WO2018190377A1 - 消し具 - Google Patents
消し具 Download PDFInfo
- Publication number
- WO2018190377A1 WO2018190377A1 PCT/JP2018/015252 JP2018015252W WO2018190377A1 WO 2018190377 A1 WO2018190377 A1 WO 2018190377A1 JP 2018015252 W JP2018015252 W JP 2018015252W WO 2018190377 A1 WO2018190377 A1 WO 2018190377A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- eraser
- particles
- plasticizer
- petal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43L—ARTICLES FOR WRITING OR DRAWING UPON; WRITING OR DRAWING AIDS; ACCESSORIES FOR WRITING OR DRAWING
- B43L19/00—Erasers, rubbers, or erasing devices; Holders therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43L—ARTICLES FOR WRITING OR DRAWING UPON; WRITING OR DRAWING AIDS; ACCESSORIES FOR WRITING OR DRAWING
- B43L19/00—Erasers, rubbers, or erasing devices; Holders therefor
- B43L19/0025—Eraser or rubber material, e.g. comprising hard particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
Definitions
- the present invention relates to an eraser that has excellent erasability of writing lines such as pencils, mechanical pencils, and colored pencils, and has a light-transmitting property that does not cause erase residue.
- erasers such as pencils and mechanical pencils for erasing written lines are mainly composed of rubber materials such as natural rubber and synthetic rubber, and plastic resins such as vinyl chloride.
- plastics, etc. Also known from the shape as a regular rectangular parallelepiped, polygonal shapes suitable for corners, etc., and further in the base material as improving the erasability of writing lines What mix
- the present applicant is characterized by containing a tubular basic magnesium carbonate, which is a liquid-absorbing porous body as a blended composition, as an eraser that is excellent in erasability of writing lines and does not generate debris.
- the eraser which performs is disclosed (for example, refer patent document 1).
- the composition of the eraser containing this tubular basic magnesium carbonate, an acrylic thermoplastic resin powder, etc. is disclosed (for example, refer patent document 2).
- the eraser described in Patent Document 1 is unprecedented in that it has excellent erasability of writing lines and no erased debris, and the basic magnesium carbonate used has a tubular structure, so that the eraser By itself, the drawn line written in a dark color such as black allows the degree of adsorption of graphite or the like to be visually observed by looking at the eraser. Further, the eraser described in Patent Document 2 does not stain the paper surface and hardly generates burrs on the surface of the eraser due to the action of the acrylic thermoplastic powder.
- the eraser of Patent Document 1 has some problems such as significant pulverization during kneading, increased viscosity during kneading, or a decrease in liquid absorbency of basic magnesium carbonate and erasability of the eraser. is there.
- many colored pencils (cores) that can be erased with an eraser have been put on the market.
- the erased color is attracted and accumulated every time it is erased. If it is a dark color such as black, it can be understood by the degree of adsorption, but if it is a light color, there is a slight problem that the adsorption is difficult to understand.
- the demand is increasing at present.
- the eraser of the above-mentioned Patent Document 2 is not high in light transmittance as can be seen by light color adsorption.
- JP 2014-111320 A (Claims, Examples, etc.)
- JP-A-2017-52275 (Claims, Examples, etc.)
- the present invention is to solve this problem in view of the above-mentioned problems of the prior art and the present situation, and there is no erase residue, and the degree of adsorption can be recognized at a glance even if it is a light color such as a colored pencil lead.
- An object of the present invention is to provide an eraser with high light transmittance that can be erased easily.
- the present inventors have found that the above-mentioned eraser can be obtained by containing those having specific structural characteristics as a blended composition.
- the present invention has been completed.
- the eraser of the present invention is characterized in that it contains a secondary aggregate having a particle diameter of 1 to 100 ⁇ m with petal-like particles as primary particles.
- the particles preferably include flakes selected from calcium silicate, calcium carbonate or calcium phosphate, and a composite thereof.
- an eraser with high light transmittance that can be erased with certainty and can be easily erased even if it is a thin color such as a colored pencil lead without any eraser residue.
- the eraser of the present invention is characterized in that it contains a secondary aggregate having a particle diameter of 1 to 100 ⁇ m with petal-like particles as primary particles.
- the petal-like particles are those in which the flaky particles have a petal-like structure resembling rose petals.
- a secondary agglomerate having petal-like particles as primary particles and a particle diameter of 1 to 100 ⁇ m is used as a blending composition.
- the particle diameter in the present invention refers to an average particle diameter that is bulked from the measurement results in the laser diffraction / scattering method.
- Microtrac manufactured by Nikkiso Co., Ltd., 3100II
- the secondary agglomerates having a particle diameter of 1 to 100 ⁇ m in which the petal-like particles to be used are agglomerated are different from ordinary porous materials and have a very large pore radius and pore volume.
- liquid-absorbing porous material having optical transparency and a very high liquid absorption rate, preferably from particles having a liquid absorption rate of 30 to 500 ml / 100 g, more preferably a liquid absorption rate of 300 to 500 ml / 100 g.
- the liquid absorption rate refers to the minimum amount of linseed oil that is obtained by dropping linseed oil onto a pile of 100 g of powder to make a trowel (flowing state) from a sand dumpling state.
- the secondary aggregate having a particle diameter of more than 100 ⁇ m does not exhibit the effects of the present invention because the feel at the time of erasure is poor.
