewith, because eradicating instrument of the present invention does not use such chemical reagent, so security is also high.
And then eradicating instrument of the present invention is compared with natural rubber eradicating instrument in the past, non-vinylchlorid eradicating instrument, the word performance that disappears height.
In addition, comprise the eradicating instrument of elastic composition of the present invention, owing to contain the eradicating instrument of making by vinyl chloride resin, preferred vinyl chloride resin composition, thus can reduce degree of dependence to fossil resource, and can further improve the word performance that disappears.
Embodiment
Elastic composition of the present invention is characterised in that, contains the island structure that is dispersed with crosslinked natural rubber particle in the matrix that comprises the biomass plastics (sea) island.
The natural rubber that uses among the present invention is categorized as sheet rubber, pale crepe, brown crepe, blanket crepe, block rubber, crumb rubber etc. according to the method that is processed into solid rubber by latex, though all size grade is arranged, but be not limited to them, all can use, also do not limit the production ground.The natural rubber derivative that in addition, can also use in epoxy natural rubber to be enumerated.They can use separately, or will be used in combination more than 2 kinds as required.
The biomass plastics that use among the present invention can be categorized as chemosynthesis class, microorganisms producing class, natural goods class.As the chemosynthesis class, can enumerate lactic acid polymerizes and polylactic resin, described lactic acid obtains carbohydrate, the amylofermentation that obtains (for example レ イ シ ア of Mitsui Chemicals corporate system) from corn, potato, sugarcane; With the succsinic acid of being made by starch and 1, the 4-butyleneglycol is the polybutylene succinate (for example GS-Pla of Mitsubishi Chemical Ind's system) of raw material; With the Viscotrol C is the polymeric amide 11 (for example リ Le サ Application B of ア Le ケ マ corporate system) of raw material.As the microorganisms producing class, can enumerate the multipolymer (for example PHBH of カ ネ カ society manufacturing) of poly--3-hydroxybutyric acid (for example PVC オ グ リ one Application of Mitsubishi's aerochemistry corporate system), 3-hydroxybutyric acid and 3-hydroxycaproic acid.Poly-(3-hydroxybutyric acid-co-3-the hydroxycaproic acid) (poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) that uses among the present invention by microorganisms, below be designated as PHBH), as described in TOHKEMY 2007-77232 communique, by microorganisms, consider that from the angle of flexibility and intensity balance the ratio of components of repeating unit preferably poly-(3-hydroxybutyric acid)/poly-(3-hydroxycaproic acid) is more than 80/20, below 99/1 (mol/mol).The ratio of components of the repeating unit by changing PHBH can change fusing point, crystallization degree, can change rerum naturas such as Young's modulus, thermotolerance, can make it have the rerum natura of polypropylene to poly scope.As the natural goods class, can enumerate rhodia (for example セ Le グ リ one Application PCA of ダ イ セ Le chemical company system), esterification starch (コ one Application Port one Le of for example Japanese コ one Application ス one チ corporate system), chitosan-Mierocrystalline cellulose-starch (for example De ロ Application CC of ア イ セ ロ chemical company system), starch-modified polyvinyl alcohol (for example ノ バ モ Application ト corporate system Mater-Bi) etc.These materials can use separately, or will be used in combination more than 2 kinds as required.
By using biological degradability material as renewable resources, can make the elastic composition of the type that conforms more as the biomass plastics.
The proportion of composing of natural rubber and biomass plastics can suitably be determined according to purposes, the rerum natura of target elastic composition, for example, as the eradicating instrument base material, preferred natural rubber is that 50～99 weight %, biomass plastics are the scope of 50～1 weight %, and more preferably natural rubber is that 70～95 weight %, biomass plastics are 30～5 weight %.The biomass plastics are during less than 1 weight %, the flowability difference of elastic composition and aspect formability existing problems.When the biomass plastics surpassed 50 weight %, elastic composition hardening and do not present caoutchouc elasticity had the tendency of not bringing into play enough word performances that disappears when for example using as the eradicating instrument base material.The proportion of composing of natural rubber and PHBH can suitably be determined according to purposes, the rerum natura of purpose elastic composition, but base material as eradicating instrument, preferred natural rubber is that 50～99 weight %, PHBH are 50～1 weight %, and more preferably natural rubber is that 70～95 weight %, PHBH are 30～5 weight %.If PHBH is less than 1 weight %, then the flowability of elastic composition is poor, aspect formability problem is arranged.If PHBH surpasses 50 weight %, then elastic composition hardening does not show caoutchouc elasticity, and the tendency that can not bring into play enough word performances that disappears is arranged when for example using as the base material of eradicating instrument.
As a rubber crosslinker that uses among the present invention, can use organo-peroxide suitably.Particularly, can enumerate dicumyl peroxide (for example パ one Network ミ Le D of Nof Corp.'s system), 2,5-dimethyl-2,5-two-t-butylperoxy hexane (for example パ one ヘ キ サ 25B of Nof Corp.'s system), two-t-butyl peroxy diisopropyl benzene (for example パ one Block チ Le P of Nof Corp.'s system), 2,5-dimethyl-2,5-two-t-butylperoxy-3-hexin (for example パ one ヘ キ シ Application 25B of Nof Corp.'s system) etc.In addition, can also use organic sulfurizing agent.Particularly, can enumerate N, N '-meta-phenylene bismaleimide (for example バ Le ノ Star Network PM of the emerging chemical company of imperial palace system), p-quinone dioxime (for example バ Le ノ Star Network GM of the emerging chemical company of imperial palace system), alkylphenol-formaldehyde resin (alkylphenolformaldehyde resin, for example Star キ ロ one Le 201 of ridge, field chemistry society system) etc.These materials can use separately, or will be used in combination more than 2 kinds as required.
