WO2003076208A1 - Ink holding member for writing material - Google Patents

Ink holding member for writing material Download PDF

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Publication number
WO2003076208A1
WO2003076208A1 PCT/JP2003/003024 JP0303024W WO03076208A1 WO 2003076208 A1 WO2003076208 A1 WO 2003076208A1 JP 0303024 W JP0303024 W JP 0303024W WO 03076208 A1 WO03076208 A1 WO 03076208A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink
writing
writing instrument
storage member
ink storage
Prior art date
Application number
PCT/JP2003/003024
Other languages
French (fr)
Japanese (ja)
Inventor
Takao Koyama
Toshimi Kamitani
Yasuaki Ogiwara
Original Assignee
Mitsubishi Pencil Kabushiki Kaisha
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP2002070291A external-priority patent/JP2003266986A/en
Priority claimed from JP2002225123A external-priority patent/JP2004066476A/en
Application filed by Mitsubishi Pencil Kabushiki Kaisha filed Critical Mitsubishi Pencil Kabushiki Kaisha
Priority to AU2003220897A priority Critical patent/AU2003220897A1/en
Publication of WO2003076208A1 publication Critical patent/WO2003076208A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K5/00—Pens with ink reservoirs in holders, e.g. fountain-pens
    • B43K5/005—Pen barrels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K7/00—Ball-point pens
    • B43K7/02—Ink reservoirs; Ink cartridges

Definitions

  • the present invention relates to an ink container for a writing instrument, such as a water-based or oil-based liquid ink or a gel ink, and an ink container for a writing instrument, such as an ink container tube, and more particularly to an ink container for a writing instrument.
  • the present invention relates to an ink storage member for a writing instrument that can prevent deterioration of the ink due to permeation of oxygen in the air, improve the scent retention of the scented ink, and prevent the ejection of the ink.
  • an ink container such as a direct liquid writing instrument having a collector structure, a batting type writing instrument, and an ink container (ink tube, refill) of a pole pen is water-based.
  • the main purpose is to accommodate ink for writing implements such as oil-based liquid ink and gel-like ink, and to prevent the solvent constituting the ink from volatilizing.
  • these ink storage containers and ink storage tubes for writing implements are made of organic polymers such as polypropylene (synthetic resin, etc.) from the viewpoints of chemical stability, solvent resistance, economy, and productivity. It is.
  • Japanese Unexamined Patent Publication No. 8-133333 / 1996 discloses a method of packaging stationery such as writing implements containing an antibacterial agent, in which a deoxidizer is included in the packaging material to allow contact with oxygen or moisture in the air.
  • a method for packaging stationery containing an antibacterial agent that can prevent discoloration of stationery by minimizing the amount of discoloration is disclosed.
  • vitamin C and other components that react or absorb with oxygen are added to the ink. Addition techniques are also known.
  • An ink container for writing implements such as a water-based or oil-based liquid ink or a gel ink. It is possible to prevent the deterioration of the ink due to the permeation of oxygen in the air into the ink container for writing implements such as the storage tube, to improve the fragrance retention of the scented ink, and to prevent the ink from being blown out for a long time.
  • Pressurized writing utensils with pressurized gas such as nitrogen gas such as pressurized pole pens, etc.
  • the present inventors have conducted intensive studies on the above-mentioned problems of the prior art and the like, and as a result, identified the outer surface portion (outer peripheral surface portion) of the writing instrument ink storage member composed of an organic polymer for accommodating the writing instrument ink. By forming a coating layer having physical properties, the present inventors have found that the ink storage member for a writing instrument with the above object can be obtained, and have completed the present invention.
  • the ink storage member for a writing instrument of the present invention resides in the following (1) to (16).
  • An ink storage member for a writing implement composed of an organic polymer for accommodating the ink for a writing implement, wherein the outer surface of the ink storage member for the writing implement has an oxygen permeability coefficient of 25. 10 _1 ° with CD ry (cc 'cm / cm 2 - sec - cmHg) for writing instruments
  • Inki housing member characterized by the following co one coat layer is formed.
  • a Inki housing member for a writing instrument constructed of an organic polymer which accommodates the writing instrument Inki, the oxygen permeability coefficient in the outer surface portion of the ink for a writing instrument housing member 10 1 25 0.
  • An ink container for writing implements characterized in that a coating layer in which tabular inorganic fine particles are dispersed in an organic polymer having a density of not more than (cm / cm 2 ⁇ sec ⁇ cmHg) is formed.
  • At least one activation treatment selected from ozone treatment, plasma treatment, corona treatment, ultraviolet irradiation treatment, high pressure discharge treatment, and acid treatment is applied to the outer surface of the ink storage member for writing implements.
  • Polyolefin-based thermoplastic organic polymers include polyolefin-based thermoplastics (13) The ink storage member for a writing implement as described in (13) above, wherein 5 to 40 parts by weight of a petroleum resin and / or a derivative thereof is blended with respect to 100 parts by weight of the organic polymer.
  • the total thickness including the thickness of the ink storage member for the writing implement and the coating layer is 0.5 to 5.0 mm, and the thickness of the coating layer is 0.1 to 2000 ⁇ m.
  • the ink storage member for a writing instrument according to any one of the above (1) to (14).
  • the thickness of the ink storage member for writing implements is L1, the oxygen permeability coefficient is P1, the thickness of the coating layer is L2, and the oxygen permeability coefficient is P2.
  • the overall oxygen transmission coefficient when the layer has been formed is P, when defining the total oxygen permeability coefficient P by the following formula (I), the total oxygen permeability coefficient P is 10- 9 (cc ⁇ cm / cm 2 -sec-cmHg)
  • the ink container for a writing instrument according to any one of the above (1) to (15), wherein
  • Oxygen permeability oxygen permeability X thickness of test specimen (II)
  • oxygen permeability oxygen permeability (oxygen permeability, unit: cc / m 2 ⁇ 24 hr ⁇ a tm) is expressed by the unit partial pressure difference.
  • the volume of oxygen that permeates a test piece in a unit area per unit time It is obtained by the following formula by actually measuring the amount of oxygen permeating a test piece at a certain time.
  • Oxygen permeability-Oxygen permeation amount [(High pressure partial pressure-Low pressure partial pressure) X Permeation area X time
  • the “oxygen permeability coefficient” defined in the present invention is, as defined above, a value obtained by multiplying the oxygen permeability by the thickness of the test piece and converting it into a permeation amount per unit thickness. If you know the thickness of the specimen and its oxygen permeability, you can determine the required oxygen permeability It is possible to understand how thick a coat layer should be selected in order to obtain.
  • “Dry” defined in the present invention means a humidity of 30% or less at each temperature, and "25 ° C Dry” The term “dry” refers to a humidity of 30% or less in an environment of 25 ° C, and “50 Dry” refers to a humidity of 30% or less in an environment of 50.
  • plate-like layered inorganic substance refers to an inorganic layered substance such as a viscous substance, and in addition to properties such as wall swelling property and swelling property, an organic or inorganic substance is intercalated to form an interlayer. Inorganic fine particles having the property of forming a compound.
  • FIG. 1 (a) is a longitudinal cross-sectional view showing an example in which the ink storage member for a writing implement of the present invention is applied to an ink storage tube for a pole pen
  • FIG. 1 (b) is a partial cross-sectional view showing a main part thereof.
  • FIG. 2 is a longitudinal sectional view of a pole pen provided with the ball-point pen ink storage tube of FIG. 1.
  • FIG. 3 is a vertical cross-sectional view showing an example in which the ink storage member for writing implement of the present invention is applied to a direct liquid type pen
  • FIG. 4 is a drawing showing the ink storage member for writing implement of the present invention provided with a valve mechanism.
  • FIG. 5 is a cross-sectional view showing an example applied to a writing implement.
  • FIG. 5 is a cross-sectional view showing an example in which the ink storage member for a writing implement of the present invention is applied to a writing implement in which the ink is inserted into an ink absorbing body such as a batting. It is. BEST MODE FOR CARRYING OUT THE INVENTION
  • the ink container for a writing instrument is an ink container for a writing instrument composed of an organic polymer that accommodates the ink for a writing instrument, specifically, an ink container for a writing instrument or the outside of an ink container tube.
  • a lower coating layer is formed
  • the ink container for writing implement of the second invention is an ink container for writing implement composed of an organic polymer for accommodating the ink for writing apparatus.
  • the oxygen permeability coefficient in the outer table surface portion of the writing instrument Inki housing member 25 in D ry 10- 1Q (cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg) tabular inorganic fine particles in the following organic polymers It is characterized in that a dispersed coat layer is formed.
  • the “present invention” includes both the first invention and the second invention.
  • Examples of the structure of the ink storage member for a writing implement of the present invention include, for example, an ink storage pipe (refill) in a pole pen in FIGS. 1 and 2 and an ink in a direct liquid writing implement having a collector structure in FIG.
  • Ink tank part that becomes a shaft body (ink container) that performs ink ink tank part that becomes a shaft body (ink container) that directly stores ink in a writing instrument having a valve mechanism in FIG. 4, and ink tank part that becomes a batting-type writing instrument in FIG.
  • a storage member that stores ink for writing implements such as an ink storage section that stores the ink for storage in the ink storage body.
  • These ink storage materials for writing instruments include polypropylene (PP), polyethylene (PE), cyclic polyolefin, polymethylpentene, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), Constructed using organic polymers such as polyacrylonitrile (PC), silicone elastomer, acrylonitrile-butadiene-styrene copolymer (ABS), nylon resin (polyamide), polyimide, and polyvinyl chloride (PVC)
  • PP polypropylene
  • PE polyethylene
  • PE cyclic polyolefin
  • polymethylpentene polymethylpentene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PC polyacrylonitrile
  • ABS acrylonitrile-butadiene-styrene copolymer
  • ABS acrylonitrile-butadiene-s
  • a coat layer having an oxygen permeability coefficient having the above characteristics is formed on an outer surface portion (outer peripheral surface portion) of the ink storage member for a writing instrument, so that the ink storage member is substantially a main body (layer). It has a structure of two or more coat layers, but the main body (layer) of the ink containing member may be formed in multiple layers using another different organic polymer layer.
  • the ink storage member has a structure of substantially two or more layers of a main body (layer) and a coat layer.
  • the main body (layer) of the ink storage member is multilayered using another different organic polymer layer. It may be formed.
  • the writing implement is further improved in that the adhesiveness between the ink storage member for the writing implement (main body) and the coating layer is further improved to further improve the effect of the present invention. It is preferable to use a body having the structure described in the following 1 to 3 for the main body of the ink storage member.
  • a writing instrument ink in which at least one activation treatment selected from an ozone treatment, a plasma treatment, a corona treatment, an ultraviolet irradiation treatment, a high-pressure discharge treatment, and an acid treatment is applied to the outer surface of the ink storage member body for the writing implement.
  • a housing member is used.
  • an ink storage container for a writing implement serving as an ink storage member for a writing implement may be used. It can be performed by subjecting the outer surface of the container or the ink storage tube or the like to a sandblasting treatment, a solvent treatment, or a roughening treatment such as a matte finish by roughening the mold surface.
  • the ozone treatment described in (1) above is intended to introduce a functional group such as a hydroxyperoxy group, a hydroxyl group, or a hydroxyl group by bringing the outer surface of the ink storage member for a writing instrument into contact with ozone molecules. This is performed by exposing the ink container for writing implements to ozone.
  • the exposure method include a method in which the film is kept in an atmosphere containing ozone for a predetermined time, a method in which the film is exposed to an ozone stream for a predetermined time, and the like, but are not particularly limited.
  • the plasma treatment in (1) above is performed by placing the ink storage member for writing implements in a container containing air, oxygen, nitrogen, carbon dioxide, argon, neon, etc., and exposing it to plasma generated by glow discharge.
  • a functional group such as a carboxylic acid group containing oxygen and nitrogen, a carbonyl group, an amino group, etc., on the outer surface of the ink container for writing implements is as follows: DC discharge, low-frequency discharge , Radio wave discharge, microwave discharge, etc., but are not particularly limited.
  • the outer surface of the ink storage member for writing implement can be activated by passing the ink storage member for writing implement into an electric field in which corona discharge occurs.
  • the ultraviolet irradiation treatment of (1) above is a method of irradiating the outer surface of the writing instrument ink storage member with ultraviolet light.
  • the outer surface of the writing instrument ink storage member is irradiated with ultraviolet light, the surface area of the writing instrument ink storage member is reduced. UV rays are absorbed by the chemical structure of the double bond, etc., and the absorbed energy breaks the chemical bond, introducing carbonyl and carboxyl groups, etc., which are obtained by bonding oxygen in the air to the resulting radical.
  • a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used, but is not particularly limited.
  • the high-pressure discharge treatment described in (1) above is a method in which a high voltage of several hundred thousand ports is applied between the electrodes provided with a large number of ink storage members for the writing implement, and the discharge is carried out in the air. By activating the surface of the ink storage container, oxygen is taken into the surface and the polar group is introduced, so that the outer surface of the writing equipment storage container can be activated.
  • the acid treatment of (1) above can be performed by directly immersing the ink storage member for writing implements in a chromium mixed acid solution, sodium hypochlorite Z hydrochloric acid / water system, chlorate-sulfuric acid system, sulfuric acid, or the like. .
  • Examples of the petroleum resin and Z or a derivative thereof described in (3) above include a hydroxyl group-containing hydrogenated petroleum resin or a derivative thereof.
  • commercially available Heylets G-100 manufactured by Mitsui Petrochemical
  • Petrozine # 100 manufactured by Mitsui Petrochemical
  • Alcon P-100 manufactured by Arakawa Chemical
  • the amount of the petroleum resin is less than 5 parts by weight, the adhesion to the coating layer will not be further improved, while if it exceeds 40 parts by weight, the effect will not be changed.
  • the mechanical strength of the member may decrease, which is not preferable.
  • the ink storage member (main body part) for writing implements of the above 1 to 3 By using the ink storage member (main body part) for writing implements of the above 1 to 3, in particular, when the above processing of the above 1 to 3 was performed using a polyolefin resin represented by PP, PVA), ethylene-vinyl alcohol copolymer (EVOH), polyamide (nylon resin), etc. Adhesion with the coating layer in which the inorganic fine particles are dispersed can be further improved.
  • the ink storage members (main body) for writing implements in (1) to (3) above may each be used individually, Accordingly, the above (1) and (2), (1) and (3), (2) and (3), and the combination of the above (1) to (3) (total of 4 types) may be used.
  • coating layer formed on the outer surface portion of the writing instrument ink receiving member comprising the above structure (outer peripheral surface) is 10_ oxygen permeability coefficient at 2 S ⁇ D ry 10 (cc ⁇ cm / cm 2 -sec-cmHg) or less
  • the ink container for a writing implement composed of an organic polymer accommodating the ink for a writing implement
  • Coat the plate-like inorganic fine particles in the oxygen permeability coefficient at 25 ° CD ry 10- 10 (cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg) in the following organic polymer on the outer surface portion of the use Inki housing member is dispersed It is necessary that a layer is formed.