- the particles include flakes selected from calcium silicate, calcium carbonate, calcium phosphate, and a composite thereof.
- the particles include flakes selected from calcium silicate, calcium carbonate, calcium phosphate, and a composite thereof.
- calcium silicate petal porous structure calcium carbonate petal porous structure, calcium phosphate petal porous structure, calcium carbonate and calcium phosphate petal porous structure composite, etc. It is desirable to use a material that satisfies the above-mentioned ranges of the particle diameter and the liquid absorption rate and has optical transparency.
- the calcium silicate petal-like porous structure that can be used is a so-called gyrolite-type calcium silicate having a petal-like crystal structure having a large pore diameter and a pore volume.
- 2CaO.3SiO 2 .mSiO 2 .nH 2 O (where m and n are positive numbers)
- SiO 2 / CaO molar ratio is 1.0 to 4.5
- light transmission Those having a particle size of 100 ⁇ m or less are particularly preferable because even if the content is small, not only the effects of the present invention are brought about, but also the molding pressure can be molded at a low pressure.
- the petal-like porous structure composite of calcium carbonate and calcium phosphate is obtained by treating calcium carbonate or phosphorus by treating heavy calcium carbonate or light calcium carbonate with phosphoric acid, and at the same time making it porous. It has a crystal structure and is light transmissive. Among these, the use of a calcium silicate petal-like porous structure is preferable because of the further effect of the present invention.
- the content of secondary agglomerates having a particle diameter of 1 to 100 ⁇ m with the petal-like particles as primary particles is 0.7 to 30% by mass (hereinafter referred to as “mass%”) with respect to the total amount of the eraser composition. (It is simply referred to as “%”), preferably 6 to 12.5%. If this content is less than 0.7%, the eraser becomes too soft, whereas if it exceeds 30%, erase scraps are likely to be formed, or the handling during kneading and stirring is reduced, making molding difficult. Therefore, it is not preferable.
- the secondary agglomerates having a particle size of 1 to 100 ⁇ m in which the particle size used in the present invention is petal-like particles as primary particles it is preferable to contain a base material component, a plasticizer, and a filler.
- a base material component e.g., ethylene glycol dimethacrylate
- a plasticizer e.g., polyethylene glycol dimethacrylate
- a filler e.g., polymer of polymer, etc.
- the light transmittance is as high as 30 to 40%. Through this piece, the distance can be seen a little, but this is about 10 mm. It is possible to visually recognize the far side slightly, and even if it is a light color such as a colored pencil lead, the degree of adsorption into the eraser can be seen at a glance, and an eraser with no erase residue can be produced It made.
- the base material component that can be used is not particularly limited, and for example, at least one of various thermoplastic resins, synthetic rubbers, thermoplastic elastomers, and the like can be used.
- thermoplastic resins include vinyl chloride resins such as vinyl chloride resins and vinyl chloride vinyl acetate copolymers, acrylic resins such as polymethyl methacrylate, ethylene vinyl acetate copolymers, ethylene acrylic acid copolymers, and polyolefins. And chlorinated polyolefin.
- the synthetic rubber include butyl rubber, butadiene rubber, nitrile rubber, nitrile butadiene rubber, and styrene butadiene rubber.
- thermoplastic elastomer examples include styrene elastomers, olefin elastomers, polyurethane elastomers, and the like.
- a vinyl chloride resin is exemplified.
- vinyl chloride resins that can be suitably used include the Kane vinyl series (manufactured by Kaneka), the vinyla series (manufactured by Mitsubishi Kasei Vinyl), and the Leuron paste series (homopolymers and copolymers: Tosoh) as polyvinyl chloride. These may be used alone or in combination of two or more. The content of these base components is preferably 20 to 60% with respect to the total amount of the eraser composition.
- the plasticizer that can be used is not particularly limited as long as it is a plasticizer that can plasticize or gel the contained thermoplastic resin.
- dioctyl phthalate (DOP, dioctyl phthalate), phthalate examples include dibutyl acrylate (DBP, dibutyl phthalate), dioctyl adipate (DOA), dioctyl sebacate (DOS), butyl sebacate (DBS), dimethyl phthalate (DMP), dihexyl phthalate, and the like.
- DOP dioctyl phthalate
- phthalate Examples include dibutyl acrylate (DBP, dibutyl phthalate), dioctyl adipate (DOA), dioctyl sebacate (DOS), butyl sebacate (DBS), dimethyl phthalate (DMP), dihexyl phthalate, and the like.
- the content is preferably 5 to 40% based on the total amount
- the filler that can be used is not particularly limited as long as it is a substance that does not dissolve or react with vinyl chloride or a plasticizer.
- these fillers preferably have a particle size of 10 to 200 nm from the viewpoint of erasability, strength and lubricity.
- a carbon material may be contained from the viewpoint of further improving the erasing power, improving the erasing comfort, and suppressing deformation, unless emphasizing the light transmittance.
- fiber particles may be included.
- the carbon material that can be used include at least one of carbon black, carbon fiber, graphite, carbon nanofiber, and the like having a particle size large enough not to be adsorbed by the petal-like particles.
- it is contained in an amount of 1 to 20% with respect to the total amount of the eraser composition.
- These carbon materials preferably have a maximum size (particle diameter or diameter) of 100 ⁇ m or less, and the carbon fiber preferably has a length of 200 ⁇ m or less.