With respect to natural rubber 100 weight parts, use 0.1～5.0 parts by weight of rubber linking agent.A rubber crosslinker becomes insufficient less than 0.1 weight part is then crosslinked, and natural rubber does not form particle and can't obtain the purpose structure, and on the other hand, then the rebound resilience of cross-linked rubber particle is excessive to surpass 5.0 weight parts, and the tendency that has problems aspect formability is arranged.
In elastic composition of the present invention, can be added on the various additives that use in biomass plastic material, the natural rubber material field.As such additive, can enumerate lubricants such as weathering resistance modifying agent, senior aliphat alcohol, aliphatic amide, metallic soap, fatty acid ester such as UV light absorber, hindered amine light stabilizer, antioxidant etc.
Elastic composition of the present invention can obtain carrying out mixing more than the melt temperature of biomass plastics and more than the crosslinking temperature at a rubber crosslinker by with biomass plastics, natural rubber and a rubber crosslinker and then in the mixing roll of as required tenderizer, weighting agent etc. being packed into.
Mixingly preferably under high-shear, carry out mixingly,, can enumerate twin-screw mixer forcing machine, Banbury, pressurization kneader, mixing roll etc., wherein preferably use the twin-screw mixer forcing machine as such mixing roll.
The preferred temperature higher 10～50 ℃ more than the melt temperature of biomass plastics than the melt temperature of biomass plastics, the preferred temperature higher 5～20 ℃ more than the crosslinking temperature of a rubber crosslinker than the crosslinking temperature of a rubber crosslinker.
Elastic composition of the present invention has excellent elasticity, resiliency, useful in fields such as cushioning material for packing, lagging material, sound-proof material, sound absorbent material, tatami floor, flooring material, wall material, be useful particularly as the eradicating instrument base material.
As elastic composition of the present invention and in the past sulfuration, crosslinked and material compare, have the reason of so unique rerum natura, be considered to produce by mixing rubber constituent is cut off.
When elastic composition of the present invention is used with base material as eradicating instrument, also can suitably use other additives such as painted material, spices, stablizer, antioxidant, UV light absorber, mould inhibitor such as tenderizer, weighting agent, organic-inorganic pigment, dyestuff to make elastomerics eradicating instrument composition arbitrarily.
As tenderizer, can use mineral oil, vegetable and animals oils or derive from their softening agent.As mineral oil, specifically can enumerate paraffin class process oil (プ ロ セ ス オ イ Le), naphthenic (Na Off テ Application system) process oil, aromatic series generic operation wet goods.As vegetable and animals oils, specifically can enumerate rapeseed oil, refining rapeseed oil (Cai Seed Bai Twisted oil), Viscotrol C, Oleum Gossypii semen, Semen Lini oil, soybean oil, sesame oil, Semen Maydis oil, Thistle oil, plam oil, Oleum Cocois, peanut oil, haze tallow, rosin, Stockholm tar, tallol etc.As the softening agent that derives from vegetable and animals oils, can enumerate glycerin fatty acid ester, specifically can enumerate glycerine diacetyl mono-laurate (グ リ セ リ Application ジ ア セ ト モ ノ ラ ウ レ one ト), triacetin, glyceryl diacetate etc.These materials can use separately or will be used in combination more than 2 kinds as required.From the viewpoint of elastic composition that the type that conforms more can be provided, the preferred use derives from as the vegetable and animals oils of the biomass of renewable resources or derives from its softening agent.
With respect to mixture 100 weight parts of natural rubber and biomass plastics, the use level of tenderizer can be 1～200 weight part.Preferred 10～150 weight parts.Tenderizer during less than 1 weight part the addition of tenderizer not enough, on the other hand, surpass 200 weight parts and then might ooze out.
As weighting agent, can enumerate water-ground limestone, light calcium carbonate, silicon-dioxide, diatomite, magnesium oxide, titanium oxide, talcum, sericite, quartz powder, montmorillonite, shell powder, the eggshell powder of scallop (ホ テ), oyster, a species of small clam living in fresh water (じ body) etc., organic hollow particle, inorganic hollow particle etc.These materials can use separately, or will be used in combination more than 2 kinds as required.From the viewpoint of elastic composition that the type that conforms more can be provided, preferably as shell powder or eggshell powder such as a large amount of scallops that come authigenic material that produce of waste, oysters.
With respect to mixture 100 weight parts of natural rubber and biomass plastics, the use level of weighting agent can be 10～1000 weight parts.Preferred 50～500 weight parts.The additive effect of weighting agent is insufficient during less than 10 weight parts, surpasses the then composition hardening of 1000 weight parts on the other hand, does not present sufficient caoutchouc elasticity, and the tendency that can't bring into play the word performance that disappears is fully arranged when for example using as the eradicating instrument base material.
With above-mentioned elastomerics eradicating instrument composition molding, and severing becomes specified dimension to the eradicating instrument of the present invention that uses above-mentioned elastomerics eradicating instrument composition, comprises elastomeric eradicating instrument thereby make by extrusion forming, injection molding, extrusion moulding etc.
