[0001] The present invention relates to an eraser made of an elastomer composition, which
can be recycled, is friendly to the environment, and corresponds to the recycling
society, without relying on fossil resources.
[0002] So far, industries and economies have been advanced using fossil resources such as
coal and petroleum oil and social systems based on mass production, mass consumption,
and mass disposal have been established and many daily necessities have been based
on the fossil resources whose depletion is now expected.
[0003] The present social systems have created economical affluence and convenience, but,
on the other hand, wastes and carbon dioxide exceeding the natural purification capabilities
have been discharged and it has resulted in serious environmental issues such as global
warming and harmful substance generation.
[0004] In order to solve such problems, it is urgently required to reform today's one-way
type social systems, in which a large quantity of commodities are produced from limited
resources, consumed and disposed, and to shift the social systems to the recycling
society, in which discharge of wastes can be suppressed and the limited resources
can be advantageously utilized. To establish this recycling society, in our country,
"Biomass Nippon Strategy" was decided upon by the Japanese government at a cabinet
meeting held in December, 2002 and Japan has now been challenging reconstruction of
the industrial competitive strength.
[0005] Biomass is sustainable and regenerable organic resources brought forth by natural
blessings. Although biomass emits carbon dioxide when burned, carbon dioxide in atmospheric
air is absorbed and fixed by photosynthesis at the time of plant growth and therefore
biomass has a characteristic that it does not practically increase carbon dioxide.
This is called "carbon neutral" and replacement of energy and commodities derived
from fossil resources with biomass makes it possible to considerably lessen the carbon
dioxide emission and accordingly, the techniques and product developments therefor
have been acutely required.
[0006] In recent years, with respect to polymer materials as well, a plenty of proposals
have been made in consideration of establishment of recycling society.
[0007] For instance, Japanese Patent Application Laid-Open (JP-A) No.
10-274494 describes a composition for rubber production containing natural rubber and biodegradable
plastics (in Examples, a vulcanizing agent and a vulcanization accelerator are used).
JP-A No. 2000-95898 describes a biodegradable material composition obtained by mixing a biodegradable
material, epoxylated polyisoprene, and if necessary a crosslinking agent.
JP-A No. 2000-319446 describes a biodegradable rubber composition obtained by adding a biodegradable resin
and a filler to natural rubber. Further,
JP-A No. 2003-183488 describes a polylactic acid type resin composition containing crystalline polylactic
acid, and a rubber component selected from natural rubber and polyisoprene, and
JP-A No. 2004-143315 describes a polymer blended material containing a continuous phase of polylactic
acid and a dispersion phase of natural rubber or the like, evenly and finely dispersed
in the continuous phase.
[0008] On the other hand, erasers can be broadly classified into three types: a vinyl chloride
type eraser made of a vinyl chloride resin; a non-vinyl chloride type eraser made
of a styrene type thermoplastic elastomer or an olefin type thermoplastic elastomer;
and a natural rubber eraser.
[0009] Among them, more than 90 % of erasers in an eraser market are a vinyl chloride type
eraser and a non-vinyl chloride type eraser. The polymer material, a plasticizer,
and a softening agent composing the erasers are all materials derived from fossil
resources such as petroleum oil and continuous use of these erasers is contradictory
to the theme of the recycling society establishment.
[0010] On the other hand, for instance, as described in
JP-A No. 2000-43492 and
Gomu Kogyo Binran (Rubber Industry Handbook) (new edition, edited by The Society of
Rubber Industry, Japan, published by The Society of Rubber Industry, Japan, Nov. 15,
1973, p. 817, Table 25.2), natural rubber erasers utilize biomass such as subs (factices) produced from natural
rubber and plant oils and is in accord with the theme of the recycling society establishment.
[0011] US 3,790,511 discloses a gum eraser composed of a base rubber material and vulcanized rubber powder
particles uniformly dispersed therein.
US 4, 393, 022 describes an eraser based on PVC.
[0012] However, in the above-mentioned conventional techniques, those obtained without vulcanizing
or crosslinking rubber are insufficient in tensile strength or elasticity and therefore
applications thereof are sometimes limited and, for instance, they are inadequate
as materials for erasers since they do not exhibit rubber elasticity. On the other
hand, those which are vulcanized or crosslinked are also sometimes limited in applications
because of excess tensile strength and elasticity and for instance, they become too
hard as materials for erasers to give rubber elasticity and therefore inadequate.