  • the first and second aspects of the present invention both, 10- 11 (cc ⁇ cm / cm 2 ⁇ sec - cmHg) or less of the coating layer, more preferably, 10- 12 ⁇ 10- 15 (cc 'cm / cm 2 -sec-cmHg).
  • the coating layer having an oxygen permeability coefficient of more than 10 1 Q (cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg) at 25 Dry or in the second invention, the oxygen permeability coefficient is 10 ° at 25 ° ⁇ 0.
  • the coat layer according to the first invention has an oxygen permeability coefficient of 10 ′′ 10 (cc ⁇ cm / cm 2 -sec-cmHg) or less at 25 ° C.Dry. as long as the oxygen permeability coefficient of a flat plate-like inorganic fine particles is coated layers which are dispersed in an organic polymer exceeding by 25 ° CD ry 10- 1Q (cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg),
  • a layer in which plate-like inorganic fine particles are dispersed in an organic polymer having the above-described characteristic oxygen permeation coefficient is exemplified.
  • the organic polymer used for the coating layer may be an organic polymer having the oxygen permeability coefficient of the above characteristics, and is preferably a thin film having excellent oxygen permeability.
  • the organic polymer is polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), or polyamide from the viewpoints of productivity, economy, safety, and skin irritation.
  • PVA polyvinyl alcohol
  • EVOH ethylene-vinyl alcohol copolymer
  • polyamide from the viewpoint of productivity, economy, safety, and skin irritation.
  • the degree of genification is 50% or more
  • the ethylene mole ratio is 8 Omo 1% or less, preferably 20 to 80 mol% or less. More preferably, it is 30 to 60 mol% or less, particularly preferably 30 to 5 Omo 1%.
  • the resin coating layer such as the PVA layer and the EVOH layer is formed by dissolving a polymer having a low oxygen permeability, such as PVA or EVOH, in a predetermined solvent in the ink container for writing implements by a dipping method or the like.
  • the gas barrier coat layer can be formed by a coating method, a co-extrusion method, or a professional molding method.
  • the metal layer can be formed by a vapor deposition method, an electroless plating method, or the like.
  • the inorganic material layer is formed by immersing the ink storage member for writing implements in a solution containing an organic metal compound capable of undergoing a hydrolysis reaction or applying the solution to the surface of the member, and subjecting the inorganic material layer to a polycondensation reaction such as dehydration condensation after hydrolysis. Can be formed.
  • the plate-like inorganic fine particles dispersed in the organic polymer having the oxygen permeability coefficient having the above characteristics are dispersed in the organic polymer in order to exert a bypass effect of gas (such as oxygen). It is.
  • the plate-like inorganic fine particles include a plate-like inorganic material of a clay mineral having a natural or synthetic thin layer structure, such as talc, myriki, natural mica, synthetic mica, smectite, montmorillonite, bentonite, kaolinite, and glass.
  • a clay mineral having a natural or synthetic thin layer structure such as talc, myriki, natural mica, synthetic mica, smectite, montmorillonite, bentonite, kaolinite, and glass.
  • At least one kind selected from titanium oxide is exemplified.
  • the interlayer between the above-mentioned tabular inorganic substances has a cation-exchanging ability or an organic treatment from the viewpoint of improving dispersibility, interfacing organic polymers, monomers, oligomers, etc. between the layers.
  • a method for imparting cation exchange ability between the layers of the plate-like layered inorganic material there is a method of performing ion exchange with an organic quaternary ammonium salt, and the like. Examples of the method include an organic treatment method using a coupling agent, a titanium coupling agent, an aluminum chelating agent, an organic monomer or an oligomer having a metal alkoxide, various reactive functional groups, or the like.
  • tabular inorganic fine particles that can be used include, for example, MK-100 (manufactured by Coop Chemical Co., Ltd., My Strength), Zeonite (manufactured by Mizusawa Chemical Co., Ltd.), SWN, SAN, STN, SEN, SPN ( Smectite, Corp Chemical Co., Ltd., Bentonite (Toyojun Mining Co., Ltd.), Synthetic inorganic polymer smecton (Kunimine Kogyo Co., Ltd.), Kunipia (Montmorinite, Kunimine Kogyo Co., Ltd.), Kaolinite (Tsuchiya Riki Korin Kogyo Co., Ltd.) And the like.
  • the content of the flat inorganic fine particles used in the second invention is 0.1 to 25% by weight, preferably 0.5 to 20% by weight, more preferably 0.5 to 1% by weight in the organic polymer. Preferably, it is dispersed at 5% by weight.
  • the plate-like inorganic fine particles are scattered in the organic polymer, making it difficult to exhibit a bypass effect of gas (such as oxygen). If it exceeds, the plate-like inorganic fine particles are excessively present in the organic polymer, and the plate-like inorganic fine particles cannot be covered with the organic polymer, so that voids are present, and conversely, gas (such as oxygen) easily permeates. It will be.
  • the flat inorganic fine particles having the above-mentioned characteristics are converted into oxygen-permeable particles having the above-mentioned characteristics.
  • a method of dispersing in an organic polymer having an excess coefficient in the case of a varnish, it can be carried out using a Paul mill, a high-speed dissolver, or ultrasonic waves.
  • the coating layer in which the flat inorganic fine particles are dispersed can be formed, for example, by immersing the ink storage member for a writing implement in a coating solution (by performing a dipping process) and drying the solvent.
  • the effect of the present invention can be exhibited by forming the coating layer having the above-mentioned characteristics.
  • the surface tackiness is further reduced, and the moisture absorption is further reduced.
  • the coat layer may be a coat layer further subjected to a water-resistant treatment.
  • the water-resistance treatment may be performed, for example, by reducing the number of hydroxyl groups by reacting with the hydroxyl groups of the organic polymer forming the coating layer.
  • Heat treatment flame treatment
  • cross-linking reaction with hydroxyl group by aldehydes cross-linking reaction with methylol compound
  • cross-linking reaction with epoxy compound cross-linking reaction with esters
  • cross-linking reaction with diisocyanate copper
  • a water-resistant treatment can be performed by reducing the number of hydroxyl groups by forming a complex with a metal compound such as aluminum, titanium, zirconium, tin, and vanadium, and the like, including boron compounds such as sodium.
  • a hydroxyl group such as PVA or EVOH is reacted with a boron compound such as boric acid or sodium borate to form a complex, or It can be carried out by partially cross-linking polymers by a cross-linking reaction such as methylol-rea.
  • the water resistance treatment method is not limited to the above method.
  • a silicone-based compound, a fluorine-based compound, or a fatty acid-based compound is contained in the varnish in order to increase the mechanical strength such as the abrasion resistance of the coat layer having the above characteristics. Wax and the like can be added.
  • Silicone compounds include, for example, silicone oil, modified silicone Examples include oils, silicone resins, and silicone-based coupling agents. Specifically, KF-100, KF-56 (silicone oil) manufactured by Shin-Etsu Chemical Co., Ltd., TSF-410, TSF-4446 manufactured by Toshiba Silicone Co., Ltd. , TSF-4710 (modified silicone oil), KP-316, 316A (silicone resin) manufactured by Shin-Etsu Chemical Co., Ltd., and the like, but are not limited thereto. You may mix and use.
  • fluorine-based compound examples include fluorine-based surfactants, and specific examples thereof include Megafac F-470, F-173, and F-177 manufactured by Dainippon Ink and Chemicals, and the like.
  • the present invention is not limited thereto, and two or more of these may be used as a mixture, or may be used as a mixture with the above-mentioned silicone compound.
  • a fatty acid amide wax from the viewpoint of imparting scratch resistance, and examples thereof include a saturated fatty acid amide, an unsaturated fatty acid amide, and a modified fatty acid amide. Specific examples include stearic acid amide and oleic acid amide manufactured by Wako Pure Chemical Industries, Ltd., but are not limited thereto, and a mixture of two or more of these may be used. It may be used as a mixture with the above-mentioned silicone compound and fluorine compound.
  • the total thickness including the thickness of the ink storage member for the writing implement (the main body) and the coating layer (the total thickness of the main body and the thickness of the coating layer). Varies depending on the type of ink to be contained, the type of organic polymer used in the main body, and the like, but is preferably 0.5 to 5.0 mm, more preferably 0.7 to 2.0 mm, and The thickness of the coat layer is preferably from 0.1 to 2000 m, more preferably from 1.0 to 200 m.
  • the total thickness 0.5 to 5.0 mm and the thickness of the coat layer to 0.1 to 200, it is possible to more reliably reduce oxygen without causing problems in moldability, mechanical strength, etc. To prevent the deterioration of the ink and blow out the ink Can be prevented.
  • the total thickness is less than 0.5 mm, problems may occur in terms of moldability and the strength of the ink containing member, and if the total thickness is more than 5.0 mm, the oxygen permeability will be poor. Although it is improved, a member having visibility (for example, the amount of remaining ink is visually recognized) becomes inferior in visibility and further reduces design flexibility.
  • the thickness of the coat layer is 0.1 m, the mechanical strength of the film will be reduced, and the oxygen permeability will be reduced. If the thickness of the coat layer exceeds 2000 tm, Although the oxygen permeability is improved, the visibility is deteriorated in order to obtain a member having visibility (for example, the amount of remaining ink is visually recognized), and the degree of freedom of design is reduced.
  • the ink remaining amount can be visually confirmed by forming the coating layer having the above-mentioned physical properties on the outer surface portion (outer peripheral surface portion) of the ink storage member for a writing instrument having the above configuration.
  • Oxygen in the air does not pass while maintaining transparency or translucency, preventing deterioration of the ink, improving the fragrance retention of the fragrance ink, and preventing the ejection of the ink for a long time.
  • the surface tackiness is further suppressed, and the film strength is further improved. In order to further improve these effects, preferably, as shown in FIG.
  • the thickness of the container is Ll
  • the oxygen transmission coefficient is PI
  • the thickness of the coating layer is L2
  • the oxygen transmission coefficient is P2
  • the total oxygen when the coating layer of the ink storage member for writing implements is formed
  • the transmission coefficient is P
  • the total oxygen permeability coefficient P it is desirable that the total oxygen permeability coefficient P is a 10- 9 (cc ⁇ cm / cm 2 ⁇ sec ⁇ c mHg) below.
  • Fig. 1 explains the refill, but Fig. 2 shows the following shafts as ink storage containers (ink Total oxygen permeability coefficient even if P is 10- 9 (cc - cm / cm 2 - sec - cmHg) Arbitrary desirable or less.
  • Total oxygen permeability coefficient P and 10- 9 (cc - cm / cm 2 ⁇ sec - cmHg) by less, further preventing the ink degradation due to transmission of oxygen in the air for a writing instrument Inki housing member , And the ink can be further prevented from being blown out.
  • the ink stored in the ink storage member for writing implement of the present invention is not particularly limited as long as it is a commonly used ink for writing implement, and may be used for pole pens, pressure pole pens, sign pens, marking pens, and the like. It contains ink for writing implements such as aqueous or oily liquid inks and gel-like inks.
  • FIGS. 1 (a), 1 (b) and 2 show the case where the ink storage member for a writing instrument of the present invention is applied to an ink storage tube (refill) of a pollen.
  • the ink storage member A for a writing implement of the present embodiment has an ink storage tube 11 provided with a pole pen type tip 10 at the tip.
  • Reference numeral 12 denotes pole pen ink filled in the ink storage tube
  • 13 denotes a joint member between the pen tip and the ink storage tube
  • 14 denotes an ink follower.
  • the ink storage tube 11 has a main body 11a (0.7 mm in thickness) made of the above-mentioned various organic polymers, in this embodiment, PP, and a main body 11a.
  • a coat layer with an oxygen permeability coefficient of 10-1 G (cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg) or less at 25 ° C Cry in this embodiment, the thickness of the coat layer made of EVOH) 1.0 m, ethylene molar ratio 38mo 1%) 11b (first invention).
  • main body portion 11 the outer surface of a (outer peripheral surface) in the oxygen permeability coefficient at 25 ° CD ry 10- 10 (cc ⁇ cm / cm 2 - sec - cmHg) or less and comprising organic
  • the configuration may be such that the thickness is 11b (second invention).
  • the outer surface of the main body 11a is composed of the rough surface of (1) above to have a structure without a smooth surface, or the ozone treatment, plasma treatment, corona treatment, ultraviolet irradiation treatment, and high pressure described in (2) above At least one type of activation treatment selected from discharge treatment and acid treatment is applied, and furthermore, a material composed of a material blended with petroleum resin or its derivative described in (3) above, and four types combining these (1) to (3) It may be a main body (the same applies to the embodiments shown in FIG. 3 and thereafter).
  • the ink storage member A for a writing instrument includes a pole pen shaft
  • 16 Used as a pole pen when attached to 15.
  • 16 is a tail plug
  • 17 is a cap body
  • 18 is a seal rubber.
  • FIG. 3 shows an ink tank portion serving as a shaft (ink container) for directly storing ink in a direct liquid type writing instrument having a collector-type structure in which the ink container for a writing instrument according to the present invention is provided.
  • the ink container B for writing implements of the present embodiment is composed of an ink container 21 serving as a shaft for directly storing the ink 20 without absorbing the ink 20 into a batting or the like.
  • the front of 1 is temporarily stopped to prevent the ink 20 pushed out from the ink tank 21 from dropping from the pen tip or air hole when the air in the ink tank 21 expands due to temperature rise etc.
  • An ink reservoir (collector member) 22 for storage is built in, and a pen tip 23 made of a fiber core is provided at the tip of the collector member 22.
  • the ink is drawn out from the ink tank section 21 to the pen tip 23 via an intermediate core 24 provided with an ink flow path 22 a provided in the center hole of the collector member 22.
  • reference numeral 25 denotes a holder member
  • reference numeral 26 denotes a rear shaft fixed to the rear of the ink tank 11
  • reference numeral 27 denotes a cap.
  • the ink may be led out by disposing the rear portion of the pen tip 23 directly in the ink tank 21 without the intermediary of the relay core 24.
  • the ink tank 21 serving as the ink container has a main body (thickness of 1. Omm) made of polypropylene and an outer surface (outer peripheral surface) of the main body having an oxygen transmission coefficient of 10-1Q at 25 ° C dry. (cc ⁇ cm / cm 2 -sec-cmHg) and a coat layer (thickness: 1.2 urn) made of PVA that has been subjected to a water-resistant treatment with boron, which is less than or equal to (the first invention). .
  • the oxygen permeation coefficient on the outer surface portion of the body portion is 25 ° CDr y at 10- 10 (cc ⁇ cm / cm 2 - cmHg - sec) in the organic polymer (this embodiment equal to or less than? And a coat layer (thickness: 2 m) in which tabular inorganic fine particles (in this embodiment, montmorillonite, content: 5% by weight) are dispersed. ).
  • the rear shaft 26 made of polypropylene may be provided with a coat layer (thickness: 7 m) made of PVA that has been subjected to the above-mentioned water resistance treatment with boron.