- the carbon fiber preferably has a length of 200 ⁇ m or less.
- it contains a chromatic pigment having a particle size large enough not to be adsorbed on the petal-like particles and a dye having a particle size large enough not to be adsorbed on the petal-like particles and not soluble in the plasticizer. You may let them.
- the light transmittance of the eraser when these color materials are not mixed is relatively high at 30 to 40%, that is, it is in a state where it is cloudy and slightly visible from the other side. It will increase the effect.
- fiber particles examples include at least one fiber particle such as polyethylene fiber, cellulose fiber, aramid fiber, vinylon fiber, polyamide fiber, polyester fiber, glass fiber, and zinc oxide single crystal. These are preferably contained in an amount of 1 to 20% based on the total amount of the eraser composition. These fiber particles preferably have a diameter of 20 ⁇ m or less at maximum.
- various stabilizers such as Ca-Zn stearate, epoxidized fatty acid alkyl ester and the like can be thermally stabilized to prevent deterioration of the base component (particularly vinyl chloride resin) at high temperatures.
- An agent can be used.
- viscosity adjusting agents, lubricants, solvents, colorants, ultraviolet absorbers, preservatives, antifungal agents, fragrances, and the like can be appropriately mixed.
- softening agents such as terpene resin, mineral oil, sulfur-free sub, vulcanizing agent, vulcanization accelerator, filler, anti-aging agent, An appropriate amount of microcapsules containing various additives can be blended.
- the eraser of the present invention comprises a secondary agglomerate having a particle size of 1 to 100 ⁇ m, a base component, a plasticizer, a filler, a carbon material, and fiber particles. Further, if necessary, after preparing a predetermined amount of each of the above-mentioned various compounding agents by a conventional method, it can be prepared by molding into a preferred shape. Examples of the shape of the eraser include a rod shape, a rectangular parallelepiped shape, a columnar shape, a prismatic shape, a triangular pyramid shape, a quadrangular pyramid shape, and a fan shape. Can be.
- the eraser of the present invention is capable of reliably erasing the writing lines such as pencils and mechanical pencils without damaging the paper surface, as compared to the conventional eraser where the erased residue appears. Whether or not it is highly transparent and the color of the color pencil core is light and the like can be recognized at a glance and no debris is formed is due to the following mechanism. That is, the eraser of the present invention contains a secondary agglomerate having a particle diameter of 1 to 100 ⁇ m, for example, a calcium silicate petal-like porous structure and the like, in which the petal-like particles are primary particles as the composition.
- the coloring material of the colored pencil core When rubbed against a writing line, the coloring material of the colored pencil core is adsorbed to the secondary aggregate having a particle diameter of 1 to 100 ⁇ m with the petal-like particles in the eraser as primary particles, and the coloring material is erased from the paper surface.
- the adsorbed coloring material is continued by diffusion due to the adsorbing ability of the secondary agglomerates having a particle diameter of 1 to 100 ⁇ m with the petal-like particles as primary particles. Since it is not applied to the paper surface again, the paper surface is not soiled and can be erased reliably. Also, since it is light transmissive, even if it is a light color such as a colored pencil lead, the degree of adsorption is at a glance. Will be understood.
- the conventional eraser using a liquid-absorbing porous material such as basic magnesium carbonate is an agglomerated particle because it is a tube-aggregated particle, and the erased color adsorbs and accumulates every time it is erased.
- a liquid-absorbing porous material such as basic magnesium carbonate
- cores erasable colored pencils
- the eraser of the present invention transmits light, it is possible to produce an eraser with excellent design, and by including a color material, various color erasers can be created, and light can be transmitted.
- the eraser of the present invention diffuses and accumulates the coloring material adsorbed each time it is erased, for example, the color of the eraser is light transmissive, and the colored pencil lead In the case of a light color such as, the color of the eraser increases with each erasure.
- Example 1 Fluorite R (particles in which petal-like particles of calcium silicate are aggregated in a spherical shape, particle diameter 30 ⁇ m, liquid absorption 440 ml / 100 g: manufactured by Tomita Pharmaceutical Co., Ltd.) 10% by mass Polyvinyl chloride (PSH-31: manufactured by Kaneka Corporation) 25% by mass Epoxidized fatty acid alkyl ester (stabilizer) 1% by mass Dioctyl phthalate (plasticizer) 39% by mass Dibutyl phthalate (plasticizer) 25% by mass The above blended materials were mixed with a vacuum mixer to prepare a blended composition (paste). This was cast into a 10 mm thick mold and heated at 130 ° C. for 2 hours while being pressurized at 200 kg / cm 2 to obtain an eraser (20 ⁇ 54 ⁇ 10 mm, hereinafter the same).
- Example 2 Fluorite RT (particles in which petal-like particles of calcium silicate are aggregated in a spherical shape, particle diameter 30 ⁇ m, liquid absorption 400 ml / 100 g: manufactured by Tomita Pharmaceutical Co., Ltd.) 10% by mass Polyvinyl chloride (PSH-31: manufactured by Kaneka Corporation) 25% by mass Epoxidized fatty acid alkyl ester (stabilizer) 1% by mass Dioctyl phthalate (plasticizer) 20% by mass Dibutyl phthalate (plasticizer) 44% by mass After mixing the above-mentioned compounding materials with a vacuum mixer to prepare a compounding composition (paste), it was cast into a mold in the same manner as in Example 1 above, and heated at 130 ° C. for 2 hours while applying pressure. Got.
