JP5606006B2 - Elastomer composition, process for producing the same, and eraser using the composition - Google Patents

Description

  The present invention relates to an elastomer composition, a method for producing the same, and an eraser using the composition. More specifically, the present invention can be recycled without depending on fossil resources, is friendly to the environment, and corresponds to a recycling society. The present invention relates to an elastomer composition, a method for producing the same, and an eraser using the composition.

Until now, industries and economies have been developed through the use of fossil resources such as oil and coal, and social systems for mass production, mass consumption and mass disposal have been established. It depends.
The current social system has created economic affluence and convenience, but on the other hand, it emits waste and carbon dioxide that exceed the natural purification capacity, aggravating environmental issues such as global warming and harmful substances. ing.

  In order to solve such problems, we have produced a large amount of products from finite resources so far, consumed and discarded a large amount of this, modified the one-way social system to reduce the generation of waste, There is a strong demand for a transition to a recycling society that effectively uses limited resources. To form this recycling-oriented society, the Cabinet decided on the “Biomass and Nippon Comprehensive Strategy” in December 2002 and is working to rebuild industrial competitiveness.

  Biomass is a continuously renewable organic resource that comes from the bounty of nature. Biomass emits carbon dioxide when combusted, but absorbs and fixes carbon dioxide in the atmosphere by photosynthesis during growth, and therefore has a feature that it does not substantially increase carbon dioxide. This is called “Carbon Neutral”, and by replacing energy and products derived from fossil resources with biomass, it is possible to significantly reduce carbon dioxide emissions. Therefore, there is a strong demand for technology and product development.

In recent years, many proposals have been made for polymer materials in consideration of the formation of a recycling society.
For example, a rubber production composition comprising natural rubber and biodegradable plastic (in the examples, vulcanizing agent and vulcanization accelerator are used) (Patent Document 1), biodegradable material and epoxidized polyisoprene, and necessary A biodegradable material composition obtained by further mixing a cross-linking agent (Patent Document 2), a biodegradable rubber composition obtained by adding a biodegradable resin and a filler to natural rubber (Patent Document 3), crystals A polylactic acid-based resin composition (patent document 4) composed of a basic polylactic acid and a rubber component selected from natural rubber and polyisoprene, and a dispersed phase composed of natural rubber or the like is uniformly fine in a continuous phase composed of polylactic acid. Examples thereof include a dispersed polymer blend material (Patent Document 5).

On the other hand, the eraser can be broadly divided into three types: PVC eraser made of vinyl chloride resin, non-PVC eraser made of styrene thermoplastic elastomer or olefin thermoplastic elastomer, and natural rubber eraser.
Of these, PVC eraser and non-PVC eraser account for over 90% of the eraser market, and the polymer materials, plasticizers, and softeners that make up these are all materials derived from fossil resources such as petroleum. Continuing to use erasure goes against the purpose of creating a recycling-based society.
On the other hand, natural rubber eraser uses biomass such as sub (factis) produced from natural rubber or vegetable oil, and is consistent with the purpose of forming a recycling society (Patent Document 6, Non-patent) Reference 1).

JP-A-10-274494 JP 2000-95898 A JP 2000-319446 A JP 2003-183488 A JP 2004-143315 A JP 2000-43492 A (see Examples 1 and 2) "Rubber Industry Handbook" (new edition) edited by Japan Rubber Association Table 25.2, pages 817, November 15, 1973 Issued by Rubber Association of Japan

  However, in the above-mentioned prior art, the rubber that is not vulcanized or crosslinked does not have sufficient tensile strength and elasticity, so its use may be limited. For example, rubber erasing material does not exhibit rubber elasticity. It is not appropriate. On the other hand, vulcanized or cross-linked ones are limited in application because they have too high tensile strength and elasticity. For example, they are not suitable because they become hard as a material for erasing and cannot provide rubber elasticity. Furthermore, the vulcanization and cross-linking steps are necessary, which not only complicates the manufacturing process, but also concerns the safety of vulcanizing agents such as sulfur as a vulcanizing agent, vulcanization accelerator, and zinc oxide as an auxiliary agent. I am confused.

  On the other hand, as described above, natural rubber eraser is suitable for the formation of a recycling-oriented society, but, for example, its eraser performance is inferior to that of PVC eraser, and it includes a vulcanization process. Compared with PVC eraser, the manufacturing process is complicated, and as described above, there are problems in the safety of vulcanizing agents such as sulfur and vulcanization accelerators. Furthermore, it is uneconomical because it is difficult to reuse the scrap generated in the manufacturing process, and there is a problem in productivity.