Further, since a vulcanizing or crosslinking step is necessary, the production process
not only becomes complicated but also contains critical issue of safety of sulfur
as a vulcanization agent and vulcanization chemical agents such as a vulcanization
accelerator and an aid such as zinc oxide.
[0013] On the other hand, as described above, although the natural rubber erasers are suitable
for satisfying the need for recycling society establishment, the natural rubber erasers
are inferior in the erasing capability as compared with the vinyl chloride type erasers
and since their production process includes a vulcanization step, the production process
is complicated as compared with that for the vinyl chloride type erasers or non-vinyl
chloride type erasers. Further, as described above, there is an issue of safety of
sulfur and vulcanization chemical agents such as a vulcanization accelerator. Moreover,
reuse of wastes generated in the production process is difficult, so that it could
result in uneconomical consequence and a problem in terms of productivity.
[0014] In view of the above state of the art, it is an object of the present invention to
solve the above-mentioned problems of the conventional techniques and to provide an
eraser made of an elastomer composition provided with physical properties such as
tensile strength and elasticity, which have never been obtained by conventional vulcanization
or crosslinking, containing a matrix of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate)
(hereinafter referred to as PHBH) and crosslinked natural rubber particles dispersed
like islands in the matrix.
[0015] The present invention has accomplished the above-mentioned object and a first aspect
of the present invention is
[0016] an eraser made of an elastomer composition containing a matrix of PHBH and crosslinked
natural rubber particles dispersed like islands in the matrix.
[0017] A second aspect of the present invention is the eraser of the first aspect, in which
the molar ratio of the repeating units of the PHBH, poly (3-hydroxybutyrate) / poly
(3-hydroxyhexanoate) is not less than 80/20 and not more than 99/1 (mol/mol).
[0018] A third aspect of the present invention is the eraser of the first or second aspect,
in which the elastomer composition is an eraser composition containing 50 to 99% by
weight of natural rubber, 50 to 1% by weight of the PHBH, and 0.1 to 5 parts by weight
of a rubber crosslinking agent to 100 parts by weight of the natural rubber.
[0019] A fourth aspect of the present invention is the eraser of any one of the first to
third aspects, which further contains a softening agent.
[0020] A fifth aspect of the present invention is the eraser of the fourth aspect, in which
the softening agent is derived from biomass.
[0021] A sixth aspect of the present invention is the eraser of the fourth or fifth aspect,
in which the softening agent is selected from animal and plant oils and a plasticizer
derived from these oils.
[0022] A seventh aspect of the present invention is the eraser of any one of the fourth
to sixth aspects, in which an amount of the softening agent is 1 to 200 parts by weight
to 100 parts by weight of the total of the natural rubber and the PHBH.
[0023] An eighth aspect of the present invention is the eraser of any one of the first to
seventh aspects, which further contains a filler.
[0024] A ninth aspect of the present invention is the eraser of the eighth aspect, in which
the filler is derived from biomass.
[0025] A tenth aspect of the present invention is the eraser of the eighth or ninth aspect,
in which the filler is selected from a shell powder and an eggshell powder.
[0026] An eleventh aspect of the present invention is the eraser of any one of the eighth
to tenth aspects, in which the amount of the filler is 10 to 1000 parts by weight
to 100 parts by weight of the total of the natural rubber and the PHBH.
[0027] With respect to the elastomer compositions used for the eraser of the present invention,
the materials to be used as raw materials not relying on the fossil resources are
all natural rubber and PHBH which is a biodegradable polyester type plastic derived
from biomass and accordingly, even if they are disposed, carbon dioxide in the atmospheric
air is not increased and thus they are environmentally adequate elastomer compositions
which are decomposed in natural environments.
[0028] Further, since the elastomer compositions used in the present invention are thermoplastic
elastomers, the refuse generated at the time of molding can be easily recycled and
accordingly, it leads to cost down and is thus adequate to the resource recycling
society.