  • FIG. 4 shows a case where the ink storage member for a writing implement of the present invention is applied to an ink tank portion serving as a shaft (ink container) for directly storing ink in a valve-type writing implement having a valve mechanism section containing a stirring ball. It is.
  • the ink-ink storage member C for a writing implement includes an ink tank 31 serving as a shaft that directly stores the ink 30 without absorbing the ink into a batting or the like. Ink is supplied to a nib 33 made of a fiber core via a valve mechanism 32 in 31.
  • reference numeral 34 denotes a holder member
  • reference numeral 35 denotes a holding member interposed between the valve mechanism 32 and the holder member 34, and holds a rear portion of the pen tip 33
  • reference numeral 36 denotes a cap
  • 37 is a stirring pole.
  • the ink is supplied to the pen tip without passing through the relay core.
  • the relay core is provided, and the ink tank part 31 is composed of the fiber mechanism through the valve mechanism part 32 and the relay core.
  • a configuration may be adopted in which 33 nibs are supplied.
  • the ink tank 31 serving as the ink container has a main body (annular thickness of 2. Omm) made of a cyclic polyolefin and an oxygen transmission coefficient of 25 ° C dry on the outer surface (outer peripheral surface) of the main body. It is composed of a coat layer (thickness: 1.0 fim) made of EVOH that is less than 10 _1Q (cc ⁇ cm / cm 2 -sec-cmHg ).
  • the outer surface portion of the body portion (outer peripheral surface), the oxygen permeability coefficient at 25 ° CD ry 10- 10 (cc ⁇ cm / cm 2 - sec - cmHg) or less and comprising organic high partial element (in this embodiment
  • FIG. 5 shows a case where the ink storage member for a writing implement of the present invention is applied to an ink tank portion of a writing implement in which ink is occluded in an ink storage body such as batting.
  • the ink storage member D for a writing implement of the present embodiment is configured by an ink tank portion 41 serving as a shaft that stores an ink storage body 40 in which the ink is stored in a batting or the like.
  • the rear end portion 42a of the pen tip 42 made of a fiber core abuts on the front portion of the ink occluding body 40, so that the ink of the ink occluding body 40 is supplied to the pen tip 42.
  • 43 is a front shaft member
  • 44 is a tail plug fixed to the rear end of the shaft body 41
  • 45 is a cap.
  • the ink tank 41 serving as the ink container is made of polypropylene.
  • the main body (thickness of l. 0 mm) and, 10 1 the outer surface portion of the body portion (outer peripheral surface) in the oxygen permeability coefficient at 25 ° CD ry () (cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg) coating layer made of EVOH to be hereinafter also is constructed from (a thickness of 1.
  • ink storage containers such as water-based or oil-based liquid ink, and inks for writing implements such as gel inks
  • a collector container structure for accommodating ink for writing implements, batting-type writing implements, etc. tube outer surface portion of the (pole pen refill Lumpur) like ink for a writing instrument housing member
  • the oxygen permeability coefficient at 25 ° CD ry 10- 1 (( cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg) Since the following coat layer (first invention) is formed, oxygen in the air does not pass through the ink storage member for writing implements, preventing deterioration of the ink and improving the scent retention of the ink containing fragrance.
  • a writing instrument accommodating member that can prevent blowout of the ink for a long period of time can be obtained.
  • the outer surface portion of the writing instrument ink containing member, the oxygen permeability coefficient is at 25t D ry 10- 10 (cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg) or less of the plate in the organic polymer Since the coating layer in which the inorganic fine particles are dispersed is formed, the mechanical strength of the coating layer is further improved, and the abrasion resistance is further improved, so that pinholes and the like hardly occur. Oxygen in the air does not permeate into the housing member, and an ink housing member for writing implements that can prevent deterioration of the ink, improve the fragrance retention of the fragrance ink, and prevent the ejection of the ink for a long time can be obtained. Becomes
  • the outer surface of the ink container for writing implements before the formation of the coating layer having the above-mentioned characteristics may be composed of a rough surface to have no smooth surface, or ozone treatment, plasma treatment, corona treatment, and ultraviolet irradiation. Treatment, high-pressure discharge treatment, or acid treatment, or at least one activation treatment.
  • the ink storage member for writing implements is made of petroleum resin or its derivative with respect to 100 parts by weight of a polyolefin-based thermoplastic organic polymer.
  • the coat layer having an oxygen permeability coefficient of 10-1 Q (cc ⁇ cm / cm 2 ⁇ sec-cmHg) at 25 t Dry on the outer surface portion of the ink storage member for writing implement.
  • first invention is formed structure (first invention), or the oxygen permeability coefficient at 25 ° CD ry 10- 10 (cc * cm / cm 2 ⁇ sec ⁇ cmHg) in the following organic polymers It has a structure in which a coat layer in which plate-like inorganic fine particles are dispersed is formed (second invention).
  • oxygen gas is more easily permeated than nitrogen gas. Therefore, by setting the oxygen permeation coefficient to be equal to or less than the above characteristic value, permeation of nitrogen gas can be further suppressed. Therefore, permeation of air and nitrogen gas used for the pressurized writing instrument can be suppressed.
  • the pressurized gas such as a nitrogen gas in the ink storage container is prevented from permeating outside the container.
  • poor writing due to a decrease in the internal pressure of the ink container can be prevented for a long period of time.
  • the ink container for a writing instrument is not limited to the above embodiment, and it goes without saying that it can be changed to various forms without changing the gist of the present invention.
  • Writing instruments Inki receiving member of the present invention the first oxygen permeability coefficient in the outer surface portion of the writing instrument Inki housing member comprised of an organic polymer which houses a writing instrument for Inki with invention in 2 ry 10- 10 (cc ⁇ CmZcm 2 ⁇ sec ⁇ cmHg)
  • the following coating layer is formed, or the oxygen permeation coefficient is applied to the outer surface of the ink container for writing implements composed of an organic polymer that contains the ink for writing implements in the second invention.
  • the coating layer in which the tabular inorganic fine particles are dispersed is formed in the organic polymer 10_ 10 (cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg) or less at 25 "D ry, the present invention
  • the structure other than the ink storage member for writing tools is not particularly limited, and the structure of various writing tools such as a pole pen, a felt-tip pen, and a marking pen is applied.
  • the present invention is also applicable to a member for storing a coating liquid of a coating implement, such as a correction liquid, a coating liquid, or a liquid cosmetic such as cosmetics, in which a writing implement ink is used.
  • a coating liquid of a coating implement such as a correction liquid, a coating liquid, or a liquid cosmetic such as cosmetics, in which a writing implement ink is used.
  • the ink storage member for writing implements is made of a material having a low oxygen permeability coefficient, for example, ethylene, vinyl alcohol copolymer (EVOH), etc.
  • oxygen permeation is reduced, but the environment such as humidified atmosphere is reduced.
  • the resin is lowered, the resin swells due to water vapor in the air, the gas barrier property is reduced, and dimensional changes occur, so that the effects of the present invention cannot be exhibited.
  • An INK container made of PP for a direct liquid type felt pen was manufactured by injection molding.
  • This The PP ink container conforms to the reference numeral 21 in FIG. 3, and has a thickness of 1. Omm, an inner diameter of 7. Omm, and a length of 5 Omm.
  • the entire outer surface of the PP ink container was matted during molding on a mold, and then the entire surface was plasma-treated by glow discharge in the presence of air.
  • the entire outer surface of the matte-treated and plasma-treated PP ink container has an oxygen permeation coefficient of about 1 X 10-13 (cc ⁇ cm / cm 2 -sec • cmHg) of EVOH (ethylene mole) at 25 ° C dry. (38% ratio) to an average thickness of about 1.0 m, using a coating solution with the coating solution viscosity and EVOH solid content adjusted to achieve a total thickness of 1001. did.
  • the whole of the oxygen permeability coefficient P of the PP-made ink container was about 9. 8X 10- 11 (cc ⁇ cm cm 2 'sec' c mH g).
  • Example 1 a direct liquid type pen similar to Example 1 except for the plasma treatment was assembled.
  • the respective oxygen permeability coefficients were the same as in Example 1.
  • Example 1 a direct liquid-type sign pen similar to Example 1 except for the satin finish treatment was assembled.
  • the respective oxygen permeability coefficients were the same as in Example 1. (Example 4, direct liquid type pen)
  • Example 1 a direct liquid type felt-tip pen similar to that of Example 1 was assembled except for both the satin finish treatment and the plasma treatment.
  • the respective oxygen permeability coefficients were the same as in Example 1. '
  • Example 5 direct liquid type felt pen
  • 20 parts by weight of a petroleum resin Alcon P-100, manufactured by Arakawa Chemical Industries
  • PP resin J226E, manufactured by Mitsui Petrochemical Co., Ltd.
  • a PP ink container having the same dimensions as in Example 1 was produced using the compounded resin composition.
  • An EVOH coat was produced in the same manner as in Example 1 above using this PP ink container (without satin finish treatment or plasma treatment). Further, the whole of the oxygen permeability coefficient P of the PP-made ink container about 9. 8 X 10- 11 (cc ⁇ cm / cm 2 - cmHg - sec) was.
  • a direct liquid type felt-tip pen was assembled in the same manner as in Example 1 using this PP ink container.
  • a plasma treatment was made of PP Inki oxygen permeability coefficient across outer surface portion of the container is 25 ° in CD ry about 5 X 10- 14 (cc ⁇ cm / cm 2 - sec - average PVA (99% degree of saponification) of cmHg) thickness of about 2 so that 0 m, and Kotin grayed processed using Deitsupingu method, 1002. the total thickness of the body layer and the coat layer 0 m. Further, the whole of the oxygen permeability coefficient P of the PP-made ink container about 2. 4X 10- 11 (cc ⁇ cm / cm 2 - cmHg - sec) is.
  • a direct liquid type water-based felt-tip pen shown in Fig. 3 was assembled.
  • Example 1 satin treatment a plasma treatment was made of PP Inki oxygen permeability coefficient across outer surface portion of the container is 25 ° in CD ry about 5 X 10- 14 (cc ⁇ cm / the cmHg PVA of complete saponification of) - cm 2 - sec
  • the complex formed with boron was subjected to a coating treatment by a dive method so as to have an average thickness of about 1.0 m, and the total thickness of the main body layer and the coat layer was set to 100. 1.
  • this ⁇ is ⁇ overall oxygen permeability coefficient of ⁇ manufactured ink container about 4. 8 X 10- 11 (cc ⁇ cm / cm 2 - cmHg - sec) first with a which was the PP made Inki container
  • the direct liquid type felt pen shown in Fig. 3 was assembled.
  • PP ink tubes (refills) for direct liquid writing instruments were manufactured by injection molding.
  • This PP ink refill conforms to the reference symbol A in Fig. 1 (a), and has a wall thickness of 0.5mm, an inner diameter of 4mm, and a length of 120mm.
  • the oxygen permeability coefficient of PP was about 5 ⁇ 10 ⁇ 9 (cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg) at 25 ° C. dry.
  • the entire outer surface of the PP ink container was plasma-treated by glow discharge in the presence of air.
  • the plasma-treated PP-made ink container about 1 oxygen permeability coefficient across outer surface portion 25 ° CD ry of X 10- 13 (cc ⁇ cm / cm 2 ⁇ sec - cmHg) of EVOH (ethylene mole ratio 20%)
  • the coating was applied by dipping to an average thickness of about 1.0 m, and the total thickness of the main body layer and the coating layer was 1001.0 m. Produced.
  • Example 8 a refill for a pole pen similar to Example 9 except for the plasma treatment was assembled.
  • the respective oxygen permeability coefficients were the same as in Example 9. (Comparative Example 1)
  • a PP ink container for a direct liquid writing instrument was manufactured by injection molding.
  • This PP ink container complies with the reference numeral 21 in FIG. 3, and has a thickness of 1.0 mm, an inner diameter of 7 mm, and a length of 5 Omm.
  • PP ink tubes (refills) for direct liquid writing instruments were manufactured by injection molding.
  • This PP ink refill conforms to the reference symbol A in Fig. 1 (a), and has a wall thickness of 0.5mm, an inner diameter of 4mm, and a length of 120mm.
  • Oxygen permeability coefficient of the PP was 25 D ry about 5 X 10- 9 (cc ⁇ cm / cm 2 ⁇ sec ⁇ c mHg).
  • Each of the writing implements was filled with the ink of the following composition to prepare each direct liquid type pen and the pole pen shown in Fig. 2, and then evaluated for the ink blowing property and fragrance retention by the following methods. .
  • n 1 within Chikaratsuki, because it was the balloon already, were not evaluated after the c
  • Example 1 1 month 3 months 6 months
  • Oxygen permeation coefficient on the outer surface of the second invention is 25: in Dry 10- 10 (cc ⁇ cm / cm 2 'sec ⁇ cmHg) tabular the organic polymer follows Forming a coating layer in which inorganic fine particles are dispersed].
  • An ink container made of PP for a direct liquid type felt pen was manufactured by injection molding.
  • This PP ink container complies with the reference numeral 21 in FIG. 3, and has a thickness of 1.0 mm, an inner diameter of 6.4 mm, and a length of 120 mm.
  • Oxygen permeability coefficient of the PP is about 10-9 at 25 ° CD ry (cc ⁇ cm / cm 2 - s ec ⁇ cmHg) filed by Was.
  • the entire outer surface of the PP ink container was matted using a mold, and then the entire surface was plasma-treated by glow discharge.
  • the satin treatment, plasma treatment and oxygen permeability coefficient across outer surface portion of the PP made Inki container is 2 5 ° CD ry about 5 X 10- 14 (cc ⁇ cm / cm 2 - sec - cmHg) EV_ ⁇ of 5% by weight of EVOH (ME-100, manufactured by Corp Chemical) dispersed as flat inorganic fine particles in H (38 mol 1% ethylene mole ratio) so as to have an average thickness of about 0.1 m
  • a coating treatment was performed using a dating method to make the total thickness of the main body layer and the coat layer 1000.lm.
  • the oxygen permeability coefficient P of the PP ink container was about 9.8 ⁇ 10 ′′ 11 (cc ⁇ cm / cm 2 ′ sec′cmHg).
  • Example 10 a direct-type felt-tip pen similar to Example 10 except for the plasma treatment was assembled.
  • the respective oxygen permeability coefficients were the same as in Example 10.
  • Example 10 a direct liquid type felt pen similar to Example 10 except for the matte finish treatment was assembled.
  • the respective oxygen permeability coefficients were the same as in Example 10.
  • Example 10 a direct liquid type felt-tip pen similar to that of Example 10 was assembled except for both the satin finish treatment and the plasma treatment.
  • the respective oxygen permeability coefficients were the same as in Example 10.
  • Example 14 direct liquid type felt pen
  • the average thickness is about 0.1 m obtained by dispersing 5% by weight of synthetic My power (MK-100, manufactured by Corp Chemical) as EVOH as flat inorganic fine particles instead of My power.