  In view of such circumstances, the present invention solves the above-mentioned problems of the prior art, and the biomass plastic, natural rubber, rubber cross-linking agent, and biomass-derived additive are not less than the melting temperature of the biomass plastic and the cross-linking temperature of the rubber cross-linking agent. By kneading under high shear and dispersing the cross-linked natural rubber particles into islands in a matrix made of biomass plastic and adding biomass-derived additives, tensile strength that cannot be obtained by conventional vulcanization or cross-linking The present invention provides an elastomer composition having physical properties such as elasticity, a production method thereof, and eraser using the composition.

The present invention has been made to achieve the above object, and claim 1 of the present invention is characterized in that crosslinked natural rubber particles are formed in a matrix made of biomass plastic selected from polylactic acid, polybutylene succinate and esterified starch. A biomass-derived filler selected from shell powder and eggshell powder , and a softener derived from biomass selected from animal and vegetable oils and plasticizers derived therefrom are contained , and natural rubber is 74 to 99% by weight. , Biomass plastic is 26 to 1% by weight, rubber cross-linking agent (excluding sulfur and zinc oxide) is 0.1 to 5 parts by weight with respect to 100 parts by weight of natural rubber, and biomass-derived filler is natural rubber and biomass plastic. 10 to 1000 parts by weight with respect to a total of 100 parts by weight, and the softener derived from biomass is natural rubber and biomass plastic And contents elastomeric composition characterized that you have been contained 1-200 parts by weight relative to 100 parts by weight in total.

Claim 2 of the present invention is a biomass plastic selected from polylactic acid, polybutylene succinate and esterified starch, natural rubber, rubber cross-linking agent (excluding sulfur and zinc oxide), shell powder and eggshell powder. A biomass-derived softening agent selected from the above fillers, animal and vegetable oils, and plasticizers derived therefrom is kneaded under high shear above the melting temperature of the biomass plastic and above the crosslinking temperature of the rubber crosslinking agent. The cross-linked natural rubber particles, which are natural rubber cross-linked with the rubber cross-linking agent, are dispersed in the matrix made of biomass plastic, and contain a biomass-derived filler and a biomass-derived softening agent . The manufacturing method of an elastomer composition is included.

Claim 3 of the present invention, the eraser characterized in that it consists of claims 1 elastomer composition according or claim 2 elastomer composition obtained by the process according to the contents.

The elastomer composition of the present invention does not rely on fossil resources, and the materials used as raw materials are natural rubber, biomass plastic, and biomass-derived fillers derived from biomass. It is an environmentally friendly elastomer composition without increasing carbon. Further, by using a biodegradable biomass plastic, it is decomposed in a natural environment, and a more environmentally adaptable elastomer composition is provided.

  In addition, since the elastomer composition of the present invention is a thermoplastic elastomer, the end material produced at the time of molding can be easily recycled. Therefore, the cost can be reduced and it can be adapted to a resource recycling society.

  Furthermore, since the method for producing an elastomer composition of the present invention simultaneously performs kneading of natural rubber and biomass plastic and crosslinking of natural rubber, the process is simplified and the productivity is high. In addition, since a vulcanizing agent such as sulfur or zinc oxide or a vulcanization accelerator is not used for crosslinking natural rubber, safety is high.

  The elastomer composition of the present invention is suitable, for example, as an erasing base material, unlike materials obtained by conventional vulcanization or crosslinking.

  The eraser made of the elastomer composition of the present invention is environmentally friendly, unlike conventional PVC erasers and non-PVC erasers that rely on fossil resources, and the scraps produced during molding are easily recycled, resulting in wasted materials. The cost is reduced because it decreases.

Further, the conventional natural rubber eraser requires a cross-linking step separately from the kneading step, whereas in the present invention, the cross-linking is performed simultaneously with the kneading, so the process is simplified and the productivity is high.
In addition, conventional natural rubber eraser uses vulcanizing agents and vulcanization accelerators such as sulfur and zinc oxide, whereas the eraser of the present invention does not use such chemicals and is therefore highly safe. .

Furthermore, erasers of the present invention, anti-shaped capacity is higher than the conventional non-PVC eraser.