- Example 3 10% by mass of Fluorite R of Example 1
- a vacuum mixer to prepare a compounding composition (paste)
- Example 4 10% by mass of Fluorite R of Example 1 Polyvinyl chloride (PSH-31: manufactured by Kaneka Corporation) 20% by mass Epoxidized fatty acid alkyl ester (stabilizer) 1% by mass Cellulose fiber (Nippon Paper Industries Co., Ltd., ⁇ 3 nm, length 100 ⁇ m) 5% by mass Dioctyl phthalate (plasticizer) 39% by mass Dibutyl phthalate (plasticizer) 25% by mass
- PSD-31 Polyvinyl chloride
- stabilizer 1% by mass Cellulose fiber
- Dioctyl phthalate plasticizer
- plasticizer dibutyl phthalate
- Example 5 10% by mass of Fluorite R of Example 1 Polyvinyl chloride (PSH-31: manufactured by Kaneka Corporation) 25% by mass Epoxidized fatty acid alkyl ester (stabilizer) 1% by mass Dioctyl phthalate (plasticizer) 20% by mass Dibutyl phthalate (plasticizer) 44% by mass After mixing the above-mentioned compounding materials with a vacuum mixer to prepare a compounding composition (paste), it was cast into a mold in the same manner as in Example 1 above, and heated at 130 ° C. for 2 hours while applying pressure. Got.
- PSH-31 manufactured by Kaneka Corporation
- stabilizer 1% by mass Dioctyl phthalate
- plasticizer 20% by mass Dibutyl phthalate
- Example 6 10% by mass of Fluorite R of Example 1 Polyvinyl chloride (PSH-31: manufactured by Kaneka Corporation) 20% by mass Epoxidized fatty acid alkyl ester (stabilizer) 1% by mass Glass fiber (Nippon Electric Glass Co., Ltd., length 150 ⁇ m) 5% by mass Dioctyl phthalate (plasticizer) 20% by mass Dibutyl phthalate (plasticizer) 44% by mass After mixing the above-mentioned compounding materials with a vacuum mixer to prepare a compounding composition (paste), it was cast into a mold in the same manner as in Example 1 above, and heated at 130 ° C. for 2 hours while applying pressure. Got.
- Example 7 10% by mass of Fluorite R of Example 1 Polyvinyl chloride (PSH-31: manufactured by Kaneka Corporation) 20% by mass Epoxidized fatty acid alkyl ester (stabilizer) 1% by mass Zinc oxide single crystal (Panatetra: Panasonic Corporation) 5% by mass Dioctyl phthalate (plasticizer) 20% by mass Dibutyl phthalate (plasticizer) 44% by mass After mixing the above-mentioned compounding materials with a vacuum mixer to prepare a compounding composition (paste), it was cast into a mold in the same manner as in Example 1 above, and heated at 130 ° C. for 2 hours while applying pressure. Got.
- Example 8 10% by mass of Fluorite R of Example 1
- Example 9 10% by mass of Fluorite R of Example 1 Calcium carbonate / calcium phosphate composite particles (particles in which petal-like particles are aggregated in a spherical shape, particle diameter 3 ⁇ m, liquid absorption 150 ml / 100 g: manufactured by Mitsubishi Pencil Co., Ltd.) 5% by mass Polyvinyl chloride (PSH-31: manufactured by Kaneka Corporation) 20% by mass Epoxidized fatty acid alkyl ester (stabilizer) 1% by mass Dioctyl phthalate (plasticizer) 20% by mass Dibutyl phthalate (plasticizer) 44% by mass After mixing the above-mentioned compounding materials with a vacuum mixer to prepare a compounding composition (paste), it was cast into a mold in the same manner as in Example 1 above, and heated at 130 ° C. for 2 hours while applying pressure. Got.
- Example 10 15% by mass of Fluorite R of Example 1
- Example 11 Fluorite R of Example 1 20% by mass Styrene elastomer (AR-731N, manufactured by Aron Kasei Co., Ltd.) 65% by mass Terpene resin (Yasuhara Chemical Co., Ltd., YS Polystar PX1250) 10% by mass Mineral oil (ExxonMobil Corp., Spectracin 4) 5% by mass
- the compounded material was kneaded with a kneader to prepare a paste. This was cast into a 10 mm thick mold and allowed to cool to obtain an eraser.
- Example 12 Fluorite R of Example 1 20% by mass Olefin-based elastomer (Mitsubishi Chemical Corporation, Lavalon TE9500C) 65% by mass Mineral oil (ExxonMobil Limited, Spectracin 4) 15% by mass The blended material was heated and kneaded with a kneader to prepare a paste. This was cast into a 10 mm thick mold and allowed to cool to obtain an eraser.
- Olefin-based elastomer Mitsubishi Chemical Corporation, Lavalon TE9500C
- Mineral oil ExxonMobil Limited, Spectracin 4
- Example 13 Fluorite R of Example 1 20% by mass 65% by mass of polyurethane elastomer (BASF Japan Ltd., Elastollan) Mineral oil (ExxonMobil Limited, Spectracin 4) 15% by mass The blended material was heated and kneaded with a kneader to prepare a paste. This was cast into a 10 mm thick mold and allowed to cool to obtain an eraser.