  • MK-100 synthetic My power
  • the coating treatment was performed using the dive method, and the total thickness of the main body layer and the coat layer was set to 1000.1 in the same manner as in Example 10 to assemble the direct liquid type pen as in Example 10.
  • the oxygen permeability coefficient P of the whole ink container made of PP was about 4.5 ⁇ 10 10 (cc ⁇ cm / cm 2 -sec-cmH).
  • Example 10 montmorillonite (Kunipia F, manufactured by Kunimine Industries Co., Ltd.) as tabular inorganic fine particles instead of my force was dispersed at 5% by weight in EVOH so as to have an average thickness of about 0.1 m. Then, a coating process was performed using a dipping method, and a direct liquid type pen as in Example 10 was assembled in the same manner as in Example 10 except that the total thickness of the main body layer and the coat layer was set to 1000.
  • montmorillonite Koreanipia F, manufactured by Kunimine Industries Co., Ltd.
  • the whole of the oxygen permeability coefficient P of the PP-made ink container about 4. 0X 10 - was 10, cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg).
  • Example 10 In Example 10 described above, 20 parts by weight of petroleum resin (Alcon P-100, Arakawa Chemical Industries) was used as the ink container material for 100 parts by weight of PP resin (J226E, manufactured by Mitsui Petrochemical Co., Ltd.). A PP ink container having the same dimensions as in Example 1 was prepared using a resin composition containing the same. Oxygen permeability coefficient of the PP-made ink container was about 10 9 25 ° CD ry (cc ⁇ cm / cm 2. Sec * cmHg).
  • Example 10 Using this PP ink container (without satin finish treatment or plasma treatment), a coat layer of EVOH + flat inorganic fine particle dispersion was produced in the same manner as in Example 10 above. Further, the whole of the oxygen permeability coefficient P of the PP-made ink container about 4. 5X 10- 10 (cc ⁇ cm / cm 2 - cmHg - sec) was. Using this PP ink container, a direct liquid signin was assembled in the same manner as in Example 10.
  • the oxygen permeation coefficient is about 10-13 (cc ⁇ cm / cm) at 25 °
  • An average of 1% by weight of synthetic smectite (Smecton SA, manufactured by Kunimine Industries, Ltd.) as tabular inorganic fine particles dispersed in PVA ( 2 -sec-cmHg) at a saponification degree of 98% was dispersed in PVA.
  • Coating was applied by dipping to a thickness of about 0.1 lm, and the total thickness of the main body layer and the coat layer was 100.1 m.
  • the oxygen permeability coefficient P of the PP ink container was about 4.0 ⁇ 10 ⁇ 10 (cc ⁇ cm / cm 2 -sec-cmHg).
  • Example 10 Example 10 and likewise satin treatment, a plasma treatment was made of PP Inki oxygen permeability coefficient across outer surface portion of the container is 25 XD ry about 5 X 10- 14 (cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg) tabular inorganic particles as synthesized My force in completely saponified PVA of (MK-100, manufactured by Co-op Chemical Co., Ltd.) dispersion allowed 5 wt% with respect to PVA, boric acid PVA fully Gen of The complex formed with the boron in it was coated by dipping so as to have an average thickness of about 0.1 m, so that the total thickness of the main body layer and the coat layer was 1000. lm. Further, the whole of the oxygen permeability coefficient P of the PP-made ink container about 4. 8X 10 one 11 was (cc - sec * cmHg - cmZcm 2).
  • PP ink tubes (refills) for direct liquid writing instruments were manufactured by injection molding.
  • This PP ink refill conforms to the reference symbol A in Fig. 1 (a), and has a wall thickness of 0.8mm, an inner diameter of 6.4mm, and a length of 12 Omm.
  • Oxygen permeability coefficient of the PP was about 5 X 10- 9 at 25 ° CD ry (cc ⁇ cm / cm 2 ⁇ sec • cmHg).
  • the entire outer surface of the PP ink container was matted using a mold, and then the entire surface was plasma-treated by glow discharge.
  • the satin treatment a plasma treatment was made of PP Inki container outer surface portion across the oxygen permeability coefficient of 2 5t: about at D ry 5X 10- 13 (cc - cm / cm 2 - sec - cmH) of P VA ( 5% by weight of PVA with synthetic My power (MK-100, manufactured by Coop Chemical Co., Ltd.) dispersed as tabular inorganic fine particles in a saponification degree of 98%) so as to have an average thickness of about 0.1 m
  • a coating treatment was performed using a dipping method to make the total thickness of the main body layer and the coat layer 1000.l m.
  • the oxygen permeability coefficient P of the whole ink container made of PP was about 4.0 ⁇ 10-1 G (cc ⁇ cm / cm 2 ⁇ sec ⁇ cmHg).
  • pole pen shown in FIG. 1 was assembled using this PP container. (Example 20, pole pen)
  • Example 19 a refill for a polpen similar to Example 19 except for the plasma treatment was assembled.
  • the respective oxygen permeability coefficients were the same as in Example 19.
  • Example 1 Coating Layer in which Flat Inorganic Fine Particles Are Not Dispersed
  • the direct liquid type pen of Example 1 described above was used.
  • a PP ink container for a direct liquid type felt pen was manufactured by injection molding.
  • This PP ink container conforms to the reference symbol 21 in FIG. 3, and has a thickness of 1.0 mm, an inner diameter of 7.0 mm, and a length of 50 mm.
  • the oxygen permeability coefficient of PP is about 5 at 25 ° C dry.
  • x 1 O— 9 (cc ⁇ cmZcm 2 'sec'cmHg).
  • the entire outer surface of the PP ink container was matted during molding on a mold, and then the entire surface was plasma-treated by glow discharge in the presence of air.
  • the oxygen permeation coefficient is about 1 X 10—13 (cc-cm / cm 2 -sec at 2 ry) over the entire outer surface of the matte-treated and plasma-treated PP ink container.
  • EVOH ethylene mole ratio 38 mo 17% is coated using a coating solution that has been adjusted for coating solution viscosity and EVOH solids so that the average thickness is about 1.0 m. And the total thickness of the coating layer was 1001.0 zm. Further, the whole of the oxygen permeability coefficient P of the PP-made ink container was about 9. 8X10- 11 (cc ⁇ cm / cm 2 'sec' c mH.
  • Each of the obtained writing implements is filled with the ink having the nucleus composition used in Example 1 of the first invention, etc., and each of the direct liquid type pens and the pole pens shown in FIG. 2 is manufactured.
  • the ink blowing performance and fragrance retention were evaluated by the following method, and the rub resistance was further evaluated by the following method.
  • each of the above-described ink composition for a direct liquid writing instrument and the ink composition for a direct liquid writing instrument was filled with each 1 g.
  • the ink compositions for the pole pens and the pole pens (perfume types) used in Example 8 and the like were filled with lg.
  • the coating layer of each of the writing instruments thus obtained was gripped with a nail, and the state of peeling of the coating layer was evaluated according to the following evaluation criteria.
  • Example 1 1 month 3 months 6 months
  • Example 1 0 ⁇ ⁇ ⁇ Example 1 1 ⁇ ⁇ ⁇ Example 1 2 ⁇ ⁇ ⁇ Example 1 3 ⁇ ⁇ ⁇ Example 1 4 ⁇ ⁇ ⁇ Example 1 5 ⁇ ⁇ ⁇ Example 1 6 ⁇ ⁇ ⁇ Example 1 7 ⁇ ⁇ ⁇ Example 1 8 ⁇ ⁇ ⁇ Example 1 9 ⁇ ⁇ ⁇ Example 2 0 ⁇ ⁇ ⁇ Table 7
  • Example 1 1 month 3 months 6 months
  • Example 1 0 ⁇ ⁇ ⁇ Example 1 1 ⁇ ⁇ ⁇ Example 1 2 ⁇ ⁇ ⁇ Example 1 3 ⁇ ⁇ ⁇ Example 1 4 ⁇ ⁇ ⁇ Example 1 5 ⁇ ⁇ ⁇ Example 1 6 ⁇ ⁇ ⁇ Example 1 7 ⁇ ⁇ ⁇ Example 1 8 ⁇ ⁇ ⁇ Example 1 9 ⁇ ⁇ ⁇ Example 2 0 ⁇ ⁇ ⁇ Table 9
  • Example 1 0-2 0 as the range of the present invention the oxygen in the air passes through the Inki housing member for a writing instrument As a result, it is possible to prevent the ejection of the ink for a long period of time, to improve the scent retention of the scented ink, and to obtain a coating layer in which the flat inorganic fine particles are not dispersed.
  • the ink storage member for writing implements a direct liquid writing implement having a collector structure for accommodating ink for writing implements, and an ink storage tube for a ballpoint pen
  • oxygen in the air does not pass through the ink storage member for writing implements, preventing deterioration of the ink, improving the scent retention of the scented ink, and extending the discharge of the ink.
  • Ink for writing implements that can prevent the period A receiving member is provided.
  • Coat layer tabular inorganic fine particles are dispersed in the following organic polymers
  • the present invention provides an ink container for writing implements, in which the mechanical strength of the coat layer is improved and the scratch resistance is excellent.
  • the outer surface of the writing instrument ink storage member is made of a rough surface to have a structure without a smooth surface, or at least one selected from ozone treatment, plasma treatment, corona treatment, ultraviolet irradiation treatment, high pressure discharge treatment, and acid treatment.
  • Various kinds of activation treatments were performed, and a petroleum resin and / or a derivative thereof was blended in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the polyolefin-based thermoplastic organic polymer in the ink storage member for writing implements.
  • the adhesion to the coat layer is further improved, oxygen is not transmitted, and the abrasion resistance is improved, and the ink is prevented from deteriorating. Furthermore, it is possible to prevent the ejection of ink for a longer period of time.

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  • Mechanical Engineering (AREA)
  • Pens And Brushes (AREA)

Abstract

An ink holding member for a writing material comprising an organic polymer, characterized in that it has, formed on the outer surface thereof, a coating layer having an oxygen permeation coefficient of 10-10 (cc·cm/cm2·sec·cmHg) under a 25˚C Dry condition or a coating layer comprising an organic polymer material having an oxygen permeation coefficient of 10-10 (cc·cm/cm2·sec·cmHg) under a 25˚C Dry condition and, dispersed therein, inorganic particles in the form of a flat plate. The above ink holding member can be used for holding an ink for a writing material, such as a water-born or oil-born liquid ink and an ink in the form of a gel, and allows the prevention of the deterioration of the ink and the blow-out of the ink due to the permeation of oxygen in the air into the member.

Description

明 細 書 筆記具用インキ収容部材 技術分野  Description Ink storage components for writing instruments Technical field
この発明は、 水性又は油性の液状インキ、 ゲル状インキなどの筆記具用イン キを収容する筆記具用ィンキ収容容器、 ィンキ収容管等の筆記具用ィンキ収容 部材に関し、 更に詳しくは、 筆記具用インキ収容部材に空気中の酸素が透過す ることによるインキの劣化防止、 並びに香料入りインキの保香性向上、 更には インキの吹き出しを防止することができる筆記具用インキ収容部材に関する。 背景技術  The present invention relates to an ink container for a writing instrument, such as a water-based or oil-based liquid ink or a gel ink, and an ink container for a writing instrument, such as an ink container tube, and more particularly to an ink container for a writing instrument. The present invention relates to an ink storage member for a writing instrument that can prevent deterioration of the ink due to permeation of oxygen in the air, improve the scent retention of the scented ink, and prevent the ejection of the ink. Background art
従来より、 多種多様の筆記具が知られているが、 一般に、 コレクター構造を 有する直液筆記具、 中綿式筆記具等のィンキ収容容器やポールペンのィンキ収 容管 （インキチューブ、 リフィール） の役目は、 水性又は油性の液状インキ、 ゲル状ィンキなどの筆記具用ィンキを収容し、 かつィンキを構成している溶媒 の揮発を防止することが主目的である。  Conventionally, a wide variety of writing instruments have been known, but in general, the function of an ink container such as a direct liquid writing instrument having a collector structure, a batting type writing instrument, and an ink container (ink tube, refill) of a pole pen is water-based. The main purpose is to accommodate ink for writing implements such as oil-based liquid ink and gel-like ink, and to prevent the solvent constituting the ink from volatilizing.
通常、 これらの筆記具用インキ収容容器やインキ収容管は、 化学的安定性、 耐溶剤性、 経済性、 生産性等の点からポリプロピレンなどの有機高分子 （合成 樹脂等） から構成されているものである。  Normally, these ink storage containers and ink storage tubes for writing implements are made of organic polymers such as polypropylene (synthetic resin, etc.) from the viewpoints of chemical stability, solvent resistance, economy, and productivity. It is.
しかしながら、 本発明者らの研究及び知見によれば、 経時的にみると、 イン キ収容容器ゃィンキ収容管に空気、 中でも酸素が透過してィンキ収容容器ゃィ ンキ収容管の中に入ることにより、 インキが酸ィ匕されインキの増粘、 色材濃度 の低下などのインキの劣化を促進し、 更にはインキの吹き出しなどの問題が加 速され、 筆記具としての寿命を短くするという課題があることが判った。 また、 加圧ポ一ルペン等では、 安価で成形性、 透明性に優れるポリプロピレ ンなどをィンキ収容部材に使用した場合、 ィンキ収容容器内の窒素ガスなどの 加圧気体が容器外に透過して容器内圧が低下することによる筆記不良を生じる という課題を有している。 However, according to the research and findings of the present inventors, over time, air, particularly oxygen, permeates into the ink container and the ink container enters the ink container. As a result, the ink is oxidized, which promotes the deterioration of the ink such as thickening of the ink and a decrease in the color material concentration, and further accelerates the problems such as the ejection of the ink and shortens the life of the writing instrument. I found it to be. In addition, pressure-sensitive pens and other materials are inexpensive and have excellent moldability and transparency. However, when an ink container or the like is used for the ink container, there is a problem in that a pressurized gas such as nitrogen gas in the ink container permeates out of the container and the internal pressure of the container decreases, resulting in poor writing.
一方、 特開平 8— 1 3 3 3 4 6号公報には、 抗菌剤入り筆記具などの文具類 の包装方法に関して、 包材中に脱酸素剤を内在せしめて空気中の酸素や湿気と の接触を極力抑えることにより文具類の変色防止を図ることができる抗菌剤入 り文具類の包装方法が開示されている。  On the other hand, Japanese Unexamined Patent Publication No. 8-133333 / 1996 discloses a method of packaging stationery such as writing implements containing an antibacterial agent, in which a deoxidizer is included in the packaging material to allow contact with oxygen or moisture in the air. A method for packaging stationery containing an antibacterial agent that can prevent discoloration of stationery by minimizing the amount of discoloration is disclosed.
しかしながら、 この公報に開示される技術は、 長期間に亘り店頭の陳列棚等 に陳列放置された場合 （製造後から消費者にわたるまで） の抗菌剤入り筆記具 などの文具類の酸ィ匕による変色を防止するものであり、 本発明とはその目的、 作用及びその構成 （技術思想） が異なるものである。  However, the technology disclosed in this official gazette discolors stationery and other stationery such as antibacterial writing instruments when left on display shelves at stores for a long period of time (from the time of manufacture to the end of consumers). The purpose, action and configuration (technical idea) of the present invention are different from those of the present invention.