The elastomer composition of the present invention has a sea-island structure in which crosslinked natural rubber particles are dispersed in islands in a matrix (sea) made of biomass plastic, and contain a biomass-derived filler and a biomass-derived softener. It is characterized by.

  The natural rubber used in the present invention is classified into sheet rubber, pale crepe, brown crepe, blanket crepe, block rubber, crumb rubber, etc., depending on the method of processing from latex to solid rubber, but there are various rating grades, but these are not limited. There are no restrictions on the production area. In addition, natural rubber derivatives such as epoxidized natural rubber can be used. These may be used alone or in combination of two or more as required.

Biomass plastics used in the present invention can be classified into chemical synthesis systems, microbial production systems, and natural product systems. Chemical synthesis systems include lactic acid obtained by fermenting saccharides and starch obtained from corn, potatoes, and sugarcane, and lactic acid obtained by polymerizing starch (for example, Lacia manufactured by Mitsui Chemicals), succinic acid produced from starch, Examples include polybutylene succinate using 4-butanediol as a raw material (for example, GS-Pla manufactured by Mitsubishi Chemical Corporation) and polyamide 11 using a castor oil as a raw material (for example, Rilsan B manufactured by Arkema). Examples of the microorganism production system include poly-3-hydroxybutyric acid (for example, Biogreen manufactured by Mitsubishi Gas Chemical Company), and a copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid (for example, PHBH manufactured by Kaneka Corporation). Examples of natural products include cellulose acetate (for example, Cell Green PCA manufactured by Daicel Chemical Industries), esterified starch (for example, Corn Paul manufactured by Nippon Corn Starch), chitosan / cellulose / starch (for example, Delon CC manufactured by Aicero Chemical), starch / modified. Examples include polyvinyl alcohol (for example, Mater-Bi manufactured by Novamont). These may be used alone or in combination of two or more as required.
By using a biodegradable material that is a renewable resource as the biomass plastic, it is possible to obtain a more environmentally adaptable elastomer composition.

  The composition ratio of natural rubber and biomass plastic may be appropriately determined depending on the intended use and physical properties of the elastomer composition. For example, as the eraser base material, natural rubber is 50 to 99% by weight, and biomass plastic is The range of 50 to 1% by weight is preferable, more preferably 70 to 95% by weight of natural rubber, and 30 to 5% by weight of biomass plastic. When the biomass plastic is less than 1% by weight, the fluidity of the elastomer composition is poor and a problem occurs in moldability. When the biomass plastic exceeds 50% by weight, the elastomer composition becomes hard and rubber elasticity does not appear. For example, when used as a erasing base material, there is a tendency that sufficient erasing performance is not exhibited.

  As the rubber cross-linking agent used in the present invention, an organic peroxide can be suitably used. Specifically, dicumyl peroxide (for example, Park Mill D manufactured by NOF Corporation), 2,5-dimethyl-2,5-di-t-butylperoxyhexane (for example, Perhexa 25B manufactured by NOF Corporation), di-t. -Butylperoxydiisopropylbenzene (for example, Perbutyl P manufactured by NOF Corporation), 2,5-dimethyl-2,5-di-t-butylperoxyhexine-3 (for example, Perxin 25B manufactured by NOF Corporation) and the like. . Other organic vulcanizing agents can also be used. Specifically, N, N′-m-phenylene dimaleimide (for example, Balnock PM manufactured by Ouchi Shinsei Chemical Co., Ltd.), p-quinone dioxime (for example, Barnock GM manufactured by Ouchi Shinsei Chemical Co., Ltd.), alkylphenol formaldehyde resin (for example, Taoka). And Tacchi roll 201) manufactured by Kagaku Corporation. These may be used alone or in combination of two or more as required.

  The rubber crosslinking agent is used in an amount of 0.1 to 5.0 parts by weight with respect to 100 parts by weight of natural rubber. If the rubber cross-linking agent is less than 0.1 parts by weight, the cross-linking is insufficient, and natural rubber does not become particles and the desired structure cannot be obtained. It tends to be too large and cause problems in formability.

  Various additives used in the fields of biomass plastic materials and natural rubber materials can be added to the elastomer composition of the present invention. Examples of such additives include ultraviolet absorbers, hindered amine light stabilizers, weather resistance improvers such as antioxidants, higher fatty acid alcohols, aliphatic amides, metal soaps, lubricants such as fatty acid esters, and the like.