- polyurethane elastomer BASF Japan Ltd., Elastollan
- Mineral oil ExxonMobil Limited, Spectracin 4
- Example 14 Fluorite R of Example 1 25% by mass Styrene elastomer (AR-731N, manufactured by Aron Kasei Co., Ltd.) 55% by mass Mineral oil (ExxonMobil Co., Ltd., Spectracin 4) 20% by mass
- the blended material was heated and kneaded with a kneader to prepare a paste. This was cast into a 10 mm thick mold and allowed to cool to obtain an eraser.
- Example 15 Calcium carbonate / calcium phosphate composite particles (particles in which petal-like particles are aggregated in a spherical shape, particle diameter 3 ⁇ m, liquid absorption 150 ml / 100 g 20% by mass Polyvinyl chloride (PSH-31: manufactured by Kaneka Corporation) 25% by mass Epoxidized fatty acid alkyl ester (stabilizer) 1% by mass Dioctyl phthalate (plasticizer) 30% by mass Dibutyl phthalate (plasticizer) 24% by mass After mixing the above-mentioned compounding materials with a vacuum mixer to prepare a compounding composition (paste), it was cast into a mold in the same manner as in Example 1 above, and heated at 130 ° C. for 2 hours while applying pressure. Got.
- the pencil used is the pencil HB specified in JIS S 6006. In this evaluation, the colored pencil of “Lemon Yellow” (manufactured by Mitsubishi Pencil Co.) was used.
- the weight change amount of the eraser before and after the measurement test of the erasure rate was measured.
- the numerical value of the change in weight (mg) is a positive value, it indicates the amount of adsorption, and when the weight is a negative value, it is the amount of debris. Further, the confirmation of the presence or absence of erased debris was confirmed by visual observation of the presence or absence of erased debris during the evaluation of the erasure rate.
- Evaluation criteria A: It was observed that the color of “lemon yellow” spread evenly in the eraser. B: It was observed that the color of “lemon yellow” gradually spread from the erased surface of the eraser to the inside. C: Although it was observed that the color of “lemon yellow” was attached to the surface of the eraser, it was not possible to observe the state of diffusion inside. D: The color of “lemon yellow” was hardly observed on the surface of the eraser or inside.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
そこで、本出願人は、筆記描線の消去性に優れ、消しカスが出ない消し具として、配合組成物としての吸液性多孔体である管状の塩基性炭酸マグネシウムなどを含有することを特徴とする消し具を開示している(例えば、特許文献1参照)。
さらには、この管状塩基性炭酸マグネシウムと、アクリル系熱可塑性樹脂粉末などを含有する消し具の組成物が開示されている(例えば、特許文献2参照)。
この特許文献1に記載の消し具は、筆記描線の消去性に優れ、消しカスが出ない点で今までにないものであり、また、用いる塩基性炭酸マグネシウムは構造が管状であるので消し具自体は不透明となり、黒などの濃い色で筆記した描線は、消し具を見れば、黒鉛等の吸着度合いが目視で見てとれるものである。また、特許文献2に記載の消し具は、アクリル系熱可塑性粉末の働きにより、紙面を汚さず、かつ、消し具表面のバリが殆ど発生しないものである。
前記粒子は、ケイ酸カルシウム、炭酸カルシウム又はリン酸カルシウム、これらの複合体から選ばれる薄片を含むことが好ましい。
更に基材成分、可塑剤、充填材を含有することが好ましい。
本発明の消し具は、花弁状粒子を1次粒子とした粒子径が1~100μmの2次凝集体を含むことを特徴とするものである。本発明において、花弁状粒子は、薄片状粒子がバラの花びらに似た花弁状構造をしているものである。
用いる花弁状粒子を1次粒子とし、これらが凝集した粒子径1~100μmの2次凝集体は、通常の多孔性物質とは異なり、極めて大きな細孔半径と細孔容積を備えたものであり、光透過性を有し、また、吸液率が極めて高い吸液性多孔体でもあり、好ましくは吸液率30~500ml/100g、より好ましくは、吸液率300~500ml/100gの粒子からなるものが挙げられる。なお、上記吸液率は粉体100gの山に亜麻仁油を滴下して行って、砂団子状態からトロー(流動状態)となる最低の亜麻仁油量をいう。
上記粒子径が100μm超過となる2次凝集体では、消去時の感触が悪くなるため、本発明の効果を発揮しないものとなる。
また、炭酸カルシウムとリン酸カルシウムの花弁状多孔質構造複合体は、重質炭酸カルシウム又は軽質炭酸カルシウムをリン酸で処理することによりカルシウムとリンの交換を行うと同時に多孔質化したものであり、花弁状結晶構造を持ち、光透過性を有するものである。
これらの中で、本発明の更なる効果の発揮などからケイ酸カルシウム花弁状多孔質構造体の使用が好ましい。
この含有量が0.7%未満であると、字消しがやわらかくなりすぎとなり、一方、30%を超えると、消しカスが生じやすくなったり、混錬攪拌時のハンドリングの低下につながり成形しづらくなるため、好ましくない。