また、 インキの調製や充填に際して取り込まれるインキ中に混入する空気 （ 酸素） によるインキの酸化劣化の防止策として、 インキ中にビタミン Cゃビタ ミン£、 その他酸素と反応又は吸収するなどの成分を添加する技術も知られて いる。  In addition, as a measure to prevent the ink from being oxidized and degraded by air (oxygen) taken into the ink when preparing and filling the ink, vitamin C and other components that react or absorb with oxygen are added to the ink. Addition techniques are also known.
しかしながら、 これらの技術は、 インキへの添加量には自ずと制限があり、 極微量の添加量となるため、 比較的短期間にその機能を喪失するという課題が あるものである。 なお、 上記技術には、 インキ収容部材の酸素透過により生じ るィンキの酸化劣化、 ィンキのペン先からの吹き出し性等の課題の認識はない ものである。  However, these techniques have a problem in that the amount added to the ink is naturally limited, and the function is lost in a relatively short time because the amount is extremely small. In the above-mentioned technology, there is no recognition of problems such as oxidative degradation of the ink caused by oxygen permeation of the ink storage member and the ability of the ink to blow out from the pen tip.
本発明は、 上記従来技術の課題及び現状等に鑑み、 これを解消しょうとする ものであり、 水性又は油性の液状インキ、 ゲル状インキなどの筆記具用インキ を収容する筆記具用ィンキ収容容器ゃィンキ収容管等の筆記具用ィンキ収容部 材に、 空気中の酸素が透過することによるインキの劣化防止、 並びに香料入り インキの保香性向上、 更にはインキの吹き出しを長期間防止することができ、 並びに、 加圧ポールペン等の窒素ガスなどの加圧気体による加圧式筆記具など は、 容器内の窒素ガスなどの加圧気体が外気側へ透過して容器内圧が低下する ことによる筆記不良を来たすので、 例えば、 安価で成形性、 透明性に優れるポ リプロピレンなどの高分子を使用できないなどの課題も解決できる筆記具用ィ ンキ収容部材を提供することを目的とする。 発明の開示 SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems and the present state of the art, and has been made to solve the problem. An ink container for writing implements, such as a water-based or oil-based liquid ink or a gel ink, is provided. It is possible to prevent the deterioration of the ink due to the permeation of oxygen in the air into the ink container for writing implements such as the storage tube, to improve the fragrance retention of the scented ink, and to prevent the ink from being blown out for a long time. Pressurized writing utensils with pressurized gas such as nitrogen gas such as pressurized pole pens, etc. In this case, poor pressurization occurs due to the reduced pressure inside the container due to the passage of pressurized gas such as nitrogen gas inside the container to the outside air side.For example, polymers such as polypropylene, which are inexpensive and have excellent moldability and transparency, are used. It is an object of the present invention to provide an ink container for writing implements that can solve problems such as the inability to use a pen. Disclosure of the invention
本発明者らは、 上記従来技術の課題等について鋭意検討を重ねた結果、 筆記 具用ィンキを収容する有機高分子から構成される筆記具用ィンキ収容部材の外 側表面部 （外周面部） に特定物性のコート層を形成することにより、 上記目的 の筆記具用インキ収容部材が得られることを見いだし、 本発明を完成するに至 つたのである。  The present inventors have conducted intensive studies on the above-mentioned problems of the prior art and the like, and as a result, identified the outer surface portion (outer peripheral surface portion) of the writing instrument ink storage member composed of an organic polymer for accommodating the writing instrument ink. By forming a coating layer having physical properties, the present inventors have found that the ink storage member for a writing instrument with the above object can be obtained, and have completed the present invention.
すなわち、 本発明の筆記具用インキ収容部材は、 次の（1)〜（16)に存する。 That is, the ink storage member for a writing instrument of the present invention resides in the following (1) to (16).
(1) 筆記具用ィンキを収容する有機高分子から構成される筆記具用ィンキ収容 部材であって、 該筆記具用インキ収容部材の外側表面部に酸素透過係数が 25 。CD r yで 10_1° (c c ' cm/ cm2 - s e c - cmHg) 以下のコ一ト 層が形成されていることを特徴とする筆記具用ィンキ収容部材。 (1) An ink storage member for a writing implement composed of an organic polymer for accommodating the ink for a writing implement, wherein the outer surface of the ink storage member for the writing implement has an oxygen permeability coefficient of 25. 10 _1 ° with CD ry (cc 'cm / cm 2 - sec - cmHg) for writing instruments Inki housing member characterized by the following co one coat layer is formed.
(2) .筆記具用ィンキを収容する有機高分子から構成される筆記具用ィンキ収容 部材であって、 該筆記具用インキ収容部材の外側表面部に酸素透過係数が 25 0 で10—1。 （じ じ ' cm/ cm2 · s e c · cmHg) 以下の有機高 分子中に平板状無機微粒子が分散されているコート層が形成されていることを 特徴とする筆記具用ィンキ収容部材。 (2). A Inki housing member for a writing instrument constructed of an organic polymer which accommodates the writing instrument Inki, the oxygen permeability coefficient in the outer surface portion of the ink for a writing instrument housing member 10 1 25 0. (Ink / cm 2 · sec · cmHg) An ink container for writing implements, characterized in that a coating layer in which tabular inorganic fine particles are dispersed in an organic polymer having a density of not more than (cm / cm 2 · sec · cmHg) is formed.
(3) 筆記具用ィンキ収容部材が筆記具用ィンキ収容容器又はィンキ収容管であ ることを特徴とする上記（1)又は (2)記載の筆記具用ィンキ収容部材。  (3) The ink container for a writing instrument according to the above (1) or (2), wherein the ink container for a writing instrument is an ink container for a writing instrument or an ink container tube.
(4) 平板状無機微粒子が天然粘土鉱物類、 合成粘土鉱物類から選ばれる薄い層 構造を有する平板層状無機物であることを特徴とする上記 (2)又は (3)記載の筆 記具用ィンキ収容部材。 (5) 平板層状無機物の層間が陽イオン交換能を有する又は有機処理されている ことを特徴とする上記 (4)記載の筆記具用ィンキ収容部材。 (4) The ink for writing implement according to the above (2) or (3), wherein the tabular inorganic fine particles are a tabular layered inorganic substance having a thin layer structure selected from natural clay minerals and synthetic clay minerals. Housing member. (5) The ink container for a writing instrument according to the above (4), wherein the interlayer of the flat layered inorganic substance has a cation exchange ability or is organically treated.
(6) 平板状無機微粒子の含有量が有機高分子中に 0 . 1〜2 5重量％分散され ていることを特徴とする上記 (2)〜（5)の何れか一つに記載の筆記具用インキ収 容部材。  (6) The writing implement as described in any one of (2) to (5) above, wherein the content of the tabular inorganic fine particles is dispersed in the organic polymer in a range of 0.1 to 25% by weight. Ink storage member.
(7) コート層がポリビエルアルコール層、 エチレン ·ビニルアルコール共重合 体層、 ポリアミド層の少なくとも一つから構成されていることを特徴とする上 記 (1)又は (3)記載の筆記具用ィンキ収容部材。  (7) The ink for a writing instrument according to the above (1) or (3), wherein the coat layer is composed of at least one of a polyvinyl alcohol layer, an ethylene / vinyl alcohol copolymer layer, and a polyamide layer. Housing member.
(8) コート層の有機高分子がポリビエルアルコール、 エチレン 'ビニルアルコ —ル共重合体、 ポリアミドの少なくとも一つから構成されていることを特徴と する上記 (2)〜（6)の何れか一つに記載の筆記具用ィンキ収容部材。  (8) Any one of the above (2) to (6), wherein the organic polymer of the coating layer is composed of at least one of polyvinyl alcohol, ethylene vinyl alcohol copolymer, and polyamide. 4. An ink container for a writing instrument according to any one of the above.
(9) コート層は耐水化処理が施されているコート層であることを特徴とする上 記 〜（8)の何れか一つに記載の筆記具用ィンキ収容部材。  (9) The ink container for a writing instrument according to any one of the above (8), wherein the coat layer is a coat layer subjected to a water-resistant treatment.
(10) 筆記具用ィンキ収容部材の外側表面部が粗面部からなり平滑でないこと を特徴とする上記（1)〜（9)の何れか一つに記載の筆記具用インキ収容部材。 (10) The ink storage member for a writing implement according to any one of the above (1) to (9), wherein the outer surface portion of the ink storage member for a writing implement has a rough surface and is not smooth.
(11) 筆記具用インキ収容部材の外側表面部には、 オゾン処理、 プラズマ処理 、 コロナ処理、 紫外線照射処理、 高圧放電処理及び酸処理から選ばれる少なく とも 1種の活性化処理が施されていることを特徴とする上記（1)〜（10)の何れ か一つに記載の筆記具用ィンキ収容部材。 (11) At least one activation treatment selected from ozone treatment, plasma treatment, corona treatment, ultraviolet irradiation treatment, high pressure discharge treatment, and acid treatment is applied to the outer surface of the ink storage member for writing implements. The ink container for a writing instrument according to any one of the above (1) to (10), which is characterized in that:
(12) 筆記具用インキ収容部材は、 熱可塑性の有機高分子から構成されている ことを特徴とする上記（1) ~ (11)の何れか一つに記載の筆記具用ィンキ収容部 材。 (12) The ink storage member for a writing implement according to any one of the above (1) to (11), wherein the ink storage member for a writing implement is made of a thermoplastic organic polymer.
(13) 筆記具用インキ収容部材は、 ポリオレフイン系熱可塑性有機高分子から 構成されていることを特徴とする上記（1)〜（12)の何れか一つに記載の筆記具 用インキ収容部材。  (13) The ink storage member for a writing implement according to any one of the above (1) to (12), wherein the ink storage member for a writing implement is composed of a polyolefin-based thermoplastic organic polymer.
(14) ポリオレフイン系熱可塑性有機高分子には、 ポリオレフイン系熱可塑性 有機高分子 100重量部に対して、 石油樹脂及び/又はその誘導体が 5〜40 重量部配合されていることを特徴とする上記（13) 3記載の筆記具用インキ収容 部材。 (14) Polyolefin-based thermoplastic organic polymers include polyolefin-based thermoplastics (13) The ink storage member for a writing implement as described in (13) above, wherein 5 to 40 parts by weight of a petroleum resin and / or a derivative thereof is blended with respect to 100 parts by weight of the organic polymer.
(15) 筆記具用インキ収容部材の肉厚とコート層とを合わせた総厚が 0. 5〜 5. 0mmであり、 コート層の厚さが 0. 1〜 2000 ^ mであることを特徴 とする上記 (1)〜(14)の何れか一つに記載の筆記具用インキ収容部材。  (15) The total thickness including the thickness of the ink storage member for the writing implement and the coating layer is 0.5 to 5.0 mm, and the thickness of the coating layer is 0.1 to 2000 ^ m. The ink storage member for a writing instrument according to any one of the above (1) to (14).
(16) 筆記具用インキ収容部材の肉厚を L 1、 酸素透過係数を P 1とし、 コー ト層の厚さを L 2、 酸素透過係数を P 2とし、 筆記具用インキ収容部材のコ一 ト層を形成した時の全体の酸素透過係数を Pとした場合に、 全酸素透過係数 P を下記式 （I) で定義したときに、 この全酸素透過係数 Pが 10—9 (c c · cm/cm2 - s e c - cmHg) 以下で'あることを特徴とする上記ひ）〜 (15)の何れか一つに記載の筆記具用ィンキ収容部材。 (16) The thickness of the ink storage member for writing implements is L1, the oxygen permeability coefficient is P1, the thickness of the coating layer is L2, and the oxygen permeability coefficient is P2. the overall oxygen transmission coefficient when the layer has been formed is P, when defining the total oxygen permeability coefficient P by the following formula (I), the total oxygen permeability coefficient P is 10- 9 (cc · cm / cm 2 -sec-cmHg) The ink container for a writing instrument according to any one of the above (1) to (15), wherein
(L 1 +L2) /P = L 1/P 1 +L 2/P 2 (I) なお、 本発明 （後述する実施例等を含む） で規定する 「酸素透過係数」 （単 位 c c · cmZcm2 · s e c · cmHg) とは、 下記式 （II) により算出さ れる値をいう。 (L 1 + L 2) / P = L 1 / P 1 + L 2 / P 2 (I) The “oxygen permeability coefficient” (unit cc · cmZcm) defined in the present invention (including the examples described later). 2 · sec · cmHg) refers to the value calculated by the following formula (II).
酸素透過係数 =酸素透過度 X試験片の厚さ （II) 上記式 （ I ) 中、 酸素透過度 （酸素透過率、 単位： c c/m2 · 24h r · a tm) は、 単位分圧差で単位時間に単位面積の試験片を透過する酸素の体積 をいい、 ある時間に試験片を透過した酸素の量を実測することによって、 下記 式により求められる。 Oxygen permeability = oxygen permeability X thickness of test specimen (II) In the above formula (I), oxygen permeability (oxygen permeability, unit: cc / m 2 · 24 hr · a tm) is expressed by the unit partial pressure difference. The volume of oxygen that permeates a test piece in a unit area per unit time. It is obtained by the following formula by actually measuring the amount of oxygen permeating a test piece at a certain time.
酸素透過度-酸素透過量ノ 〔 （高圧側分圧一低圧側分圧） X透過面積 X時間 Oxygen permeability-Oxygen permeation amount [(High pressure partial pressure-Low pressure partial pressure) X Permeation area X time
) )
また、 本発明で規定する 「酸素透過係数」 は、 上記で定義されるように、 酸 素透過度に試験片の厚さを乗じて、 単位厚さ当たりの透過量に換算したもので あるので、 試験片の厚さと、 その酸素透過度がわかれば、 必要な酸素透過度を 得るためにどれだけの厚さのコート層を選択すればよいかがわかるものとなる 更に、 本発明で規定する 「Dry」 とは、 各温度で湿度 30%以下をいい、 「25°C Dry」 とは、 25 °Cの環境下において湿度 30 %以下をいい、 ま た、 「50 D ry」 は、 50での環境下において湿度 30 %以下をいう。 また、 本発明で規定する 「平板層状無機物」 とは、 粘度銥物等の無機層状物 質であり、 壁かい性、 膨潤性などの性質の他に有機物や無機物をインターカレ ートして層間化合物を形成する性質を有する無機微粒子をいう。 図面の簡単な説明 The “oxygen permeability coefficient” defined in the present invention is, as defined above, a value obtained by multiplying the oxygen permeability by the thickness of the test piece and converting it into a permeation amount per unit thickness. If you know the thickness of the specimen and its oxygen permeability, you can determine the required oxygen permeability It is possible to understand how thick a coat layer should be selected in order to obtain. Furthermore, "Dry" defined in the present invention means a humidity of 30% or less at each temperature, and "25 ° C Dry" The term “dry” refers to a humidity of 30% or less in an environment of 25 ° C, and “50 Dry” refers to a humidity of 30% or less in an environment of 50. In addition, the term “plate-like layered inorganic substance” as defined in the present invention refers to an inorganic layered substance such as a viscous substance, and in addition to properties such as wall swelling property and swelling property, an organic or inorganic substance is intercalated to form an interlayer. Inorganic fine particles having the property of forming a compound. BRIEF DESCRIPTION OF THE FIGURES
第 1図 （a) は、 本発明の筆記具用インキ収容部材をポールペン用インキ収 容管に適用した一例を断面態様で示す縦断面図であり、 （b) は、 その要部を 示す部分横断面図であり、 第 2図は、 第 1図のボールペン用インキ収容管を備 えたポ一ルペンの縦断面図である。  FIG. 1 (a) is a longitudinal cross-sectional view showing an example in which the ink storage member for a writing implement of the present invention is applied to an ink storage tube for a pole pen, and FIG. 1 (b) is a partial cross-sectional view showing a main part thereof. FIG. 2 is a longitudinal sectional view of a pole pen provided with the ball-point pen ink storage tube of FIG. 1.