As above obtain comprising elastomeric eradicating instrument (hereinafter referred to as the elastomerics eradicating instrument) by containing vinyl chloride resin, preferably containing the eradicating instrument (hereinafter referred to as the vinyl chloride resin eradicating instrument) that comprises vinyl chloride resin, can further improve the word performance that disappears.
Such height disappears word performance eradicating instrument can be with elastomerics and vinyl chloride resin with additive melting mixings such as tenderizer, packing material, softening agent, tinting material, spices, carry out moulding, above-mentioned elastomerics eradicating instrument and vinyl chloride resin eradicating instrument mixed carry out melting mixing and can effectively improve the word performance that disappears, thus preferred.Therefore, describe according to this preferable methods below.
The vinyl chloride resin that uses in the vinyl chloride resin eradicating instrument of the present invention is not particularly limited, and uses known vinyl chloride resin, can be paste resin (ペ one ス ト Trees fat), also can be unmodified resin.Softening agent can also be in vinyl chloride resin, added, and then as required, additives such as stablizer, coloured material, spices can also be suitably added arbitrarily.
As softening agent, can enumerate dioctyl phthalate (DOP) (DOP), Dinonylphthalate (DNP), diisononyl phthalate (DINP), Di Iso Decyl Phthalate (DIDP), phthalic acid two (tridecyl) ester (DTDP), phthalic acid two (undecyl) ester phthalic ester plasticizers such as (DUP); Trimellitic acid di-isooctyl trimellitic acid ester plasticizers such as (TIOTM); Polyester softening agent etc., these materials can use separately, or will be used in combination more than 2 kinds as required.
With respect to vinyl chloride resin 100 weight parts, add softening agent 60～180 weight parts, preferably add 100～160 weight parts.Composition hardening during less than 100 weight parts and do not bring into play the word performance that disappears fully, on the other hand, the possibility that has softening agent to move or ooze out when surpassing 160 weight parts.
During for paste resin, the eradicating instrument composition that will comprise paste resin and softening agent, other additive as required is mixing, after the deaeration, flow in the mold for forming of prescribed depth, cool off after the heating specified time, become specified dimension from mould taking-up and severing, thereby make eradicating instrument.
On the other hand, during for unmodified resin, will comprise unmodified resin and softening agent, as required the eradicating instrument composition molding of other additive, and severing becomes specified dimension, thereby make eradicating instrument by injection moulding machine, extrusion shaper etc.
As above, take by weighing elastomerics eradicating instrument and vinyl chloride resin eradicating instrument with required ratio, mixing in warmed-up kneader, be ground into particle after the cooling, carry out moulding by injection molding, extrusion moulding etc., and severing becomes specified dimension, thereby makes the disappear eradicating instrument of word performance of height of the present invention.
Blending ratio for elastomerics eradicating instrument and vinyl chloride resin eradicating instrument is not particularly limited, lay particular emphasis on recirculation, when reducing the load to environment, increase the ratio of the former elastomerics eradicating instrument, on the other hand, lay particular emphasis on when disappearing the word performance, the ratio that increases the latter's vinyl chloride resin eradicating instrument gets final product, but the vinyl chloride resin eradicating instrument after a little while, diminishes as the raising effect of the word performance that disappears of the object of the invention.Therefore, preferably with respect to elastomerics eradicating instrument 30～90 weight %, the vinyl chloride resin eradicating instrument is 70～10 weight %, and more preferably with respect to elastomerics eradicating instrument 30～80 weight %, the vinyl chloride resin eradicating instrument is 70～20 weight %.Even the vinyl chloride resin eradicating instrument surpasses 70 weight %, the word performance that disappears is also roughly certain, but the tendency of the load increase of pair environment is arranged.
Embodiment
Below, illustrate in greater detail the present invention based on embodiment, reference example and comparative example, but these examples to scope of the present invention without any restriction.
The material that uses in following embodiment, reference example and the comparative example is shown in table 1.
[table 1]
| Trade(brand)name | The material name | Manufacturers |
| RSS#1 | Natural rubber | Indonesia produces |
| レイシアH-100 | Biomass plastics poly(lactic acid) (melt temperature: 164 ℃) | Mitsui Chemicals, Inc |
| GS PLa | Biomass plastics polybutylene succinate (melt temperature: 112 ℃) | Mitsubishi chemical Co., Ltd |
| Refining rapeseed oil | The tenderizer vegetables oil | コ ス モ oiling Co., Ltd. |
| リ ケ マ one Le PL-004 | Tenderizer glycerine diacetyl mono-laurate | Reason is ground PVC ミ Application Co., Ltd. |
| SS#80 | The weighting agent water-ground limestone | Eastern efflorescence of day Industrial Co., Ltd |
| The scallop shell powder | Weighting agent scallop oyster shell whiting flour | Eastern efflorescence of day Industrial Co., Ltd |
| パ one Network ミ Le D-40 | A rubber crosslinker dicumyl peroxide 40% dilution (crosslinking temperature: 150～180 ℃) | NOF Corp |