[0029] Further, in the elastomer composition production methods used in the present invention,
since kneading of natural rubber and the PHBH and crosslinking of the natural rubber
are simultaneously carried out, the process can be simplified and the productivity
is high. Further, vulcanization agents and vulcanization accelerators such as sulfur
and zinc oxide are not used for crosslinking the natural rubber, the safety is also
high.
[0030] The elastomer compositions used in the present invention differ from materials obtained
by the conventional vulcanization or crosslinking and are therefore suitable, for
instance, for base materials of erasers.
[0031] The erasers of the present invention are friendly to the environment, being different
from the conventional vinyl chloride erasers and non-vinyl chloride erasers which
rely on fossil resources and the refuse generated at the time of molding is easily
recycled and vain loss of materials is suppressed to result in cost down.
[0032] Further, with respect to the conventional natural rubber erasers, a crosslinking
step is required in addition to a kneading step whereas kneading and crosslinking
are carried out simultaneously in the present invention and the steps are simplified
to increase the productivity.
[0033] Further, with respect to the conventional natural rubber erasers, vulcanization agents
and vulcanization accelerators such as sulfur and zinc oxide are used whereas such
chemical agents are not used for the erasers of the present invention and therefore
the safety is high.
[0034] Moreover, the erasers of the present invention are provided with high erasing capability
as compared with the conventional natural rubber erasers and non-vinyl chloride erasers.
[0035] Furthermore, the erasers made of the elastomer compositions containing the PHBH of
the present invention are provided with higher erasing capability as compared with
the erasers made of the elastomer compositions containing, for example, polylactic
acid as a biodegradable plastic. This is presumably attributable to a melting point
of 100 to 160°C of the PHBH which is lower than that of 170 to 180°C of the polylactic
acid.
[0036] With respect to the erasing mechanism by an eraser, an eraser is closely contacted
with letters written on a paper and rubbed against the letters. As a result, the letters
are not only adsorbed on the eraser, but the surface of the eraser adsorbing letters
is separated off from the eraser as erased scraps to renew the surface so as to be
able to adsorb the letters again. Accordingly, it is considered that the erasing capability
is greatly affected by proper abrasive performance caused by light stress such as
human hands' force. The elastomer compositions used in the present invention comprise
a discontinuous phase of rubber particles and a continuous phase of the PHBH and thus
the abrasive performance is considered to be greatly influenced by physical properties
of the continuous phase. In order to effect abrasion by light stress, the strength
of the continuous phase should preferably be small. It is surmised that since the
PHBH is lower in melting point than the polylactic acid, its strength is liable to
decrease by the friction heat at the time of using an eraser, so that more suitable
abrasive performance as an eraser can be provided.
[0037] The elastomer compositions used for the erasers of the present invention are characterized
in that the compositions have a sea-island structure in which a matrix (sea) of the
PHBH, crosslinked natural rubber particles are dispersed like islands in the matrix
of the PHBH.
[0038] The natural rubber to be used in the present invention can be classified into sheet
rubber, pale crepe, brown crepe, blanket crepe, block rubber, and crumb rubber, according
to a method for processing the rubber from latex into solid type rubber, and various
ranking grades are made available, and any natural rubber may be used regardless of
production areas. Further, natural rubber derivatives, for example, epoxylated natural
rubber, may also be used. They may be used alone or if necessary, two or more types
may be used in combination.
[0039] The PHBH used in the present invention is, as described in
JP-A No.2007-77232, produced from microorganisms and the molar ratio of the repeating units, i.e. poly
(3-hydroxybutyrate) / poly (3-hydroxyhexanoate) is preferably not less than 80/20
and not more than 99/1 (mol/mol) from a viewpoint of the balance of flexibility and
strength. By changing the composition ratio of the repeating unit, it is possible
to change a melting point and a degree of crystallinity and further to change physical
properties such as Young's modulus and heat resistance so that the physical properties
ranging from polypropylene to polyethylene can be imparted.
[0040] The composition ratio of the natural rubber and the PHBH may be properly determined
in accordance with applications and physical properties of the intended elastomer
compositions, however, for base materials of erasers, the natural rubber is preferably
in a range of 50 to 99% by weight and the PHBH in a range of 50 to 1% by weight; the
natural rubber is more preferably in a range of 70 to 95% by weight and the PHBH in
a range of 30 to 5% by weight. If the PHBH is less than 1% by weight, the fluidity
of the elastomer compositions is worsened to cause a problem of moldability. If the
PHBH exceeds 50% by weight, the elastomer compositions become too hard to exhibit
rubber elasticity, and for instance, in the case of using them as base materials for
erasers, it tends to become difficult to obtain a sufficient erasing capability.