第 3図は、 本発明の筆記具用インキ収容部材を直液式サインペンに適用した 一例を示す縦断面図であり、 第 4図は、 本発明の筆記具用インキ収容部材をバ ルブ機構を備えた筆記具に適用した一例を示す断面図であり、 第 5図は、 本発 明の筆記具用ィンキ収容部材をィンキを中綿等のィンキ吸蔵体に吸蔵させた筆 記具に適用した一例を示す断面図である。 発明を実施するための最良の形態  FIG. 3 is a vertical cross-sectional view showing an example in which the ink storage member for writing implement of the present invention is applied to a direct liquid type pen, and FIG. 4 is a drawing showing the ink storage member for writing implement of the present invention provided with a valve mechanism. FIG. 5 is a cross-sectional view showing an example applied to a writing implement. FIG. 5 is a cross-sectional view showing an example in which the ink storage member for a writing implement of the present invention is applied to a writing implement in which the ink is inserted into an ink absorbing body such as a batting. It is. BEST MODE FOR CARRYING OUT THE INVENTION
以下に、 本発明の実施の形態を図面を参照しながら詳しく説明する。  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
本発明となる第 1発明の筆記具用ィンキ収容部材は、 筆記具用ィンキを収容 する有機高分子から構成される筆記具用インキ収容部材、 具体的には、 筆記具 用インキ収容容器又はインキ収容管の外側表面部 （外側周面部） に、 酸素透過 係数が 25°CD r yで 10— 10 (c c · cm/cm2 · s e c · cmHg) 以 下のコート層が形成されていることを特徴とするものであり、 また、 第 2発明 の筆記具用ィンキ収容部材は、 筆記具用ィンキを収容する有機高分子から構成 される筆記具用ィンキ収容部材であって、 該筆記具用ィンキ収容部材の外側表 面部に酸素透過係数が 25 :D r yで 10— 1Q (c c · cm/cm2 · s e c · cmHg) 以下の有機高分子中に平板状無機微粒子が分散されているコート 層が形成されていることを特徴とするものである。 The ink container for a writing instrument according to the first aspect of the present invention is an ink container for a writing instrument composed of an organic polymer that accommodates the ink for a writing instrument, specifically, an ink container for a writing instrument or the outside of an ink container tube. the surface portion (outer peripheral surface), the oxygen permeability coefficient at 25 ° CD ry 10- 10 (cc · cm / cm 2 · sec · cmHg) or less A lower coating layer is formed, and the ink container for writing implement of the second invention is an ink container for writing implement composed of an organic polymer for accommodating the ink for writing apparatus. there, the oxygen permeability coefficient in the outer table surface portion of the writing instrument Inki housing member 25: in D ry 10- 1Q (cc · cm / cm 2 · sec · cmHg) tabular inorganic fine particles in the following organic polymers It is characterized in that a dispersed coat layer is formed.
以下において、 「本発明」 というときは、 上記第 1発明及び第 2発明の両方 を含むものである。  Hereinafter, the “present invention” includes both the first invention and the second invention.
本発明の筆記具用インキ収容部材の構造としては、 例えば、 第 1図及び第 2 図におけるポールペンにおけるインキ収容管 （リフィール） 、 第 3図における コレクター構造を備えた直液式筆記具におけるィンキを直接貯溜する軸体 （ィ ンキ容器） となるインキタンク部、 第 4図におけるバルブ機構を有する筆記具 におけるインキを直接貯溜する軸体 （インキ容器） となるインキタンク部、 第 5図における中綿式筆記具におけるィンキをィンキ吸蔵体に吸蔵させて収容す るインキ収容部などが挙げられ、 筆記具用インキを収容する収容部材であれば 、 特に限定されるものではない。  Examples of the structure of the ink storage member for a writing implement of the present invention include, for example, an ink storage pipe (refill) in a pole pen in FIGS. 1 and 2 and an ink in a direct liquid writing implement having a collector structure in FIG. Ink tank part that becomes a shaft body (ink container) that performs ink, ink tank part that becomes a shaft body (ink container) that directly stores ink in a writing instrument having a valve mechanism in FIG. 4, and ink tank part that becomes a batting-type writing instrument in FIG. There is no particular limitation as long as it is a storage member that stores ink for writing implements, such as an ink storage section that stores the ink for storage in the ink storage body.
これらの筆記具用インキ収容部材は、 ポリプロピレン （PP) 、 ポリエチレ ン （PE) 、 環状ポリオレフイン、 ポリメチルペンテン、 ポリエチレンテレフ 夕レート （PET) 、 ポリブチレンテレフタレ一ト （PBT) 、 ポリスチレン (PS) 、 ポリ力一ポネート （PC) 、 シリコーンエラストマ一、 ァクリロ二 トリル一ブタジエン—スチレン共重合体 （ABS) 、 ナイロン樹脂 （ポリアミ ド） 、 ポリイミド、 ポリ塩化ビニル （PVC) などの有機高分子を用いて構成 されるものであり、 好ましくは、 熱可塑性の有機高分子、 更に好ましくは、 耐 溶剤性、 経済性、 生産性等からポリプロピレン （PP) 、 ポリエチレン （PE ) 、 環状ポリオレフイン、 ポリメチルペンテン、 ブテン一 1、 ペンテン一 1、 へキセン— 1、 ォクテン— 1などの任意の a—ォレフィンの単独重合体若し くはこれらの二種以上の共重合体、 または、 これらの単独重合体及び Z又は共 重合体の混合物を適宜使用したものが望ましい。 These ink storage materials for writing instruments include polypropylene (PP), polyethylene (PE), cyclic polyolefin, polymethylpentene, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), Constructed using organic polymers such as polyacrylonitrile (PC), silicone elastomer, acrylonitrile-butadiene-styrene copolymer (ABS), nylon resin (polyamide), polyimide, and polyvinyl chloride (PVC) Preferably, it is a thermoplastic organic polymer, and more preferably, polypropylene (PP), polyethylene (PE), cyclic polyolefin, polymethylpentene, butene-one, from the viewpoint of solvent resistance, economy, productivity and the like. 1, a-pentene-1, hexene-1, octene-1, etc. Homopolymer of Preferably, a copolymer of two or more of these, or a mixture of these homopolymers and Z or a copolymer is appropriately used.
本第 1発明では、 筆記具用インキ収容部材の外側表面部 （外側周面部） に、 上記特性の酸素透過係数のコ一卜層を形成して該ィンキ収容部材を実質的に本 体 （層） +コート層の 2層以上の構造とするものであるが、 該インキ収容部材 の本体 （層） を他の異なる有機高分子層を用いて多層形成してもよいものであ る。  In the first invention, a coat layer having an oxygen permeability coefficient having the above characteristics is formed on an outer surface portion (outer peripheral surface portion) of the ink storage member for a writing instrument, so that the ink storage member is substantially a main body (layer). It has a structure of two or more coat layers, but the main body (layer) of the ink containing member may be formed in multiple layers using another different organic polymer layer.
また、 本第 2発明では、 筆記具用インキ収容部材の外側表面部 （外側周面部 ) に、 上記特性の酸素透過係数の有機高分子中に平板状無機微粒子が分散され ているコート層を形成して該インキ収容部材を実質的に本体 （層） +コート層 の 2層以上の構造とするものであるが、 該インキ収容部材の本体 （層） を他の 異なる有機高分子層を用いて多層形成してもよいものである。  Further, in the second invention, a coating layer in which plate-like inorganic fine particles are dispersed in an organic polymer having an oxygen permeability coefficient of the above characteristics is formed on the outer surface (outer peripheral surface) of the ink storage member for a writing instrument. In this case, the ink storage member has a structure of substantially two or more layers of a main body (layer) and a coat layer. However, the main body (layer) of the ink storage member is multilayered using another different organic polymer layer. It may be formed.
更に、 本発明 （第 1発明及び第 2発明） では、 筆記具用インキ収容部材 （本 体部） とコート層との密着性をより確実にして本発明の効果を更に向上せしめ る点から、 筆記具用インキ収容部材の本体部は下記①〜③に記載の構造等とな るものを用いることが好ましい。  Further, in the present invention (the first invention and the second invention), the writing implement is further improved in that the adhesiveness between the ink storage member for the writing implement (main body) and the coating layer is further improved to further improve the effect of the present invention. It is preferable to use a body having the structure described in the following ① to ③ for the main body of the ink storage member.
①筆記具用ィンキ収容部材本体部の外側表面部を粗面部から構成して平滑面が ない構造となる筆記具用インキ収容部材を用いる。  (1) Use an ink storage member for writing implements that has a rough surface on the outside surface of the ink storage body for writing implements and has no smooth surface.
②筆記具用インキ収容部材本体部の外側表面部をオゾン処理、 プラズマ処理、 コロナ処理、 紫外線照射処理、 高圧放電処理及び酸処理から選ばれる少なくと も 1種の活性化処理を施した筆記具用ィンキ収容部材を用いる。  (2) A writing instrument ink in which at least one activation treatment selected from an ozone treatment, a plasma treatment, a corona treatment, an ultraviolet irradiation treatment, a high-pressure discharge treatment, and an acid treatment is applied to the outer surface of the ink storage member body for the writing implement. A housing member is used.
③筆記具用インキ収容部材本体部の材料として、 上述のポリオレフィン系熱可 塑性有機高分子 1 0 0重量部に対して、 石油樹脂及び Z又はその誘導体が 5〜 4 0重量部配合されたものから成形された筆記具用インキ収容部材を用いる。 上記①の本体部の外側表面部を粗面部から構成して平滑面がない構造とする 方法としては、 例えば、 筆記具用インキ収容部材となる筆記具用インキ収容容 器又はインキ収容管などの外側表面をサンドブラスト処理、 溶剤処理、 金型表 面を粗面状にすることにより梨地化などの粗面化処理を施すことにより行うこ とができる。 (3) As a material for the ink storage member main body of the writing implement, a mixture of 100 to 100 parts by weight of the above-mentioned polyolefin-based thermoplastic organic polymer and 5 to 40 parts by weight of petroleum resin and Z or a derivative thereof. A formed ink storage member for a writing implement is used. As a method of forming the outer surface portion of the main body portion from the rough surface portion and having no smooth surface in the above (1), for example, an ink storage container for a writing implement serving as an ink storage member for a writing implement may be used. It can be performed by subjecting the outer surface of the container or the ink storage tube or the like to a sandblasting treatment, a solvent treatment, or a roughening treatment such as a matte finish by roughening the mold surface.
また、 上記②のオゾン処理としては、 筆記具用インキ収容部材の外側表面を オゾン分子と接触させて、 ヒドロキシペルォキシ基や水酸基や力ルポ二ル基等 の官能基を導入することを目的とし、 筆記具用ィンキ収容部材をオゾンに暴露 することにより行われる。 暴露方法としては、 オゾンが存在する雰囲気に所定 時間保持する方法、 オゾン気流中に所定時間暴露する方法等が挙げられるが、 特に限定されない。  In addition, the ozone treatment described in (1) above is intended to introduce a functional group such as a hydroxyperoxy group, a hydroxyl group, or a hydroxyl group by bringing the outer surface of the ink storage member for a writing instrument into contact with ozone molecules. This is performed by exposing the ink container for writing implements to ozone. Examples of the exposure method include a method in which the film is kept in an atmosphere containing ozone for a predetermined time, a method in which the film is exposed to an ozone stream for a predetermined time, and the like, but are not particularly limited.
上記②のプラズマ処理としては、 筆記具用インキ収容部材を空気、 酸素、 窒 素、 二酸化炭素、 アルゴン、 ネオンなどを含む容器内におき、 グロ一放電によ り生じるプラズマに晒すことにより行われ、 筆記具用ィンキ収容部材の外側表 面に酸素、 窒素などを含むカルボン酸基、 カルポニル基、 アミノ基などの官能 基を導入することを目的とし、 プラズマ発生の放電形式は、 直流放電、 低周波 放電、 ラジオ波放電、 マイクロ波放電などがあるが特に限定されない。  The plasma treatment in (1) above is performed by placing the ink storage member for writing implements in a container containing air, oxygen, nitrogen, carbon dioxide, argon, neon, etc., and exposing it to plasma generated by glow discharge. The purpose of introducing a functional group such as a carboxylic acid group containing oxygen and nitrogen, a carbonyl group, an amino group, etc., on the outer surface of the ink container for writing implements is as follows: DC discharge, low-frequency discharge , Radio wave discharge, microwave discharge, etc., but are not particularly limited.
上記②のコ口ナ処理としては、 コロナ放電が生じる電界内に筆記具用インキ 収容部材を通過等させることにより、 筆記具用ィンキ収容部材の外側表面を活 性化処理することができる。  In the edge treatment described in the above (1), the outer surface of the ink storage member for writing implement can be activated by passing the ink storage member for writing implement into an electric field in which corona discharge occurs.