| バルノツクPM | A rubber crosslinker N, N '-meta-phenylene bismaleimide (crosslinking temperature: 150～190 ℃) | The emerging KCC of imperial palace |
| White サ Block No.1 | Surrogate (サ Block ス チ チ ユ one ト) sulfur subchloride ointment (salt Sulfur Off ア Network チ ス) | It full サ Block Chemical Co., Ltd |
| ダィアナプロセスNP-24 | Tenderizer naphthenic process oil | Idemitsu Kosen Co., Ltd. |
| サルフアツクス200S | Vulcanizing agent sulphur powder | Crane sees chemical industry Co., Ltd. |
| ノ Network セ ラ one TT | The thiurams vulcanization accelerator | The emerging KCC of imperial palace |
| ノ Network セ ラ one DM | The thiazoles vulcanization accelerator | The emerging KCC of imperial palace |
| ノ Network セ ラ one BG | Guanidine class vulcanization accelerator | The emerging KCC of imperial palace |
| Zinc oxide | Zinc oxide | Sakai Chemical Industry Co., Ltd. |
| ZEST P-21 | Vinyl chloride resin | New first salt PVC Co., Ltd. |
| DOP | The plasticizer phthalic acid dioctyl ester | The ジ エ イ プ ラ ス of Co., Ltd. |
| NS#400 | The weighting agent water-ground limestone | Eastern efflorescence of day Industrial Co., Ltd |
| ES-A | The stablizer calcium stearate | Plumbous city chemical industry Co., Ltd. |
| ES-Z | The stablizer Zinic stearas | Plumbous city chemical industry Co., Ltd. |
| PHBH | Poly-(3-hydroxybutyric acid-co-3-hydroxycaproic acid) | The カ ネ カ of Co., Ltd. |
| ユニカ | Light calcium carbonate | Rice village lime Industrial Co., Ltd |
| マルチZ | Compound zinc white | Rice village lime Industrial Co., Ltd |
| パ one ヘ キ サ C-40 | 1,1-two (tert-butyl hydroperoxide) hexanaphthene 40 % dilutions | NOF Corp |
| アデカスブLA-32 | The benzotriazole category UV light absorber | Asahi Denka Co., Ltd. |
| アデカスブLA-77G | Hindered amine light stabilizer | Asahi Denka Co., Ltd. |
Embodiment 1～11
With the pressurization kneader that the natural rubber in the material shown in the table 2, tenderizer, packing material is mixing in advance, add a rubber crosslinker with roller and obtain the compounding rubber thing.Particulate state about gained compounding rubber thing is become 5mm square by severing.Then, twin screw extruder KZW-15 TW-60 (equidirectional complete occlusal pattern with テ Network ノ ベ Le corporate system, screw diameter 15mm, L/D=60), compounding rubber composition granule and biomass plastic grain are supplied with the weight feed device separately with the cooperation ratio shown in the table 2, carried out mixing with screw speed 400rpm.Setting barrel temperature is 120～190 ℃, and making melting temperature is that the fusing point (170 ℃) of biomass plastics is above and more than rubber cross temperature (180 ℃).
Is the square rod shape with the resulting composition particle with single screw extrusion machine (90～110 ℃ of barrel temperatures, 120 ℃ of head temperatures) extrusion moulding, and severing makes elastomerics eradicating instrument (size: 12 * 18 * 43mm).
As the eradicating instrument characteristic, the evaluation hardness and the word performance (the word rate disappears) that disappears.The results are shown in table 2.
Hardness is according to " JIS S 6050 plastics eradicating instruments ", measures with C type hardness tester meter (polymer gauge system C type hardness tester meter).
In addition, the word rate that disappears is measured with following method.
(1) sample is cut into the tabular of thickness 5mm, and the part that will contact with test pater makes the circular arc of radius 6mm, with it as test film.
(2) make test film vertical with coating paper and contact with coloring line with meeting at right angles, mounting weight on test film, make weight and upholder (ホ Le ダ) quality and be 0.5kg, wipe painted 4 back and forth with the speed of 150 ± 10cm/min.
(3) with densitometer (DENSITOMETER PDA65 sakura corporate system), be 0 with the concentration of coating paper non-staining part, measure painted and wipe the concentration of portion respectively.
(4) the word rate that disappears is calculated by following formula.
The word rate that disappears (%)=(1-(wiping the concentration of the painted portion of concentration ÷ of portion)) * 100
[table 2]
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | |
| Natural rubber | RSS#1 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| The biomass plastics | レイシアH-100 | 30 | 30 | 30 | 30 | 30 | 20 | 30 | 30 | 30 | 35 | |
| GS Pla | 30 | |||||||||||
| A rubber crosslinker | パ one Network ミ Le D-40 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | |
| バルノツクPM | 3 | |||||||||||
| Tenderizer | Refining rapeseed oil | 20 | ||||||||||
| リ ケ マ one Le Le PL-004 | 20 | 20 | 20 | 50 | 70 | 80 | 150 | 100 | 70 | |||
| Weighting agent | SS#80 | 50 | 50 | 100 | 200 | 250 | 500 | 200 | ||||
| The scallop shell powder | 200 | |||||||||||
| Natural rubber: the ratio of biomass plastics | 77∶23 | 77∶23 | 77∶23 | 77∶23 | 77∶23 | 83∶17 | 77∶23 | 77∶23 | 77∶23 | 74∶26 | 77∶23 | |
| Characteristic | Hardness (C type) | 82 | 73 | 75 | 85 | 82 | 60 | 72 | 70 | 82 | 66 | 82 |
| The word rate that disappears (%) | 81 | 85 | 85 | 90 | 89 | 93 | 92 | 93 | 88 | 93 | 92 | |
Comparative example 1
Use the material shown in the table 3, use two rollers mill that whole compounding ingredients are mixing in natural rubber, obtain the compounding rubber thing.Gained compounding rubber thing is prepared moulding, make to be fit to the regulation die size, with thermocompressor under 130 ℃, 20 minutes condition, vulcanize, moulding.The severing of gained rubber-moulding thing is become specified dimension, obtain natural rubber eradicating instrument (size: 12 * 18 * 43mm).