熱可塑性樹脂としては、例えば、塩化ビニル樹脂、塩化ビニル酢酸ビニル共重合体などの塩化ビニル系樹脂、ポリメチルメタクリレートなどのアクリル系樹脂、エチレン酢酸ビニル共重合体、エチレンアクリル酸共重合体、ポリオレフィン、塩素化ポリオレフィンなどが挙げられる。合成ゴムとしては、例えば、ブチルゴム、ブタジエンゴム、ニトリルゴム、ニトリルブタジエンゴム、スチレンブタジエンゴムなどが挙げられる。熱可塑性エラストマーとしては、スチレン系エラストマー、オレフィン系エラストマー、ポリウレタン系エラストマーなどが挙げられる。特に好ましい基材成分としては、塩化ビニル系樹脂が挙げられる。
これらの基材成分の含有量は、消し具組成物全量に対して、好ましくは、20~60%含有されていることが望ましい。
特に、これらの充填材は、消去性、強度、潤滑性の点から、粒子径が10~200nmであることが好ましい。
この場合、用いることができる炭素材料としては、例えば、上記花弁状粒子に吸着されない程度に大きな粒子径のカーボンブラック、カーボンファイバー、黒鉛、カーボンナノファイバー等の少なくとも1種が挙げられ、これらは、消し具組成物全量に対して、好ましくは、1~20%含有されていることが望ましい。これらの炭素材料の大きさ(粒子径または直径)は、最大(粒子径)で100μm以下となるものを用いることが好ましく、カーボンファイバーについては長さ200μm以下となるものを用いることが好ましい。
また、意匠性を向上させる見地から、上記花弁状粒子に吸着されない程度に大きな粒子径の有彩色の顔料、上記花弁状粒子に吸着されない程度に大きな粒子径かつ上記可塑剤に溶解しない染料を含有させてもよい。この場合、これら色材を混入しない場合の消し具の光透過性が30~40%と比較的高いこと、即ち、白濁して僅かに向こう側が透けて見える程度の状態であることが、彩色の効果を高めてくれるものである。
更に、基材成分としてゴムや、エラストマーを用いた場合には、例えば、テルペン樹脂、鉱物油、無硫黄性サブなどの軟化剤、加硫剤、加硫促進剤、充填剤、老化防止剤、各種添加剤入りのマイクロカプセルなどを適宜量配合することができる。
消し具の形状としては、例えば、棒状、直方体状、円柱状、角柱状、三角錐状、四角錐状、扇形状などを挙げることができ、更に、ペン型ホルダーで使用したり、テープ形状としたりすることができる。
すなわち、本発明の消し具では、配合組成物として花弁状粒子を1次粒子とした粒子径1~100μmの2次凝集体、例えば、ケイ酸カルシウム花弁状多孔質構造体等を含有することにより、筆記描線に擦り付けると消し具内の上記花弁状粒子を1次粒子とした粒子径1~100μmの2次凝集体に色鉛筆芯の色材等を吸着し、紙面から色材等が消去され、吸着された色材等は上記花弁状粒子を1次粒子とした粒子径1~100μmの2次凝集体の吸着能力により拡散で継続され、消しカスを生じることなく、しかも、一旦吸着した色材等を再度紙面に塗布等することがないので紙面を汚すことがなく、確実に消去することができ、また、光透過性を備えるので色鉛筆芯等の薄い色等であっても吸着度合いが一目で分かるものとなる。従来の塩基性炭酸マグネシウムなどの吸液性多孔体を用いた消し具では、管状に凝集した粒子であるので、不透明な消し具となり、消去の度毎に消去した色の吸着が起こり蓄積されていくこととなり、消去性の色鉛筆(芯)などの薄い色などの場合、吸着が分かりにくいという課題があるものであった。
従って、本発明の消し具は、光を透過するので意匠性に優れる消し具の製造が可能となり、色材の含有により、いろいろな色の消し具を作成することができ、また、光を透過し、使用によって減らず、更に減らないので、原形を維持するので最後まで使いやすく、使用することができ、しかも、消しカスを生じることなく、筆記描線の消去性に優れたものとなる。なお、本発明の消し具は、消去の度に吸着した色材等を消し具内に拡散、蓄積していくものであり、例えば、消し具の色を光透過性を有するものとし、色鉛筆芯等の薄い色とした場合には、消去の度ごとに消し具の色は薄い色度が増加していくものとなる。
(実施例1)
フローライトR(ケイ酸カルシウムの花弁状粒子が球状に凝集した粒子、粒子径30μm、吸液率440ml/100g:富田製薬株式会社製) 10質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 25質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
ジオクチルフタレート(可塑剤) 39質量%
ジブチルフタレート(可塑剤) 25質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した。これを厚さ10mmの金型に流し込み成形し、200kg/cm2で加圧しながら130℃で2時間加熱して消し具(20×54×10mm、以下同様)を得た。
フローライトRT(ケイ酸カルシウムの花弁状粒子が球状に凝集した粒子、粒子径30μm、吸液率400ml/100g:富田製薬株式会社製) 10質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 25質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
ジオクチルフタレート(可塑剤) 20質量%
ジブチルフタレート(可塑剤) 44質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した後、上記実施例1と同様にして、金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
実施例1のフローライトR 10質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 20質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
アクリル系重合体(LP-3202:三菱レイヨン株式会社製) 5質量%
ジオクチルフタレート(可塑剤) 39質量%
ジブチルフタレート(可塑剤) 25質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した後、上記実施例1と同様にして、金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
実施例1のフローライトR 10質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 20質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
セルロースファイバー(日本製紙株式会社製、φ3nm、長さ100μm) 5質量%
ジオクチルフタレート(可塑剤) 39質量%
ジブチルフタレート(可塑剤) 25質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した。これを金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
実施例1のフローライトR 10質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 25質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
ジオクチルフタレート(可塑剤) 20質量%
ジブチルフタレート(可塑剤) 44質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した後、上記実施例1と同様にして、金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