上記②の紫外線照射処理としては、 筆記具用ィンキ収容部材の外側表面に紫 外線を照射する方法で、 筆記具用ィンキ収容部材の外側表面に紫外線が照射さ れると、 筆記具用ィンキ収容部材の表面領域の二重結合等の化学構造に紫外線 が吸収され、 吸収されたエネルギーにより化学結合が切断され、 生じたラジカ ルに空気中の酸素が結合することによって得られるカルポニル基、 カルポキシ ル基などを導入することを目的とし、 紫外線を照射する光源としては、 低圧水 銀灯、 高圧水銀灯、 超高圧水銀灯、 キセノンランプ、 メタルハライドランプ等 を用いることができるが特に限定されない。 上記②の高圧放電処理としては、 筆記具用ィンキ収容部材を多数設けた電極 間に数十万ポルトの高電圧を加え、 空気中で放電させて処理する方法で、 放電 によって空気中の酸素と筆記具用ィンキ収容部材の表面が活性化され、 表面に 酸素が取り込まれ、 極性基を導入することにより筆記具ィンキ収容部材の外側 表面を活性化処理することができる。 The ultraviolet irradiation treatment of (1) above is a method of irradiating the outer surface of the writing instrument ink storage member with ultraviolet light. When the outer surface of the writing instrument ink storage member is irradiated with ultraviolet light, the surface area of the writing instrument ink storage member is reduced. UV rays are absorbed by the chemical structure of the double bond, etc., and the absorbed energy breaks the chemical bond, introducing carbonyl and carboxyl groups, etc., which are obtained by bonding oxygen in the air to the resulting radical. As a light source for irradiating ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used, but is not particularly limited. The high-pressure discharge treatment described in (1) above is a method in which a high voltage of several hundred thousand ports is applied between the electrodes provided with a large number of ink storage members for the writing implement, and the discharge is carried out in the air. By activating the surface of the ink storage container, oxygen is taken into the surface and the polar group is introduced, so that the outer surface of the writing equipment storage container can be activated.
上記②の酸処理としては、 筆記具用インキ収容部材をクロム混酸液、 次亜塩 素酸ソ一ダ Z塩酸/水系、 塩素酸塩—硫酸系、 硫酸などに直接浸漬させること により行うことができる。  The acid treatment of (1) above can be performed by directly immersing the ink storage member for writing implements in a chromium mixed acid solution, sodium hypochlorite Z hydrochloric acid / water system, chlorate-sulfuric acid system, sulfuric acid, or the like. .
上記③の石油樹脂及び Z又はその誘導体としては、 例えば、 水酸基含有水素 化石油樹脂又はその誘導体など挙げられる。 具体的には、 市販のハイレッツ G - 1 0 0 (三井石油化学社製） 、 ペトロジン # 1 0 0 (三井石油化学社製） 、 アルコン P— 1 0 0 (荒川化学工業社製） などが挙げられる。  Examples of the petroleum resin and Z or a derivative thereof described in (3) above include a hydroxyl group-containing hydrogenated petroleum resin or a derivative thereof. Specifically, commercially available Heylets G-100 (manufactured by Mitsui Petrochemical), Petrozine # 100 (manufactured by Mitsui Petrochemical), Alcon P-100 (manufactured by Arakawa Chemical), etc. Can be
この石油樹脂の使用量が 5重量部未満であると、 コート層との更なる密着性 が向上せず、 一方、 4 0重量部を越えてもその効果は変わらず、 また、 筆記具 用インキ収容部材の機械的強度が低下する場合があり、 好ましくない。  If the amount of the petroleum resin is less than 5 parts by weight, the adhesion to the coating layer will not be further improved, while if it exceeds 40 parts by weight, the effect will not be changed. The mechanical strength of the member may decrease, which is not preferable.
上記①〜③の筆記具用インキ収容部材 （本体部） を用いることにより、 特に 、 P Pに代表されるポリオレフイン系樹脂を用いて上記①〜③の処理を施した には、 後述するポリビエルアルコール （P VA) 、 エチレン 'ビニルアルコー ル共重合体 （E V OH) 、 ポリアミド （ナイロン樹脂） などから構成される所 定の酸素透過係数のコート層又は所定の酸素透過係数の有機高分子中に平板状 無機微粒子が分散されているコート層との密着性が更に向上できるものとなる 上記①〜③の筆記具用インキ収容部材 （本体部） は、 夫々各単独のものを用 いてもよいが、 必要に応じて、 更に、 上記①及び②、 ①及び③、 ②及び③、 並 びに、 上記①〜③を組合わせたもの （合計 4種のもの） を用いてもよいもので  By using the ink storage member (main body part) for writing implements of the above ① to ③, in particular, when the above processing of the above ① to ③ was performed using a polyolefin resin represented by PP, PVA), ethylene-vinyl alcohol copolymer (EVOH), polyamide (nylon resin), etc. Adhesion with the coating layer in which the inorganic fine particles are dispersed can be further improved. The ink storage members (main body) for writing implements in (1) to (3) above may each be used individually, Accordingly, the above (1) and (2), (1) and (3), (2) and (3), and the combination of the above (1) to (3) (total of 4 types) may be used.
0 ある。 0 is there.
本発明において、 第 1発明では、 上記構成となる筆記具用インキ収容部材の 外側表面部 （外側周面部） に形成するコート層は、 酸素透過係数が 2 S^D r yで 10_10 (c c · cm/ cm2 - s e c - cmHg) 以下とすることが必 要であり、 また、 第 2発明では、 筆記具用インキを収容する有機高分子から構 成される筆記具用ィンキ収容部材であって、 該筆記具用ィンキ収容部材の外側 表面部に酸素透過係数が 25°CD r yで 10— 10 (c c · cm/cm2 · s e c · cmHg) 以下の有機高分子中に平板状無機微粒子が分散されているコー ト層が形成されていることが必要である。 In the present invention, in the first invention, coating layer formed on the outer surface portion of the writing instrument ink receiving member comprising the above structure (outer peripheral surface) is 10_ oxygen permeability coefficient at 2 S ^ D ry 10 (cc · cm / cm 2 -sec-cmHg) or less, and in the second invention, the ink container for a writing implement composed of an organic polymer accommodating the ink for a writing implement, Coat the plate-like inorganic fine particles in the oxygen permeability coefficient at 25 ° CD ry 10- 10 (cc · cm / cm 2 · sec · cmHg) in the following organic polymer on the outer surface portion of the use Inki housing member is dispersed It is necessary that a layer is formed.
好ましくは、 第 1発明及び第 2発明共に、 10— 11 (c c · cm/cm2 · s e c - cmHg) 以下のコート層、 更に好ましくは、 10— 12〜 10-15 ( c c ' cm/cm2 - s e c - cmHg) のコート層とすることが望ましい。 上記第 1発明において、 酸素透過係数が 25 D r yで 10 1Q (c c · c m/cm2 · s e c · cmHg) を越えるコート層又は上記第 2発明において 、 酸素透過係数が 25°〇0 で10—1() (c c · cm/ cm2 · s e c · c mHg) を越える有機高分子中に平板状無機微粒子が分散されているコート層 では、 本発明の効果、 すなわち、 筆記具用インキを収容する筆記具用インキ収 容部材に、 空気中の酸素が透過することによるインキの劣化防止、 並びにイン キの吹き出しを長期間防止するという効果を達成することができないものとな る。 Preferably, the first and second aspects of the present invention both, 10- 11 (cc · cm / cm 2 · sec - cmHg) or less of the coating layer, more preferably, 10- 12 ~ 10- 15 (cc 'cm / cm 2 -sec-cmHg). In the above first invention, the coating layer having an oxygen permeability coefficient of more than 10 1 Q (cc · cm / cm 2 · sec · cmHg) at 25 Dry or in the second invention, the oxygen permeability coefficient is 10 ° at 25 ° 〇0. 1 () (cc · cm / cm 2 · sec · cmHg), a coating layer in which tabular inorganic fine particles are dispersed in an organic polymer exceeding The effect of preventing the deterioration of the ink due to the permeation of oxygen in the air to the ink storage member for use and the effect of preventing the ejection of the ink for a long time cannot be achieved.
本発明におけるコート層は、 第 1発明では、 酸素透過係数が 25°CD r yで 10"10 (c c · cm/ cm2 - s e c - cmHg) 以下となるコート層、 ま た、 第 2発明では、 酸素透過係数が 25°CD r yで 10— 1Q (c c · cm/c m2 · s e c · cmHg) を越える有機高分子中に平板状無機微粒子が分散さ れているコート層となるものであれば、 特に限定されず、 例えば、 第 1発明で は、 酸素透過率が少ない有機高分子からなる層、 金属層、 有機金属化合物など を加水分解することにより得られる無機物層などが挙げられ、 第 2発明では、 上記特性の酸素透過係数となる有機高分子中に平板状無機微粒子が分散されて いる層などが挙げられる。 In the first invention, the coat layer according to the first invention has an oxygen permeability coefficient of 10 ″ 10 (cc · cm / cm 2 -sec-cmHg) or less at 25 ° C.Dry. as long as the oxygen permeability coefficient of a flat plate-like inorganic fine particles is coated layers which are dispersed in an organic polymer exceeding by 25 ° CD ry 10- 1Q (cc · cm / cm 2 · sec · cmHg), There is no particular limitation. For example, in the first invention, a layer made of an organic polymer having a low oxygen permeability, a metal layer, an organometallic compound, etc. In the second invention, a layer in which plate-like inorganic fine particles are dispersed in an organic polymer having the above-described characteristic oxygen permeation coefficient is exemplified.
本発明 （第 1発明及び第 2発明） においてコート層に用いる有機高分子とし ては、 上記特性の酸素透過係数となる有機高分子であればよく、 好ましくは、 薄膜でも優れた耐酸素透過性、 製造性、 経済性、 安全性、 皮膚刺激性などの点 から、 有機高分子がポリビニルアルコール （PVA) 、 エチレン ·ビニルアル コール共重合体 （EVOH) 、 ポリアミドであるものが望ましい。 中でも、 低 吸湿性の点から PVAの場合は、 ゲン化度が 50%以上のものが更に好ましく 、 EVOHの場合は、 エチレンモル比率が 8 Omo 1 %以下、 好ましくは、 2 0〜80mo l %以下、 更に好ましくは、 30〜60mo l %以下、 特に、 3 0〜5 Omo 1 %が更に好ましい。  In the present invention (the first invention and the second invention), the organic polymer used for the coating layer may be an organic polymer having the oxygen permeability coefficient of the above characteristics, and is preferably a thin film having excellent oxygen permeability. It is desirable that the organic polymer is polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), or polyamide from the viewpoints of productivity, economy, safety, and skin irritation. Among them, from the viewpoint of low hygroscopicity, in the case of PVA, it is more preferable that the degree of genification is 50% or more, and in the case of EVOH, the ethylene mole ratio is 8 Omo 1% or less, preferably 20 to 80 mol% or less. More preferably, it is 30 to 60 mol% or less, particularly preferably 30 to 5 Omo 1%.
本第 1発明において、 上記 PVA層、 EVOH層などの樹脂のコート層の形 成は、 筆記具用ィンキ収容部材を P V Aや E V O Hなどの酸素透過率の小さい 高分子を所定溶剤に溶解させディッピング法などによりコ一ティングする方法 や、 共押し出し法、 更にはプロ一成形方法などによりガスバリアコート層を形 成することができる。 また、 金属層の成形では、 蒸着法、 無電界メツキ法など で形成できる。 無機物層は、 筆記具用インキ収容部材を加水分解反応可能な有 機金属化合物などを含む溶液中に浸漬又は溶液を部材表面に塗布し、 加水分解 を経て脱水縮合等の重縮合反応により無機物層を形成できる。  In the first invention, the resin coating layer such as the PVA layer and the EVOH layer is formed by dissolving a polymer having a low oxygen permeability, such as PVA or EVOH, in a predetermined solvent in the ink container for writing implements by a dipping method or the like. The gas barrier coat layer can be formed by a coating method, a co-extrusion method, or a professional molding method. The metal layer can be formed by a vapor deposition method, an electroless plating method, or the like. The inorganic material layer is formed by immersing the ink storage member for writing implements in a solution containing an organic metal compound capable of undergoing a hydrolysis reaction or applying the solution to the surface of the member, and subjecting the inorganic material layer to a polycondensation reaction such as dehydration condensation after hydrolysis. Can be formed.
本第 2発明において、 上記特性の酸素透過係数となる有機高分子中に分散さ れる平板状無機微粒子は、 気体 （酸素など） の迂回効果を発現させるために有 機高分子中に分散させるものである。  In the second invention, the plate-like inorganic fine particles dispersed in the organic polymer having the oxygen permeability coefficient having the above characteristics are dispersed in the organic polymer in order to exert a bypass effect of gas (such as oxygen). It is.
平板状無機微粒子としては、 例えば、 タルク、 マイ力、 天然雲母、 合成雲母 、 スメクタイト、 モンモリロナイト、 ベントナイト、 カオリナイト等の天然又 は合成の薄い層構造を有する粘土鉱物の平板層状無機物、 並びに、 ガラス、 酸  Examples of the plate-like inorganic fine particles include a plate-like inorganic material of a clay mineral having a natural or synthetic thin layer structure, such as talc, myriki, natural mica, synthetic mica, smectite, montmorillonite, bentonite, kaolinite, and glass. The acid
2 化チタンから選ばれる少なくとも 1種 （各単独又は 2種以上の混合物） が挙げ られる。 Two At least one kind (each alone or a mixture of two or more kinds) selected from titanium oxide is exemplified.
これらの平板状無機微粒子のうち上記平板層状無機物の層間は、 分散性の向 上、 有機高分子、 モノマー、 オリゴマーなどを層間にインター力レートさせる などの点から陽イオン交換能を有する又は有機処理されていることが望ましい この平板層状無機物の層間を陽イオン交換能を付与する方法としては、 有機 四級アンモニゥム塩でイオン交換を行う方法などが挙げられ、 また、 有機処理 する方法としては、 シランカップリング剤、 チタンカップリング剤、 アルミキ レート剤、 金属アルコシキドなどや各種反応性官能基などを有する有機モノマ 一、 オリゴマーなどによる有機処理方法が挙げられる。  Among these tabular inorganic fine particles, the interlayer between the above-mentioned tabular inorganic substances has a cation-exchanging ability or an organic treatment from the viewpoint of improving dispersibility, interfacing organic polymers, monomers, oligomers, etc. between the layers. As a method for imparting cation exchange ability between the layers of the plate-like layered inorganic material, there is a method of performing ion exchange with an organic quaternary ammonium salt, and the like. Examples of the method include an organic treatment method using a coupling agent, a titanium coupling agent, an aluminum chelating agent, an organic monomer or an oligomer having a metal alkoxide, various reactive functional groups, or the like.
用いることができる平板状無機微粒子の市販品として、 例えば、 MK— 1 0 0 (コープケミカル社製、 マイ力） 、 ィォナイト （水澤化学社製） 、 S WN, S AN, S T N, S E N, S P N (スメクタイト、 コープケミカル社製） 、 ベ ントナイト （豊順鉱業社製） 、 合成無機高分子スメクトン （クニミネ工業社製 ) 、 クニピア （モンモリナイト、 クニミネ工業社製） 、 カオリナイト （土屋力 ォリン工業社製） などが挙げられる。  Commercially available tabular inorganic fine particles that can be used include, for example, MK-100 (manufactured by Coop Chemical Co., Ltd., My Strength), Zeonite (manufactured by Mizusawa Chemical Co., Ltd.), SWN, SAN, STN, SEN, SPN ( Smectite, Corp Chemical Co., Ltd., Bentonite (Toyojun Mining Co., Ltd.), Synthetic inorganic polymer smecton (Kunimine Kogyo Co., Ltd.), Kunipia (Montmorinite, Kunimine Kogyo Co., Ltd.), Kaolinite (Tsuchiya Riki Korin Kogyo Co., Ltd.) And the like.