The hardness of gained eradicating instrument and the word rate that disappears used with the same method of embodiment 1～11 carry out evaluation of measuring.The results are shown in table 3.
[table 3]
| Form | Comparative example 1 | |
| Natural rubber | RSS#1 | 100 |
| Surrogate | White サ Block No.1 | 300 |
| Weighting agent | SS#80 | 400 |
| Tenderizer | ダイアナプロセスNP-24 | 150 |
| Vulcanizing agent | サルフアツクス200S | 4 |
| Vulcanization accelerator | ノクセラ-TT | 1 |
| ノクセラ-DM | 0.5 | |
| ノクセラ-BG | 0.5 | |
| Vulcanization aid | Zinc oxide | 5 |
| Characteristic | Hardness (C type) | 60 |
| The word rate that disappears (%) | 90 | |
Reference example 1～2: the manufacturing of elastomerics eradicating instrument
In the material shown in the table 4, with the pressurization kneader that natural rubber, tenderizer, packing material is mixing in advance, add a rubber crosslinker with roller and obtain the compounding rubber thing.Particulate state about becoming 5mm square the severing of gained compounding rubber thing.Then, twin screw extruder KZW-15 TW-60 (equidirectional complete occlusal pattern with テ Network ノ ベ Le corporate system, screw diameter 15mm, L/D=60), compounding rubber composition granule and biomass plastic grain are supplied with the weight feed device separately with the cooperation ratio shown in the table 4, screw speed is set at 400rpm, barrel temperature is set at 120～190 ℃ carries out mixingly, and severing becomes the square particulate state of 3mm.
Is the square rod shape with the resulting composition particle with single screw extrusion machine (100～120 ℃ of barrel temperatures, 130 ℃ of head temperatures) extrusion moulding, and severing makes elastomerics eradicating instrument (size: 12 * 18 * 43mm).
With with the hardness and the word rate that disappears of the same method evaluation of measuring gained eradicating instrument of embodiment 1～11.Show the result in table 4.
[table 4]
| Reference example 1 | Reference example 2 | ||
| Natural rubber | RSS#1 | 100 | 100 |
| The biomass plastics | レイシアH-100 | 30 | |
| GS Pla | 30 | ||
| Tenderizer | リ ケ マ one Le PL-004 | 70 | 70 |
| Weighting agent | SS#80 | 200 | 200 |
| A rubber crosslinker | パ one Network ミ Le D-40 | 2 | 2 |
| Natural rubber: the ratio of biomass plastics | 77∶23 | 77∶23 | |
| Characteristic | Hardness (C type) | 72 | 82 |
| The word rate that disappears (%) | 92.3 | 91.6 | |
Reference example 3: the manufacturing of vinyl chloride resin eradicating instrument
As shown in table 5, vinyl chloride resin, softening agent, weighting agent, stablizer are mixed stirring, obtain pasty state colloidal sol (ペ one ス ト ゾ Le).After gained pasty state colloidal sol carried out vacuum defoamation, flow into insulation 130 ℃ mold for forming (inside dimension: 100 * 100 * 10mm), heat and cool off after 26 minutes, from mould, take out, vinyl chloride resin eradicating instrument (size: 10 * 18 * 43mm) is made in severing.
With with the hardness and the word rate that disappears of the same method evaluation of measuring gained eradicating instrument of embodiment 1～11.Show the result in table 5.
[table 5]
| Reference example 3 | ||
| Vinyl chloride resin | ZEST P-21 | 100 |
| Softening agent | DOP | 160 |
| Weighting agent | NS#400 | 100 |
| Stablizer | ES-A | 0.5 |
| ES-Z | 0.5 | |
| Characteristic | Hardness (C type) | 60 |
| The word rate that disappears (%) | 97.7 | |
Embodiment 12～19
Elastomerics eradicating instrument that will obtain in reference example 1～2 and the vinyl chloride resin eradicating instrument that obtains in reference example 3 mix with the blending ratio shown in the table 6, usefulness insulation mixing 5 minutes at 120 ℃ pressurization kneader.With pulverizing the making particle after the resulting composition cooling, be the regulation shape with the single screw extrusion machine extrusion moulding, eradicating instrument (size 12 * 18 * 43mm) is made in severing.
With with the hardness and the word rate that disappears of the same method evaluation of measuring gained eradicating instrument of embodiment 1～11.Show the result in table 6.
[table 6]
| Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | ||
| The elastomerics eradicating instrument (weight %) of reference example 1 | 90 | 70 | 50 | 30 | |||||
| The elastomerics eradicating instrument (weight %) of reference example 2 | 90 | 70 | 50 | 30 | |||||
| The vinyl chloride resin eradicating instrument (weight %) of reference example 3 | 10 | 30 | 50 | 70 | 10 | 30 | 50 | 70 | |
| Characteristic | Hardness (C type) | 72 | 66 | 61 | 60 | 80 | 75 | 69 | 62 |
| The word rate that disappears (%) | 92.6 | 94.1 | 95.6 | 97.2 | 92.4 | 93.8 | 95.4 | 96.5 | |
Embodiment 20～30
With the pressurization kneader that the natural rubber in the material shown in the table 7, tenderizer, packing material, light deterioration preventing agent (light deterioration preventing drug) is mixing in advance, add a rubber crosslinker with roller and obtain the compounding rubber thing.Particulate state about gained compounding rubber thing is become 5mm square by severing.Then, twin screw extruder KZW-15 TW-60 (equidirectional complete occlusal pattern with テ Network ノ ベ Le corporate system, screw diameter 15mm, L/D=60), compounding rubber composition granule and biodegradable plastic particle are supplied with the weight feed device separately with the cooperation ratio shown in the table 7, and the setting screw speed is that 400rpm, barrel temperature are 110～155 ℃ and carry out mixing.