  Other additives such as softeners, fillers, organic / inorganic pigments, coloring materials such as dyes, fragrances, stabilizers, antioxidants, ultraviolet absorbers, and fungicides are appropriately added to the elastomer composition of the present invention. It is also possible to use arbitrarily.

  As the softener, mineral oil, animal and vegetable oil, or a plasticizer derived therefrom can be used. Specific examples of the mineral oil include paraffinic process oil, naphthenic process oil, and aromatic process oil. Specific animal and vegetable oils include rapeseed oil, castor oil, cottonseed oil, linseed oil, soybean oil, sesame oil, corn oil, safflower oil, palm oil, coconut oil, peanut oil, wood wax, rosin, pine tar, tall oil, etc. . Examples of plasticizers derived from animal and vegetable oils include glycerin fatty acid esters, and specific examples include glycerin diacetate monolaurate, glycerin triacetate, and glycerol diacetate. These may be used alone or in combination of two or more as required. From the standpoint of providing a more environmentally adaptable elastomer composition, it is preferable to use a biomass-derived animal or vegetable oil or a plasticizer derived therefrom, which is a renewable resource.

  The amount of the softening agent added can be 1 to 200 parts by weight with respect to 100 parts by weight of the mixture of natural rubber and biomass plastic. The amount is preferably 10 to 150 parts by weight. If the amount of the softener is less than 1 part by weight, the amount of the softener added is not sufficient, while if it exceeds 200 parts by weight, bleeding may occur.

Fillers include heavy calcium carbonate, light calcium carbonate, silica, diatomaceous earth, magnesium oxide, titanium oxide, talc, sericite, quartz powder, montmorillonite, scallops, oysters, spotted shell powder, eggshell powder, organic hollow particles And inorganic hollow particles. These may be used alone or in combination of two or more as required. From the standpoint of providing a more environmentally adaptable elastomer composition, it is preferable to use shellfish powders such as scallops and oysters, oysters or eggshell powders that are generated in large quantities as waste.
The blending amount of the filler can be 10 to 1000 parts by weight with respect to 100 parts by weight of the mixture of natural rubber and biomass plastic. Preferably it is 50-500 weight part. If the amount is less than 10 parts by weight, the effect of adding the filler is not sufficient. On the other hand, if the amount exceeds 1000 parts by weight, the composition becomes hard and sufficient rubber elasticity does not appear. There is a tendency that the erasing performance is not demonstrated.

The elastomer composition of the present invention comprises a biomass plastic, natural rubber and a rubber cross-linking agent, and if necessary, a softener, a filler and the like in a kneading machine, which are above the melting temperature of the biomass plastic and above the cross-linking temperature of the rubber cross-linking agent. And kneading under high shear.
Examples of the kneading machine capable of kneading under high shear include a biaxial kneading extruder, a Banbury mixer, a pressure kneader, a mixing roll, and the like, and a biaxial kneading extruder is preferably used.
The temperature higher than the melting temperature of the biomass plastic is preferably 10 to 50 ° C. higher than the melting temperature of the biomass plastic, and the temperature higher than the crosslinking temperature of the rubber cross-linking agent is 5 to 20 ° C. higher than the cross-linking temperature of the rubber cross-linking agent. preferable.

The elastomer composition of the present invention has excellent elasticity and cushioning properties, and is useful in the fields of packaging cushioning materials, heat insulating materials, sound insulating materials, sound absorbing materials, tatami floors, flooring materials, wall materials, etc. It is useful as a substrate for erasing.
The reason why the elastomer composition of the present invention has such a unique physical property compared to the conventional vulcanized or cross-linked one is that the rubber component is cut by kneading under high shear. Conceivable.

  The eraser of the present invention using the elastomer composition is formed by press molding, injection molding, extrusion molding, or the like, and cut into a predetermined size to obtain a product.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, these do not restrict | limit the scope of the present invention at all.

  The materials used in the following examples and comparative examples are shown in Table 1.