実施例1のフローライトR 10質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 20質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
ガラスファイバー(日本電気硝子株式会社製、長さ150μm) 5質量%
ジオクチルフタレート(可塑剤) 20質量%
ジブチルフタレート(可塑剤) 44質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した後、上記実施例1と同様にして、金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
実施例1のフローライトR 10質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 20質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
酸化亜鉛単結晶(パナテトラ:パナソニック株式会社) 5質量%
ジオクチルフタレート(可塑剤) 20質量%
ジブチルフタレート(可塑剤) 44質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した後、上記実施例1と同様にして、金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
実施例1のフローライトR 10質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 20質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
無硫黄性サブ 5質量%
ジオクチルフタレート(可塑剤) 20質量%
ジブチルフタレート(可塑剤) 44質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した後、上記実施例1と同様にして、金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
実施例1のフローライトR 10質量%
炭酸カルシウム・リン酸カルシウム複合粒子(花弁状粒子が球状に凝集した粒子、粒子径3μm、吸液率150ml/100g:三菱鉛筆株式会社で製造) 5質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 20質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
ジオクチルフタレート(可塑剤) 20質量%
ジブチルフタレート(可塑剤) 44質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した後、上記実施例1と同様にして、金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
実施例1のフローライトR 15質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 15質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
ジオクチルフタレート(可塑剤) 30質量%
ジブチルフタレート(可塑剤) 39質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した後、上記実施例1と同様にして、金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
実施例1のフローライトR 20質量%
スチレン系エラストマー(アロン化成株式会社製、AR-731N) 65質量%
テルペン樹脂(ヤスハラケミカル株式会社製、YSポリスターPX1250) 10質量%
鉱物油(エクソンモービル有限会社製、スペクトラシン4) 5質量%
上記配合材料をニーダーにより加熱混錬しペーストを調製した。これを厚さ10mmの金型に流し込み成形し冷却させて消し具を得た。
実施例1のフローライトR 20質量%
オレフィン系エラストマー(三菱化学株式会社製、ラバロンTE9500C) 65質量%
鉱物油(エクソンモービル有限会社製、スペクトラシン4) 15質量%
上記配合材料をニーダーにより加熱混練しペーストを調製した。これを厚さ10mmの金型に流し込み成形し冷却させて消し具を得た。
実施例1のフローライトR 20質量%
ポリウレタン系エラストマー(BASFジャパン株式会社社製、エラストラン) 65質量%
鉱物油(エクソンモービル有限会社製、スペクトラシン4) 15質量%
上記配合材料をニーダーにより加熱混練しペーストを調製した。これを厚さ10mmの金型に流し込み成形し冷却させて消し具を得た。
実施例1のフローライトR 25質量%
スチレン系エラストマー(アロン化成株式会社製、AR-731N) 55質量%
鉱物油(エクソンモービル有限会社製、スペクトラシン4) 20質量%
上記配合材料をニーダーにより加熱混練しペーストを調製した。これを厚さ10mmの金型に流し込み成形し冷却させて消し具を得た。
炭酸カルシウム・リン酸カルシウム複合粒子(花弁状粒子が球状に凝集した粒子、粒子径3μm、吸液率150ml/100g 20質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 25質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
ジオクチルフタレート(可塑剤) 30質量%
ジブチルフタレート(可塑剤) 24質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した後、上記実施例1と同様にして、金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
酸化マグネシウム(スターマグPSF:神島化学株式会社) 25質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 20質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
ジオクチルフタレート(可塑剤) 30質量%
ジブチルフタレート(可塑剤) 24質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した後、上記実施例1と同様にして、金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
炭酸カルシウム(NEOLIGHT SS:竹原化学工業株式会社製) 40質量%
ポリ塩化ビニル(PSM-154:株式会社カネカ製) 40質量%
ステアリン酸Ca-Zn(安定剤) 1質量%
ジオクチルフタレート(可塑剤) 19質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した後、上記実施例1と同様にして、金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
FRTP用グラスファイバー(カット長3mm) 40質量%
ポリ塩化ビニル(PSM-154:株式会社カネカ製) 40質量%
ステアリン酸Ca-Zn(安定剤) 1質量%
ジオクチルフタレート(可塑剤) 19質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した。これを金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
炭酸カルシウム(NEOLIGHT SS:竹原化学工業株式会社製) 39質量%