Is the square rod shape with the resulting composition particle with single screw extrusion machine (100～120 ℃ of barrel temperatures, 130 ℃ of head temperatures) extrusion moulding, and severing makes eradicating instrument.
As the characteristic of eradicating instrument, use method evaluation hardness and the disappear word rate same with embodiment 1～11.The result is as shown in table 7.
[table 7]
| Form | Embodiment 20 | Embodiment 21 | Embodiment 22 | Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | Embodiment 29 | Embodiment 30 | |
| Natural rubber | RSS#1 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Biodegradable plastic | PHBH | 45 | 45 | 45 | 35 | 45 | 45 | 45 | 45 | 45 | 45 | 45 |
| Tenderizer | リ ケ マ one Le PL-004 | 70 | 70 | 70 | 70 | 70 | 70 | 70 | 80 | 70 | 70 | 70 |
| Weighting agent | SS#80 | 200 | 200 | 200 | 200 | 200 | 200 | 200 | 150 | 100 | ||
| SS#30 | 50 | 100 | ||||||||||
| The scallop shell powder | 200 | 200 | ||||||||||
| ユニカ | 10 | 10 | 10 | 10 | ||||||||
| マルチZ | 10 | |||||||||||
| A rubber crosslinker | パ one ヘ キ サ C-40 | 1.0 | 1.5 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 1.5 | 2.0 | 2.0 | 2.0 |
| The light deterioration preventing agent | アテカスブLA-32 | 1.0 | 1.0 | 1.0 | ||||||||
| アデカスブLA-77G | 1.0 | |||||||||||
| Natural rubber: the ratio of biodegradable plastic | 69∶31 | 69∶31 | 69∶31 | 74∶26 | 69∶31 | 69∶31 | 69∶31 | 69∶31 | 69∶31 | 69∶31 | 69∶31 | |
| Characteristic | Hardness (C type) | 79 | 82 | 84 | 78 | 85 | 84 | 85 | 81 | 84 | 84 | 83 |
| Cancellation ability (%) | 94 | 94 | 94 | 93 | 94 | 95 | 95 | 94 | 95 | 95 | 95 | |
Comparative example 2
As shown in table 8, PHBH is replaced with poly(lactic acid) (レ イ シ ア H-100, the trade(brand)name of Mitsui Chemicals, Inc), eradicating instrument is made in operation similarly to Example 26, and estimates its characteristic.In order to be fit to the melt temperature (170～180 ℃) of poly(lactic acid), a rubber crosslinker is become パ one Network ミ Le D-40, barrel temperature is set at 125～190 ℃.The result is as shown in table 8.
[table 8]
| Form | Comparative example 2 | |
| Natural rubber | RSS#1 | 100 |
| The biomass plastics | レイシアH-100 | 45 |
| Tenderizer | リ ケ マ one Le PL-004 | 70 |
| Weighting agent | SS#80 | 200 |
| SS#30 | ||
| The scallop shell powder | ||
| ユニカ | ||
| マルチZ | 10 | |
| A rubber crosslinker | パ one Network ミ Le D-40 | 2.0 |
| The light deterioration preventing agent | アテカスブLA-32 | |
| アデカスブLA-77G | ||
| Natural rubber: the ratio of biomass plastics | 69∶31 | |
| Characteristic | Hardness (C type) | 91 |
| Cancellation ability (%) | 88 | |
Comparative example 3
Use the material shown in the table 9, use two rollers mill that whole compounding ingredients are mixing in natural rubber, obtain the compounding rubber thing.Gained compounding rubber thing is prepared moulding, make to be fit to the regulation die size, with thermocompressor under 130 ℃, 20 minutes condition, vulcanize, moulding.The severing of gained rubber-moulding thing is become specified dimension, obtain eradicating instrument, and estimate its characteristic.The result is as shown in table 9.
[table 9]
| Form | Comparative example 3 | |
| Natural rubber | RSS#1 | 100 |
| Surrogate | White サ Block No.1 | 300 |
| Weighting agent | SS#80 | 400 |
| Tenderizer | ダイアナプロセスNP-24 | 150 |
| Vulcanizing agent | サルフアツクス200S | 4 |
| Vulcanization accelerator | ノ Network セ ラ one TT | 1 |
| ノクセラ-DM | 0.5 | |
| ノクセラ-BG | 0.5 | |
| Vulcanization aid | Zinc oxide | 5 |
| Characteristic | Hardness (C type) | 80 |
| Cancellation ability (%) | 90 | |
Industrial applicability
As mentioned above, elastic composition of the present invention since since living beings plastics and the natural rubber of authigenic material be principal component, so do not rely on that fossil resource discardedly can not increase carbon dioxide in the atmosphere yet, can recycle, useful to environment, corresponding with Circular Society Construction elastic composition even be. In addition, when using elastic composition of the present invention as the base material of eradicating instrument, can provide the eradicating instrument of disappear word performance, excellent in safety. And then, by also using vinyl chloride resin as the eradicating instrument base material, can reduce the dependence to fossil resource, and the more excellent eradicating instrument of word performance that disappears is provided. In addition, by using biological degradability living beings plastics as the living beings plastics, can be provided in elastic composition and the eradicating instrument of the type that more conforms that decomposes under the natural environment.