Examples 1 to 10, Comparative Example 1
Of the materials shown in Table 2, natural rubber, softener, and filler were previously kneaded with a pressure kneader, and a rubber cross-linking agent was added using a roll to obtain a rubber kneaded product. The obtained rubber kneaded product was cut into pellets of about 5 mm square. Next, rubber kneaded pellets and biomass plastic pellets are shown in Table 2 using a twin-screw extruder KZW-15TW-60 (same direction complete meshing type, screw diameter 15 mm, L / D = 60) manufactured by Technobel. Each was supplied with a quantitative feeder so as to have a blending ratio, and kneaded at a screw rotation speed of 400 rpm to obtain an elastomer composition of the present invention. The cylinder temperature was set to 120 to 190 ° C. so that the kneading temperature was higher than the melting point (170 ° C.) of the biomass plastic and higher than the rubber crosslinking temperature (180 ° C.).

  The obtained elastomer composition pellets of the present invention were extruded into a square bar shape with a single screw extruder (cylinder temperature 90 to 110 ° C., head temperature 120 ° C.) and cut to produce the eraser of the present invention.

Hardness and erasure rate were evaluated as erasing characteristics.
The hardness was measured in accordance with “JIS S 6050 Plastic Eraser” using a C-type hardness meter (Type C hardness meter manufactured by Kobunshi Keiki).
The erasure rate was measured by the following method.
(1) A sample was cut into a plate having a thickness of 5 mm, and a test piece was prepared by finishing a contact portion with a test paper into an arc having a radius of 6 mm.
(2) The test piece is brought into contact with the colored paper perpendicularly and at right angles to the colored line, and the weight is placed on the test piece so that the sum of the weight of the weight and the holder is 0.5 kg. The colored part was brushed back and forth four times at a speed of 150 ± 10 cm / min.
(3) Using a densitometer (DENSITOMETER PDA65 made by Sakura), the density of the non-colored part of the colored paper was set to 0, and the density of the colored part and the erosion part was measured.
(4) The erasure rate was calculated by the following formula.
Erase rate (%) = (1− (density of wear part ÷ density of colored part)) × 100

Comparative Example 2
Using the materials shown in Table 3, a rubber kneaded product was obtained by kneading all the compounding materials into natural rubber using two rolls. The obtained rubber kneaded material was preformed according to the dimensions of a predetermined mold, and vulcanized and molded under conditions of 130 ° C. for 20 minutes using a hot press. The obtained rubber molding was cut into a predetermined size to obtain an eraser.

As described above, the elastomer composition of the present invention is mainly composed of biomass-derived biomass plastic and natural rubber, and further contains biomass-derived additives, so it does not depend on fossil resources and is discarded. However, it is an elastomer composition that does not increase carbon dioxide in the atmosphere, can be recycled, is environmentally friendly, and is compatible with a recycling society.
When the elastomer composition of the present invention is used as a base material for erasing, it can provide erasing with excellent erasing ability and safety.
Further, by using biodegradable biomass plastic as biomass plastic, it is possible to provide a more environmentally adaptable elastomer composition and eraser that are decomposed in a natural environment.

Claims (3)

Cross-linked natural rubber particles are dispersed in islands in a matrix made of biomass plastics selected from polylactic acid, polybutylene succinate, and esterified starch, and a biomass-derived filler and animal and vegetable oils selected from shell powder and eggshell powder. It contains a softener derived from biomass selected from plasticizers derived from , natural rubber is 74 to 99% by weight, biomass plastic is 26 to 1% by weight, rubber cross-linking agent (excluding sulfur and zinc oxide) is natural 0.1 to 5 parts by weight with respect to 100 parts by weight of rubber, 10 to 1000 parts by weight with respect to a total of 100 parts by weight of a biomass-derived filler and natural rubber and biomass plastic, and a softener derived from biomass with natural rubber It is characterized that you have been contained 1-200 parts by weight per 100 parts by weight of a biomass plastic Elastomer composition. Biomass plastic selected from polylactic acid, polybutylene succinate, esterified starch , natural rubber, rubber cross-linking agent (excluding sulfur and zinc oxide) , shell powder, biomass-derived filler selected from egg shell powder, animal and vegetable oil, and this In the matrix comprising the biomass plastic, characterized in that a biomass-derived softener selected from plasticizers derived from the above is kneaded under high shear above the melting temperature of the biomass plastic and above the crosslinking temperature of the rubber crosslinking agent. The method for producing an elastomer composition according to claim 1, wherein crosslinked natural rubber particles, which are natural rubber crosslinked with the rubber crosslinking agent, are dispersed and contain a biomass-derived filler and a biomass-derived softening agent . An erasure comprising the elastomer composition according to claim 1 or the elastomer composition obtained by the production method according to claim 2.