[0041] The rubber crosslinking agents to be used preferably in the present invention may
be organic peroxides. Practical examples are dicumyl peroxide (e.g. PERCUMYL® D, manufactured
by NOF Corporation), 2,5-dimethyl-2,5-di-tert-butyl peroxyhexane (e.g. PERHEXA 25B,
manufactured by NOF Corporation), di-tert-butylperoxydiisopropylbenzene (e.g. PERBUTYL
P, manufactured by NOF Corporation), and 2,5-dimethyl-2,5-di-tert-butylperoxyhexyne-3
(e.g. PERHEXYNE® 25 B, manufactured by NOF Corporation). Additionally, other organic
vulcanization agents may also be used. Practical examples are N,N'-m-phenylene dimaleimide
(e.g. VULNOC PM, manufactured by Ouchi Shinko Chemical Industrial Co., Ltd.), p-quinonedioxime
(e.g. VULNOC GM, manufactured by Ouchi Shinko Chemical Industrial Co., Ltd.), and
alkylphenol-formaldehyde resin (e.g. TACKROL® 201, manufactured by Taoka Chemical
Co., Ltd.). They may be used alone or if necessary, two or more kinds of them may
be used in combination.
[0042] The rubber crosslinking agents may be used in an amount of 0.1 to 5.0 parts by weight
to 100 parts by weight of natural rubber. If the amount of the rubber crosslinking
agents is less than 0.1 part by weight, the crosslinking becomes insufficient and
the natural rubber does not become particles, and therefore, it becomes impossible
to obtain an intended structure and on the other hand, if the amount exceeds 5.0 parts
by weight, the impact resilience of the crosslinked rubber particles tends to become
so high to cause a problem of moldability.
[0043] The elastomer compositions used in the present invention may contain various kinds
of additives to be used in fields of biodegradable plastic materials and natural rubber
materials. Examples of such additives are ultraviolet absorbents, hindered amine type
photo-stabilizers, weathering resistance improvers such as antioxidants, and lubricants
of such as higher fatty acid alcohols, aliphatic amides, metal soaps, and fatty acid
esters.
[0044] In the case where the elastomer compositions are used as base materials for erasers,
other additives such as a softening agent, a filler, an organic or inorganic pigment,
a coloring material such as dyes, a fragrance, a stabilizer, an antioxidant, a UV
absorbent, and an anti-mold agent may be arbitrarily added to give elastomer eraser
compositions.
[0045] Examples of the softening agent may be mineral oils, animal and plant oils, and plasticizers
derived from them.
[0046] Practical examples of the mineral oils are paraffin type process oil, naphthene type
process oil, and aromatic type process oil. Practical examples of the animal and plant
oils are rapeseed oil, castor oil, cotton seed oil, linseed oil, soy oil, sesame oil,
corn oil, safflower oil, palm oil, coconut oil, peanut oil, Japan tallow, rosin, pine
tar, and tall oil. Plasticizers derived from animal and plant oils may include glycerin
fatty acid esters and practical examples may be glycerin diacetomonolaurate, glycerin
triacetate, and glycerol diacetate. They may be used alone or if necessary two or
more of them may be used in combination. In terms of availability of elastomer compositions
with further improved environmental friendliness, animal and plant oils derived from
biomass, which are regenerable resources, or plasticizers derived from them are more
preferable to be used.
[0047] The addition amount of the softening agent is 1 to 200 parts by weight to 100 parts
by weight of a mixture of the natural rubber and the PHBH. It is preferably 10 to
150 parts by weight. If the softening agent is less than 1 part by weight, the addition
amount of the softening agent is insufficient and on the other hand, if it exceeds
200 parts by weight, it may possibly result in occurrence of bleeding.