Claims (35)
1, a kind of elastic composition is characterized in that, is dispersed with crosslinked natural rubber particle in the matrix that comprises the biomass plastics island.
2, the described elastic composition of claim 1, it is characterized in that the biomass plastics are to be selected from least a in poly(lactic acid), polybutylene succinate, polymeric amide 11, poly--the 3-hydroxybutyric acid, rhodia, esterification starch, chitosan-Mierocrystalline cellulose starch, the starch-modified polyvinyl alcohol.
3, the described elastic composition of claim 1 is characterized in that, the biomass plastics are biological degradability biomass plastics.
4, the manufacture method of elastic composition, it is characterized in that, by with biomass plastics, natural rubber and a rubber crosslinker more than the melt temperature of biomass plastics and carry out mixingly more than the crosslinking temperature at a rubber crosslinker, described cross-linked rubber particle is dispersed in the described matrix that comprises the biomass plastics.
5, the manufacture method of the described elastic composition of claim 4, it is characterized in that the biomass plastics are to be selected from least a in poly(lactic acid), polybutylene succinate, polymeric amide 11, poly--the 3-hydroxybutyric acid, rhodia, esterification starch, chitosan-Mierocrystalline cellulose starch, the starch-modified polyvinyl alcohol.
6, the manufacture method of the described elastic composition of claim 4 is characterized in that, the biomass plastics are biological degradability biomass plastics.
7, a kind of eradicating instrument is characterized in that, it is included in the elastic composition that is dispersed with crosslinked natural rubber particle in the matrix that comprises the biomass plastics island.
8, the described eradicating instrument of claim 7, it is characterized in that the biomass plastics are to be selected from least a in poly(lactic acid), polybutylene succinate, polymeric amide 11, poly--the 3-hydroxybutyric acid, rhodia, esterification starch, chitosan-Mierocrystalline cellulose starch, the starch-modified polyvinyl alcohol.
9, the described eradicating instrument of claim 7 is characterized in that, the biomass plastics are biological degradability biomass plastics.
10, each described eradicating instrument in the claim 7～9, it is characterized in that elastic composition is the biomass plastics of the natural rubber that contains 50～99 weight %, 50～1 weight % and is the elastomerics eradicating instrument composition of a rubber crosslinker of 0.1～5 weight part with respect to natural rubber 100 weight parts.
11, each described eradicating instrument in the claim 7～10 is characterized in that, further contains tenderizer.
12, the described eradicating instrument of claim 11 is characterized in that tenderizer derives from biomass.
13, claim 11 or 12 described eradicating instruments is characterized in that, tenderizer is selected from vegetable and animals oils, derives from the softening agent of vegetable and animals oils.
14, each described eradicating instrument in the claim 11～13 is characterized in that, with respect to total 100 weight parts of natural rubber and biomass plastics, tenderizer is 1～200 weight part.
15, each described eradicating instrument in the claim 7～14 is characterized in that, further contains weighting agent.
16, the described eradicating instrument of claim 15 is characterized in that weighting agent derives from biomass.
17, claim 15 or 16 described eradicating instruments is characterized in that, weighting agent is selected from shell powder, eggshell powder.
18, each described eradicating instrument in the claim 15～17 is characterized in that, with respect to total 100 weight parts of natural rubber and biomass plastics, weighting agent is 10～1000 weight parts.
19, a kind of eradicating instrument is characterized in that containing elastomerics and vinyl chloride resin, and described elastomerics is the elastomerics that is dispersed with crosslinked natural rubber particle in the matrix that comprises the biomass plastics island.
20, the described eradicating instrument of claim 19, it is characterized in that the biomass plastics are to be selected from least a in poly(lactic acid), polybutylene succinate, polymeric amide 11, poly--the 3-hydroxybutyric acid, rhodia, esterification starch, chitosan-Mierocrystalline cellulose starch, the starch-modified polyvinyl alcohol.
21, the described eradicating instrument of claim 19 is characterized in that, the biomass plastics are biological degradability biomass plastics.
22, each described eradicating instrument in the claim 19～21, it is characterized in that elastomerics is the biomass plastics of the natural rubber that contains 50～99 weight %, 50～1 weight % and is the elastomerics eradicating instrument composition of a rubber crosslinker of 0.1～5 weight part with respect to natural rubber 100 weight parts.
23, the described eradicating instrument of claim 22 is characterized in that, further contains tenderizer.
24, the described eradicating instrument of claim 23 is characterized in that tenderizer derives from biomass.
25, claim 23 or 24 described eradicating instruments is characterized in that, tenderizer is selected from vegetable and animals oils, derives from the softening agent of vegetable and animals oils.
26, each described eradicating instrument in the claim 23～25 is characterized in that, with respect to total 100 weight parts of natural rubber and biomass plastics, tenderizer is 1～200 weight part.
27, each described eradicating instrument in the claim 22～26 is characterized in that, further contains weighting agent.
28, the described eradicating instrument of claim 27 is characterized in that weighting agent derives from biomass.
29, claim 27 or 28 described eradicating instruments is characterized in that, weighting agent is selected from shell powder, eggshell powder.
30, each described eradicating instrument in the claim 27～29 is characterized in that, with respect to total 100 weight parts of natural rubber and biomass plastics, weighting agent is 10～1000 weight parts.