スチレン系エラストマー(アロン化成株式会社製、AR-731N) 50質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
鉱物油 10質量%
上記配合材料をニーダーにより加熱混錬しペーストを調製した。これを厚さ10mmの金型に流し込み成形し、冷却させて消し具を得た。
マグチューブ(吸液性多孔体、塩基性炭酸マグネシウムの薄片状微細結晶が管状に凝集した粒子、外径3.5μm、長さ20μm、内径1μm、比表面積150m2/g、吸液率300ml/100g:日鉄鉱業社製) 10質量%
ポリ塩化ビニル(PSH-31:株式会社カネカ製) 25質量%
エポキシ化脂肪酸アルキルエステル(安定剤) 1質量%
ジオクチルフタレート(可塑剤) 39質量%
ジブチルフタレート(可塑剤) 25質量%
上記配合材料を真空ミキサーにて混合し配合組成物(ペースト)を調製した後、上記実施例1と同様にして、金型に流し込み成形し、加圧しながら130℃で2時間加熱して消し具を得た。
JIS S 6050-2008に開示されているプラスチック字消しの消し能力(消字率)試験に準拠し、E(消字率:=消去率)=(1-M/C)×100〔M:摩消部の濃度、C:着色部の濃度〕により、消去率(4往復)を測定した。消去率の数値が高いほど消去性に優れることを示す。なお、JIS S 6050-2008では、使用鉛筆はJIS S 6006に規定する鉛筆のHBを用いるものであるが、本評価では、ユニ アーテレーズカラーの「レモン イエロー」(三菱鉛筆株式会社製)の色鉛筆を用いた。
上記消字率の測定試験前後の消し具の重量変化量を測定した。重量の変化(mg)の数値がプラス値である場合、吸着量を示すものとなり、重量がマイナス値である場合は、消しかカスの量となる。
また、消しカスの有無の確認は、上記消去率の評価の際に消しカスの有無を目視により確認した。
紫外可視赤外分光光度計(株式会社日立製作所製、U-3300)により厚さ0.25mmの消し具片を測定した。光源にはヨウ素タングステンランプ(750nm)を用いた。光透過率(%)が0(ゼロ)の場合は、不透明となり、数値が高いほど透明となるものである。
上記消去率の評価で用いた消し具を一日置いて観察し「レモン イエロー」の色味が消し具内に広がっているかを下記評価基準で官能評価した。
評価基準:
A:「レモン イエロー」の色味が消し具内に均一に広がっているのが観察できた。
B:「レモン イエロー」の色味が消し具の消去面から内部へ徐々に広がっているのが観察できた。
C:「レモン イエロー」の色味が消し具表面に付着しているのが観察できたが内部へ拡散している様子は観察できなかった。
D:「レモン イエロー」の色味が消し具表面にも内部にもほとんど観察できなかった。
Claims (3)
- 花弁状粒子を1次粒子とした粒子径1~100μmの2次凝集体を含むことを特徴とする消し具。
- 前記粒子がケイ酸カルシウム、炭酸カルシウム又はリン酸カルシウム、これらの複合体から選ばれる薄片を含むことを特徴とする請求項1に記載の消し具。
- 更に基材成分、可塑剤、充填材を含有することを特徴とする請求項1又は2に記載の消し具。
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201880024759.XA CN110494298B (zh) | 2017-04-13 | 2018-04-11 | 擦除工具 |
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| KR1020197029666A KR102535562B1 (ko) | 2017-04-13 | 2018-04-11 | 지우기 도구 |
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| CN111960721A (zh) * | 2020-07-17 | 2020-11-20 | 温州阿珥楠文具有限公司 | 一种清洁麂皮鞋橡皮的制作方法 |
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| JP2007277322A (ja) * | 2006-04-04 | 2007-10-25 | Pentel Corp | 修正テープ用隠蔽剤組成物 |
| JP2014111320A (ja) | 2012-12-05 | 2014-06-19 | Mitsubishi Pencil Co Ltd | 消し具 |
| JP2017052275A (ja) | 2015-09-08 | 2017-03-16 | 三菱鉛筆株式会社 | 消し具 |
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| JPS6242898A (ja) * | 1985-08-21 | 1987-02-24 | 三菱化成ビニル株式会社 | 塩化ビニル系樹脂製字消し |
| JP6674181B2 (ja) * | 2012-07-03 | 2020-04-01 | 株式会社サクラクレパス | 字消し |
| JP6198420B2 (ja) * | 2013-03-15 | 2017-09-20 | 三菱鉛筆株式会社 | 消去具 |
| US11207913B2 (en) * | 2012-12-05 | 2021-12-28 | Mitsubishi Pencil Company, Limited | Erasing member and erasing tool using the same |
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Patent Citations (3)
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| JP2007277322A (ja) * | 2006-04-04 | 2007-10-25 | Pentel Corp | 修正テープ用隠蔽剤組成物 |
| JP2014111320A (ja) | 2012-12-05 | 2014-06-19 | Mitsubishi Pencil Co Ltd | 消し具 |
| JP2017052275A (ja) | 2015-09-08 | 2017-03-16 | 三菱鉛筆株式会社 | 消し具 |
Cited By (2)
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| JP2021167088A (ja) * | 2020-04-10 | 2021-10-21 | 株式会社サクラクレパス | 字消し |
| JP7450878B2 (ja) | 2020-04-10 | 2024-03-18 | 株式会社サクラクレパス | 字消し |
Also Published As
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| CN110494298A (zh) | 2019-11-22 |
| EP3611031A1 (en) | 2020-02-19 |
| JP7066680B2 (ja) | 2022-05-13 |
| EP3611031A4 (en) | 2020-12-23 |
| US11787225B2 (en) | 2023-10-17 |
| CN110494298B (zh) | 2022-05-13 |
| JPWO2018190377A1 (ja) | 2020-05-14 |
| KR20190138792A (ko) | 2019-12-16 |
| US20200101787A1 (en) | 2020-04-02 |
| KR102535562B1 (ko) | 2023-05-24 |
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