[0048] Examples of the fillers may be heavy calcium carbonate, light calcium carbonate,
silica, diatomaceous earth, magnesium oxide, titanium oxide, talc, sericite, quartz
powder, montmorillonite, shell powder of scallop, oyster, and freshwater clam, eggshell
powder, organic hollow particles, and inorganic hollow particles. They may be used
alone or if necessary, two or more of them may be used in combination. In terms of
availability of elastomer compositions with further improved environmental friendliness,
shell powders of scallop and oyster and eggshell powder derived from biomass, which
are generated in a large quantity as wastes, are more preferable to be used.
[0049] The addition amount of the filler is 10 to 1000 parts by weight to 100 parts by weight
of a mixture of the natural rubber and the PHBH. It is preferably 50 to 500 parts
by weight. If the filler is less than 10 parts by weight, the addition amount of the
filler is insufficient and on the other hand, if it exceeds 1000 parts by weight,
the composition may possibly become hard and no sufficient rubber elasticity can be
exhibited, and in the case of using the composition as a base material for an eraser,
it tends to become difficult to obtain sufficient erasing capability.
[0050] The elastomer compositions used in the present invention can be obtained by putting
the PHBH, natural rubber, a rubber crosslinking agent, and if necessary, a softening
agent, and a filler in a kneader and kneading them at a temperature not lower than
the melting temperature of the PHBH and not lower than the crosslinking temperature
of the rubber crosslinking agent.
[0051] The kneading is preferable to be carried out under high shearing condition. Examples
of such a kneader as enabling kneading under high shearing condition may be a biaxial
kneading extruder, a Bambury mixer, a pressurizing kneader, and a mixing roll and
among them is preferably the biaxial kneading extruder.
[0052] The word "a temperature not lower than the melting temperature of the PHBH" preferably
means a temperature higher than the melting temperature of the PHBH by 10 to 50°C
and the word "a temperature not lower than the crosslinking temperature of the rubber
crosslinking agent" preferably means a temperature higher than the crosslinking temperature
of the rubber crosslinking agent by 5 to 20°C.
[0053] The elastomer compositions used in the present invention have excellent elasticity
and cushioning property and are thus useful for cushioning materials for wrapping,
heat insulators, sound insulators, sound absorbing materials, tatami mat beds, floor
materials and wall materials and particularly useful for base materials for erasers.
[0054] A reason for that the elastomer compositions used in the present invention has such
unique physical properties as compared with conventionally vulcanized or crosslinked
compositions is supposedly attributed to that the rubber component is cut in the course
of kneading.
[0055] The erasers of the present invention using the above-mentioned elastomer eraser compositions
are obtained by molding the elastomer eraser compositions by press molding, injection
molding, and extrusion molding or the like, and cutting molded products into prescribed
sizes to give erasers of elastomers.
[0056] Hereinafter, the present invention will be explained in more detail with reference
to Examples and Comparative Examples, however it is not intended that the present
invention be limited to them.
[0057] Materials employed in the following Examples and Comparative Examples are shown in
Table 1.
Table 1
| Product name |
Material name |
Maker |
| RSS#1 |
natural rubber |
Produced in Indonesia |
| PHBH |
poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (melting temp.: 120°C) |
Kaneka Corporation |
| LACEA®H-100 |
polylactic acid (melting temp.: 164°C) |
Mitsui Chemicals, Inc. |
| RIKEMAL PL-004 |
glycerin diacetomonolaurate |
Riken Vitamin Co., Ltd. |
| SS#80 |
heavy calcium carbonate |
Nitto Funka Kogyo K.K. |
| Scallop shell powder |
scallop shell crushed powder |
Nitto Funka Kogyo K.K. |
| UNICA |
light calcium carbonate |
KOMESHO SEKKAI KOGYO CO., LTD. |
| MULTI Z |
composite chinese white |
KOMESHO SEKKAI KOGYO CO., LTD. |
| PERHEXA®C-40 |
40% diluted product of 1,1-di (t-butylperoxy) cyclohexane (crosslinking temp.: 120∼150°C) |
NOF Corporation |
| PERCUMYL® D-40 |