31, each described eradicating instrument in the claim 19～30 is characterized in that, vinyl chloride resin is the vinyl chloride resin eradicating instrument composition that contains vinyl chloride resin 100 weight parts, softening agent 60～180 weight parts.
32, the manufacture method of eradicating instrument is characterized in that, will comprise the eradicating instrument and the eradicating instrument melting mixing that comprises vinyl chloride resin eradicating instrument composition of elastomerics eradicating instrument composition, carries out moulding.
33, the manufacture method of the described eradicating instrument of claim 32, it is characterized in that, elastomerics eradicating instrument composition contain 50～99 weight % natural rubber, 50～1 weight % the biomass plastics and be a rubber crosslinker of 0.1～5 weight part with respect to natural rubber 100 weight parts.
34, the manufacture method of claim 32 or 33 described eradicating instruments is characterized in that, vinyl chloride resin eradicating instrument composition contains vinyl chloride resin 100 weight parts, softening agent 60～180 weight parts.
35, the manufacture method of each described eradicating instrument in the claim 32～34, it is characterized in that, the eradicating instrument that comprises elastomerics eradicating instrument composition is 30～90 weight %, and the eradicating instrument that comprises vinyl chloride resin eradicating instrument composition is 70～10 weight %.
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| JP2007016000 | 2007-01-26 | ||
| JP2007016000A JP4402698B2 (en) | 2007-01-26 | 2007-01-26 | Eraser elastomer composition, method for producing the same, and eraser using the composition |
| JP2007290488 | 2007-11-08 | ||
| JP2007309928 | 2007-11-30 |
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Cited By (4)
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| CN104292824A (en) * | 2014-09-30 | 2015-01-21 | 苏州博利迈新材料科技有限公司 | Polymer nano-modified nylon 11 composite material and preparation method thereof |
| CN104672807A (en) * | 2013-11-29 | 2015-06-03 | 中国科学院理化技术研究所 | Poly-butylene succinate/natural rubber composite degradable toughness material and preparation method thereof |
| CN106030023A (en) * | 2014-03-07 | 2016-10-12 | 株式会社吴羽 | Degradable rubber member for downhole tool, degradable seal member, degradable protective member, downhole tool, and well-drilling method |
| US10208559B2 (en) | 2013-12-27 | 2019-02-19 | Kureha Corporation | Diameter-expandable annular degradable seal member for downhole tool, plug for well drilling, and method for well drilling |
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| JP2008184543A (en) * | 2007-01-30 | 2008-08-14 | Tokai Rubber Ind Ltd | Manufacturing method for thermoplastic elastomer product and thermoplastic elastomer product obtained by it |
| WO2009060554A1 (en) * | 2007-11-08 | 2009-05-14 | Seed Company Ltd. | Elastomer composition, method for producing the same, and eraser using the composition |
| JP5606006B2 (en) * | 2009-04-08 | 2014-10-15 | 株式会社シード | Elastomer composition, process for producing the same, and eraser using the composition |
| JP2011074354A (en) * | 2009-09-03 | 2011-04-14 | Nishikawa Rubber Co Ltd | Resin composition |
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| JP3345630B2 (en) * | 1992-10-08 | 2002-11-18 | 独立行政法人産業技術総合研究所 | Biodegradable resin composition |
| JPH0812813A (en) * | 1994-07-04 | 1996-01-16 | Showa Kako Kk | Natural rubber composition |
| JPH0872493A (en) * | 1994-09-07 | 1996-03-19 | Rabitsuto Kk | Degradable eraser |
| JPH10274494A (en) * | 1997-03-31 | 1998-10-13 | Showa Rubber Kk | Sponge ball for cleaning heat exchanger |
| JP2999188B1 (en) * | 1998-11-25 | 2000-01-17 | 横浜ゴム株式会社 | Thermoplastic elastomer composition and pneumatic tire and hose using the same |
| JP4154994B2 (en) * | 2002-10-25 | 2008-09-24 | トヨタ自動車株式会社 | Polymer blend and process for producing the same |
| JP4781714B2 (en) * | 2005-05-18 | 2011-09-28 | 株式会社カネカ | Impact-resistant biodegradable composition and molded article thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104672807A (en) * | 2013-11-29 | 2015-06-03 | 中国科学院理化技术研究所 | Poly-butylene succinate/natural rubber composite degradable toughness material and preparation method thereof |
| US10208559B2 (en) | 2013-12-27 | 2019-02-19 | Kureha Corporation | Diameter-expandable annular degradable seal member for downhole tool, plug for well drilling, and method for well drilling |
| CN106030023A (en) * | 2014-03-07 | 2016-10-12 | 株式会社吴羽 | Degradable rubber member for downhole tool, degradable seal member, degradable protective member, downhole tool, and well-drilling method |
| US10280699B2 (en) | 2014-03-07 | 2019-05-07 | Kureha Corporation | Degradable rubber member for downhole tools, degradable seal member, degradable protecting member, downhole tool, and method for well drilling |
| CN106030023B (en) * | 2014-03-07 | 2019-07-30 | 株式会社吴羽 | Drilling tool decomposability rubber component, decomposability containment member, decomposability protection component, drilling tool and boring method |
| CN104292824A (en) * | 2014-09-30 | 2015-01-21 | 苏州博利迈新材料科技有限公司 | Polymer nano-modified nylon 11 composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008179742A (en) | 2008-08-07 |
| JP4402698B2 (en) | 2010-01-20 |
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