40% diluted product of dicumyl peroxide (crosslinking temp.: 150∼180°C) |
NOF Corporation |
| ADEKASTAB LA-32 |
benzotriazole type ultraviolet absorbent |
ADEKA CORPORATION |
| ADEKASTAB LA-77G |
hindered amine type photo-stabilizer |
ADEKA CORPORATION |
| White Sub No. 1 |
sulfur chloride factice |
Tenma Factice Manufacturing Co., Ltd. |
| DIANA PROCESS OIL NP-24 |
naphthenic type process oil |
Idemitsu Kosan Co., Ltd. |
| Sulfax 200S |
sulfur powder |
Tsurumi Chemical Industry Co., Ltd. |
| NOCCELER TT |
thiuram type vulcanization accelerator |
Ouchi Shinko Chemical Industrial Co., Ltd. |
| NOCCELER DM |
thiazole type vulcanization accelerator |
Ouchi Shinko Chemical Industrial Co., Ltd. |
| N OCCELER BG |
guanidine type vulcanization accelerator |
Ouchi Shinko Chemical Industrial Co., Ltd. |
| Zinc oxide |
zinc oxide |
Sakai Chemical Industry Co., Ltd. |
Examples 1 to 11
[0058] The natural rubber, softening agents, fillers and photo-stabilizers among the materials
shown in Table 2 were previously kneaded by a pressurizing kneader and the rubber
crosslinking agents were added using rolls to obtain kneaded rubber materials. The
obtained kneaded rubber materials were cut into pellets with about 5 mm square. Next,
using a biaxial extruder KZW-15TW-60 (completely intermeshed type in same directions,
screw diameter 15 mm, L/D = 60) manufactured by Technovel Corporation, the kneaded
rubber pellets and biodegradable plastic pellets were supplied at the mixing ratio
as shown in Table 2 by respective quantitative supplying units and kneaded at a screw
rotation speed of 400 rpm and at a cylinder temperature in a range of 110 to 155°C.
[0059] The obtained composition pellets were extrusion-molded into a square rod-like shape
by a uniaxial extruder (cylinder temperature 100 to 120°C, and head temperature 130°C)
and cut into elastomer erasers to obtain erasers having a size of 12 × 18 × 43mm.
[0060] As the properties of the erasers were evaluated hardness and erasing capability (erasing
ratio). The results are shown in Table 2.
[0061] The hardness was measured using C type hardness meter (Type C hardness meter, manufactured
by Kobunshi Keiki Co., Ltd.) according to JIS S 6050 Plastic Erasers.
[0062] The erasing ratio was measured by the following method.
- (1) A test specimen was obtained by cutting each sample into a 5 mm-thick plate-like
piece and finishing the part to be brought into contact with testing paper to be an
arc shape with a radius of 6 mm.
- (2) The test specimen was brought into contact with colored paper perpendicularly
and at right angles to colored lines and while a weight to be 0.5 kg in total of the
weight and the weight of a holder was put on the test specimen, the test specimen
was reciprocated 4 times on the colored part at 150 ± 10 cm/min for erasing the colored
part.
- (3) The densities of the colored part and the erased part were measured by a densitometer
(DENSITOMETER PDA 65, manufactured by Sakura Co.) on the basis of the density, which
was set 0, of non-colored parts of the colored paper.
- (4) The erasing ratio was calculated according to the following equation.

Table 2
| Composition |
Ex.1 |
Ex.2 |
Ex.3 |
Ex.4 |
Ex.5 |
Ex.6 |
Ex.7 |
Ex.8 |
Ex.9 |
Ex. 10 |
Ex. 11 |
| 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 |
| Softening agent |
RIKEMAL PL-004 |
70 |
70 |
70 |
70 |
70 |
70 |
70 |
80 |
70 |
70 |
70 |
| Filler |
SS#80 |
200 |
200 |
200 |
|
|
200 |
200 |
200 |
200 |
150 |
100 |
| SS#30 |
|
|
|
|
|
|
|
|
|
50 |
100 |
| Scallop shell powder |
|
|
|
200 |
200 |
|
|
|
|
|
|
| UNICA |
|
|
|
|
|
10 |
|
|
10 |
10 |
10 |
| MULTI Z |
|
|
|
|
|
|
10 |
|
|
|
|
| Rubber agent |
crosslinking PERHEXA C-40 |
1.0 |
1.5 |
2.0 |
2.0 |
2.0 |
2.0 |
2.0 |
1.5 |
2.0 |
2.0 |
2.0 |
| photo-stabilizer |
ADEKASTAB LA-32 |
|
|
|
|
|
|
|
|
1.0 |
1.0 |
1.0 |
| ADEKASTAB LA-77G |
|
|
|
|
|
|
|
|
1.0 |
|
|
| Natural rubber: biodegradable plastic ratio |
69:31 |
69:31 |
69:31 |
74:26 |
69:31 |
69:31 |
69:31 |
69:31 |
69:31 |
69:31 |
69: 31 |
| Properties |
Hardness (Ctype) |
79 |
82 |
84 |
78 |
85 |
84 |
85 |
81. |
84 |
84 |
83 |
| Erasing ratio (%) |
94 |
94 |
94 |
93 |
94 |
95 |
95 |
94 |
95 |
95 |
95 |
Comparative Example 1
[0063] An eraser was obtained in the same manner as in Example 7, except that the PHBH was
replaced with polylactic acid (LACE® H-100, trade name of Mitsui Chemicals, Inc.)
and the properties were evaluated.
However, in order to correspond to the melting temperature (160 to 170°C) of polylactic
acid, the rubber crosslinking agent was changed to PERCUMYL® D-40 and the cylinder
temperature was set at a range of 125 to 190°C. The results are shown in Table 3.
Table 3
| Composition |
Comp. Ex. 1 |
| Natural rubber |
RSS#1 |
100 |
| Biomass plastic |
LACEA ® H-100 |
45 |
| Softening agent |
PIKEMAL L-004 |
70 |
| Filler |
SS#80 |
200 |
| SS#30 |
|
| Scallop shell powder |
|
| UNICA |
|
| MULTI Z |
10 |
| Rubber crosslinking agent |
PERCUMYL® D-40 |
2.0 |
| photo-stabilizer |
ADEKASTAB LA-32 |
|
| ADEKASTAB LA―77G |
|
| Natural rubber: biomass plastic ratio |
69:31 |
| Properties |
Hardness (Ctype) |
91 |
| Erasing ratio (%) |
88 |
Comparative Example 2
[0064] Using the materials shown in Table 4, all of the addition materials were kneaded
with natural rubber using two rolls to obtain a kneaded rubber material. The obtained
kneaded rubber material was previously molded corresponding to the prescribed size
of a metal mold and vulcanized and molded using a heat press at 130°C for 20 minutes.
The obtained molded rubber product was cut into prescribed size to obtain a natural
rubber eraser and the properties of the obtained eraser were evaluated. The results
are shown in Table 4.
Table 4
| Composition |
Comp. Ex. 2 |
| Natural rubber |
RSS#1 |
100 |
| Substitute |
White sub No.1 |
300 |
| Filler |
SS#80 |
400 |
| Softening agent |
DIANA PROCESS OIL NP-24 |
150 |
| Vulcanization agent |
Sulfax 200S |
4 |
| Vulcanization accelerator |
NOCCELER TT |
1 |
| NOCCELER DM |
0.5 |
| NOCCELER BG |
0.5 |
| Vulcanization aid |
zinc oxide |
5 |
| Properties |
Hardness (C type) |
60 |
| Erasing ratio (%) |
90 |
[0065] As described above, since the elastomer composition used in the present invention
comprises a biodegradable PHBH and natural rubber as main components, it is an elastomer
composition which does not depend on fossil resources and is recycled without increasing
carbon dioxide in the atmospheric air even if being discarded and thus it is friendly
to the environment and responds to recycling societies. By using the elastomer composition
as a base material for an eraser according to the present invention, it is possible
to provide an eraser not only excellent in erasing capability and safety, but friendly
to environments since it can be decomposed in natural environments.
1. Eine Löschvorrichtung, hergestellt aus einer Elastomerzusammensetzung, enthaltend
eine Matrix aus Poly (3-hydroxybutyrat-co-3-hydroxyhexanoat) (nachstehend als PHBH
bezeichnet), hergestellt aus Mikroorganismen, und vernetzte Naturkautschukteilchen,
die wie Inseln in der Matrix dispergiert sind.
2. Die Löschvorrichtung nach Anspruch 1, wobei das Molverhältnis der Wiederholungseinheiten
des PHBH, Poly (3-hydroxybutyrat)/Poly (3-hydroxyhexanoat) nicht weniger als 80/20
und nicht mehr als 99/1 (Mol/Mol) beträgt.
3. Die Löschvorrichtung nach Anspruch 1 oder 2, wobei die Elastomerzusammensetzung eine
Löschvorrichtungszusammensetzung ist, die 50 bis 99 Gew.-% Naturkautschuk, 50 bis
1 Gew.-% des PHBHs und 0,1 bis 5 Gewichtsteile eines Kautschukvernetzungsmittels,
auf 100 Gewichtsteile des Naturkautschuks, enthält.
4. Die Löschvorrichtung nach einem der Ansprüche 1 bis 3, wobei ferner ein Erweichungsmittel
enthalten ist.
5. Die Löschvorrichtung nach Anspruch 4, wobei das Erweichungsmittel von Biomasse abstammt.
6. Die Löschvorrichtung nach Anspruch 4 oder 5, wobei das Erweichungsmittel ausgewählt
ist aus Tier- und Pflanzenölen und einem Weichmacher, der von diesen Ölen abstammt.
7. Die Löschvorrichtung nach einem der Ansprüche 4 bis 6, wobei die Menge des Erweichungsmittels
1 bis 200 Gewichtsteile, auf 100 Gewichtsteile der Gesamtmenge an Naturkautschuk und
PHBH, beträgt.
8. Die Löschvorrichtung nach einem der Ansprüche 1 bis 7, wobei ferner ein Füllstoff
enthalten ist.
9. Die Löschvorrichtung nach Anspruch 8, wobei der Füllstoff von Biomasse abstammt.
10. Die Löschvorrichtung nach Anspruch 8 oder 9, wobei der Füllstoff ausgewählt ist aus
einem Muschelpulver und einem Eierschalenpulver.
11. Die Löschvorrichtung nach einem der Ansprüche 8 bis 10, wobei die Menge des Füllstoffs
10 bis 1000 Gewichtsteile, auf 100 Gewichtsteile der Gesamtmenge an Naturkautschuk
und PHBH, beträgt.
1. Gomme à effacer faite d'une composition élastomère contenant une matrice de poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)
(désigné par PHBH ci-après) produit à partir de microorganismes et des particules
de caoutchouc naturel réticulé dispersées comme des îlots dans la matrice.
2. Gomme à effacer selon la revendication 1, dans laquelle le rapport molaire des unités
répétitives du PHBH, poly(3-hydroxybutyrate)/poly(3-hydroxyhexanoate) n'est pas inférieur
à 80/20 et pas supérieur à 99/1 (mol/mol).
3. Gomme à effacer selon la revendication 1 ou 2, dans laquelle la composition élastomère
est une composition de gomme à effacer contenant 50 à 99% en poids de caoutchouc naturel,
50 à 1% en poids du PHBH, et 0,1 à 5 parties en poids d'un agent de réticulation du
caoutchouc pour 100 parties en poids du caoutchouc naturel.
4. Gomme à effacer selon l'une quelconque des revendications 1 à 3, contenant en outre
un agent adoucissant.
5. Gomme à effacer selon la revendication 4, dans laquelle l'agent adoucissant est dérivé
de la biomasse.
6. Gomme à effacer selon la revendication 4 ou 5, dans laquelle l'agent adoucissant est
choisi parmi les huiles animales et de plantes et un plastifiant dérivé de ces huiles.
7. Gomme à effacer selon l'une quelconque des revendications 4 à 6, dans laquelle la
quantité d'agent adoucissant est de 1 à 200 parties en poids pour 100 parties en poids
du total du caoutchouc naturel et du PHBH.
8. Gomme à effacer selon l'une quelconque des revendications 1 à 7, contenant en outre
une charge.
9. Gomme à effacer selon la revendication 8, dans laquelle la charge est dérivée de la
biomasse.
10. Gomme à effacer selon la revendication 8 ou 9, dans laquelle la charge est choisie
parmi une poudre de coquillage et une poudre de coquille d'oeuf.
11. Gomme à effacer selon l'une quelconque des revendications 8 à 10, dans laquelle la
quantité de charge est de 10 à 1000 parties en poids pour 100 parties en poids du
total du caoutchouc naturel et du PHBH.