本第 2発明に用いる平板状無機微粒子の含有量は、 有機高分子中に 0 . 1〜 2 5重量％、 好ましくは、 0 . 5〜2 0重量％、 更に好ましくは、 0 . 5〜1 5重量％分散されていることが好ましい。  The content of the flat inorganic fine particles used in the second invention is 0.1 to 25% by weight, preferably 0.5 to 20% by weight, more preferably 0.5 to 1% by weight in the organic polymer. Preferably, it is dispersed at 5% by weight.
この含有量が 0 . 1 %未満であると、 平板状無機微粒子が有機高分子中に点 在する格好になり気体 （酸素など） の迂回効果を発現し難くなり、 また、 2 0 重量％を超えると、 平板状無機微粒子が有機高分子中に過剰に存在し平板状無 機微粒子を有機高分子で覆いきれなくなりボイドが存在するようになり逆に気 体 （酸素など） が透過し易くなつてしまうことことになる。  If the content is less than 0.1%, the plate-like inorganic fine particles are scattered in the organic polymer, making it difficult to exhibit a bypass effect of gas (such as oxygen). If it exceeds, the plate-like inorganic fine particles are excessively present in the organic polymer, and the plate-like inorganic fine particles cannot be covered with the organic polymer, so that voids are present, and conversely, gas (such as oxygen) easily permeates. It will be.
本第 2発明において、 上記特性の平板状無機微粒子を上記特性となる酸素透 過係数の有機高分子中に分散させる方法としては、 ワニスの場合は、 ポールミ ル、 高速ディゾルバ一、 超音波などにより行うことができる。 In the second aspect of the present invention, the flat inorganic fine particles having the above-mentioned characteristics are converted into oxygen-permeable particles having the above-mentioned characteristics. As a method of dispersing in an organic polymer having an excess coefficient, in the case of a varnish, it can be carried out using a Paul mill, a high-speed dissolver, or ultrasonic waves.
また、 この平板状無機微粒子が分散されているコート層の形成は、 筆記具用 インキ収容部材を塗布液に浸潰し （デイツピング処理し） 、 溶剤を乾燥させる ことなどにより行うことができる。  The coating layer in which the flat inorganic fine particles are dispersed can be formed, for example, by immersing the ink storage member for a writing implement in a coating solution (by performing a dipping process) and drying the solvent.
本発明 （第 1発明及び第 2発明） では、 上記特性のコ一ト層を形成すること により、 本発明の効果を発揮できるものであるが、 更に、 表面タック性の軽減 、 更なる低吸湿性の点から、 コート層は、 更に耐水化処理が施されているコー ト層であってもよいものである。  In the present invention (the first invention and the second invention), the effect of the present invention can be exhibited by forming the coating layer having the above-mentioned characteristics. However, the surface tackiness is further reduced, and the moisture absorption is further reduced. From the viewpoint of properties, the coat layer may be a coat layer further subjected to a water-resistant treatment.
この耐水化処理としては、 例えば、 コート層を形成している有機高分子の水 酸基と反応して実質的に水酸基の数を減らすことにより、 具体的には、 1 0 0 °C以上で熱処理 （フレーム処理） 、 アルデヒド類による水酸基との架橋反応、 メチロール化合物との架橋反応、 エポキシ化合物との架橋反応、 エステル類と の架橋反応、 ジイソシァネートとの架橋反応、 銅、 硼素 （ホウ砂、 硼酸ナトリ ゥム等の硼素化合物も含む） 、 アルミニウム、 チタン、 ジルコニウム、 スズ、 バナジウムなどの金属化合物との錯体形成などにより水酸基の数を減らして耐 水化処理を行うことができる。  The water-resistance treatment may be performed, for example, by reducing the number of hydroxyl groups by reacting with the hydroxyl groups of the organic polymer forming the coating layer. Heat treatment (flame treatment), cross-linking reaction with hydroxyl group by aldehydes, cross-linking reaction with methylol compound, cross-linking reaction with epoxy compound, cross-linking reaction with esters, cross-linking reaction with diisocyanate, copper, boron (borax, boric acid) A water-resistant treatment can be performed by reducing the number of hydroxyl groups by forming a complex with a metal compound such as aluminum, titanium, zirconium, tin, and vanadium, and the like, including boron compounds such as sodium.
例えば、 上記 P VA層、 E VOH層などのコート層を用いた場合には、 P V Aや E VOH等の水酸基を硼酸、 硼酸ナトリゥム等の硼素化合物と反応せしめ て錯体形成することにより、 または、 ジメチロールゥレアなどの架橋反応によ り部分的に高分子同士を架橋させることにより行うことができる。 耐水化処理 方法は、 上記方法に限定されるものではない。  For example, when a coat layer such as the above PVA layer or EVOH layer is used, a hydroxyl group such as PVA or EVOH is reacted with a boron compound such as boric acid or sodium borate to form a complex, or It can be carried out by partially cross-linking polymers by a cross-linking reaction such as methylol-rea. The water resistance treatment method is not limited to the above method.
更に、 本発明 （第 1発明及び第 2発明） において、 上記特性のコート層の耐 擦過性等の機械強度を高めるために、 ワニス中に、 シリコーン系化合物、 フッ 素系化合物、 または、 脂肪酸系ワックス等を添加することができる。  Further, in the present invention (the first and second inventions), a silicone-based compound, a fluorine-based compound, or a fatty acid-based compound is contained in the varnish in order to increase the mechanical strength such as the abrasion resistance of the coat layer having the above characteristics. Wax and the like can be added.
シリコーン系化合物としては、 例えば、 シリコーンオイル、 変性シリコーン オイル、 シリコーンレジン、 シリコーン系カップリング剤等が挙げられ、 具体 的には、 信越化学工業社製の KF— 100、 KF-56 (シリコーンオイル） 、 東芝シリコーン社製の TSF— 410、 TSF— 4446、 TSF-471 0 (変性シリコーンオイル） 、 信越化学工業社製の KP— 316、 316 A ( シリコーンレジン） 等が挙げられるが、 これらに限定されるものではなく、 こ れらの 2種以上を混合して使用してもよい。 Silicone compounds include, for example, silicone oil, modified silicone Examples include oils, silicone resins, and silicone-based coupling agents. Specifically, KF-100, KF-56 (silicone oil) manufactured by Shin-Etsu Chemical Co., Ltd., TSF-410, TSF-4446 manufactured by Toshiba Silicone Co., Ltd. , TSF-4710 (modified silicone oil), KP-316, 316A (silicone resin) manufactured by Shin-Etsu Chemical Co., Ltd., and the like, but are not limited thereto. You may mix and use.
フッ素系化合物としては、 例えば、 フッ素系界面活性剤等が挙げられ、 具体 的には、 大日本インキ化学工業社製のメガファック F— 470、 F— 173、 F— 177等が挙げられるが、 これらに限定されるものではなく、 これらの 2 種以上を混合して使用してもよく、 また、 上記のシリコーン系化合物と混合し て使用してもよい。  Examples of the fluorine-based compound include fluorine-based surfactants, and specific examples thereof include Megafac F-470, F-173, and F-177 manufactured by Dainippon Ink and Chemicals, and the like. The present invention is not limited thereto, and two or more of these may be used as a mixture, or may be used as a mixture with the above-mentioned silicone compound.
脂肪酸系ワックスとしては、 耐擦過性を与える点から脂肪酸アミド系ヮック スを使用することが好ましく、 飽和脂肪酸アミド、 不飽和脂肪酸アミド、 変性 脂肪酸アミド等が挙げられる。 具体的には、 和光純薬社製のステアリン酸アミ ド、 ォレイン酸アミド等が挙げられるが、 これらに限定されるものではなく、 これらの 2種以上を混合して使用してもよく、 また、 上記のシリコーン系化合 物、 フッ素系化合物と混合して使用してもよい。  As the fatty acid wax, it is preferable to use a fatty acid amide wax from the viewpoint of imparting scratch resistance, and examples thereof include a saturated fatty acid amide, an unsaturated fatty acid amide, and a modified fatty acid amide. Specific examples include stearic acid amide and oleic acid amide manufactured by Wako Pure Chemical Industries, Ltd., but are not limited thereto, and a mixture of two or more of these may be used. It may be used as a mixture with the above-mentioned silicone compound and fluorine compound.
本発明 （第 1発明及び第 2発明） において、 筆記具用インキ収容部材 （本体 部） の肉厚とコート層とを合わせた総厚 （本体部の厚さ +コート層の厚さの合 計） は、 収容するインキ種、 用いる本体部の有機高分子種などにより変動する が、 好ましくは 0. 5〜5. 0mm、 更に好ましくは、 0. 7〜2. Ommと することが望ましく、 また、 コート層の厚さは、 好ましくは 0. 1〜2000 m、 更に好ましくは、 1. 0〜200 mとすることが望ましい。  In the present invention (the first invention and the second invention), the total thickness including the thickness of the ink storage member for the writing implement (the main body) and the coating layer (the total thickness of the main body and the thickness of the coating layer). Varies depending on the type of ink to be contained, the type of organic polymer used in the main body, and the like, but is preferably 0.5 to 5.0 mm, more preferably 0.7 to 2.0 mm, and The thickness of the coat layer is preferably from 0.1 to 2000 m, more preferably from 1.0 to 200 m.
上記総厚を 0. 5〜5. 0mmとし、 かつ、 コート層の厚さを 0. 1〜20 0 とすることにより、 成形性、 機械的強度等に問題を生じることなく、 より確実に酸素の透過を防止して、 ィンキの劣化防止及びィンキの吹き出し等 を防止することができるものとなる。 By setting the total thickness to 0.5 to 5.0 mm and the thickness of the coat layer to 0.1 to 200, it is possible to more reliably reduce oxygen without causing problems in moldability, mechanical strength, etc. To prevent the deterioration of the ink and blow out the ink Can be prevented.
上記総厚が 0. 5mm未満であると、 成形性、 インキ収容部材の強度の面で 不具合を生じることがあり、 また、 総厚が 5. 0mmを越える厚みであると、 耐酸素透過性は向上するが、 視認性 （インキ残量を視認等） を有する部材とす るためには視認性が劣ることとなり、 更に、 設計の自由度の低下を招くことと なる。  If the total thickness is less than 0.5 mm, problems may occur in terms of moldability and the strength of the ink containing member, and if the total thickness is more than 5.0 mm, the oxygen permeability will be poor. Although it is improved, a member having visibility (for example, the amount of remaining ink is visually recognized) becomes inferior in visibility and further reduces design flexibility.
また、 コート層の厚さが 0. 1 mであると、 膜の機械的強度の低下を招き 、 耐酸素透過性の低下を生じることとなり、 また、 コート層の厚さが 2000 tmを越えると、 耐酸素透過性は向上するが、 視認性 （インキ残量を視認等） を有する部材とするためには視認性が劣ることとなり、 更に、 設計の自由度の 低下を招くこととなる。  Further, if the thickness of the coat layer is 0.1 m, the mechanical strength of the film will be reduced, and the oxygen permeability will be reduced. If the thickness of the coat layer exceeds 2000 tm, Although the oxygen permeability is improved, the visibility is deteriorated in order to obtain a member having visibility (for example, the amount of remaining ink is visually recognized), and the degree of freedom of design is reduced.
本発明 （第 1発明及び第 2発明） では、 上記構成となる筆記具用インキ収容 部材の外側表面部 （外周面部） に上記各物性のコート層を形成することにより 、 ィンキ残量視認確認可能な透明性又は半透明性を維持しながら空気中の酸素 が透過することがなくなり、 インキの劣化防止、 香料インキの保香性向上、 並 びにインキの吹き出しを長期間防止することができ、 第 2発明では、 更に、 表 面タック性が抑制され、 更に膜強度が向上するものであるが、 更にこれらの効 果を向上させるために、 好ましくは、 第 1図に示すように、 筆記具用インキ収 容部材の肉厚を Ll、 酸素透過係数を PIとし、 コート層の厚さを L 2、 酸素 透過係数を P 2とし、 筆記具用インキ収容部材のコ一ト層を形成した時の全体 の酸素透過係数を Pとした場合に、 全酸素透過係数 Pを下記式 （I) で定義し たときに、 この全酸素透過係数 Pが 10—9 (c c · cm/ cm2 · s e c · c mHg) 以下とすることが望ましい。 In the present invention (the first invention and the second invention), the ink remaining amount can be visually confirmed by forming the coating layer having the above-mentioned physical properties on the outer surface portion (outer peripheral surface portion) of the ink storage member for a writing instrument having the above configuration. Oxygen in the air does not pass while maintaining transparency or translucency, preventing deterioration of the ink, improving the fragrance retention of the fragrance ink, and preventing the ejection of the ink for a long time. In the invention, the surface tackiness is further suppressed, and the film strength is further improved. In order to further improve these effects, preferably, as shown in FIG. The thickness of the container is Ll, the oxygen transmission coefficient is PI, the thickness of the coating layer is L2, the oxygen transmission coefficient is P2, and the total oxygen when the coating layer of the ink storage member for writing implements is formed When the transmission coefficient is P , When defining the total oxygen permeability coefficient P by the following formula (I), it is desirable that the total oxygen permeability coefficient P is a 10- 9 (cc · cm / cm 2 · sec · c mHg) below.
(L 1 +L 2) ZP = L 1ZP 1 +L 2/P 2 (I) なお、 第 1図はリフィールについて説明するものであるが、 第 2図に以下の 軸体がインキ収容容器 （インク収容部） となるものであっても全酸素透過係数 Pが 10- 9 (c c - cm/cm2 - s e c - cmHg) 以下とすることが望ま しい。 (L 1 + L 2) ZP = L 1 ZP 1 + L 2 / P 2 (I) Fig. 1 explains the refill, but Fig. 2 shows the following shafts as ink storage containers (ink Total oxygen permeability coefficient even if P is 10- 9 (cc - cm / cm 2 - sec - cmHg) Arbitrary desirable or less.
全酸素透過係数 Pを 10— 9 (c c - cm/cm2 · s e c - cmHg) 以下 とすることにより、 筆記具用ィンキ収容部材に空気中の酸素が透過することに よるインキの劣化の更なる防止、 並びにインキの吹き出しの更なる防止を発揮 せしめることができるものとなる。 Total oxygen permeability coefficient P and 10- 9 (cc - cm / cm 2 · sec - cmHg) by less, further preventing the ink degradation due to transmission of oxygen in the air for a writing instrument Inki housing member , And the ink can be further prevented from being blown out.
本発明の筆記具用ィンキ収容部材に収容されるィンキは、 一般に用いられて いる筆記具用インキであれば、 特に限定されず、 ポールペン用、 加圧ポールべ ン用、 サインペン用、 マーキングペン用などの水性又は油性の液状インキ、 ゲ ル状ィンキなどの筆記具用ィンキが収容されるものである。  The ink stored in the ink storage member for writing implement of the present invention is not particularly limited as long as it is a commonly used ink for writing implement, and may be used for pole pens, pressure pole pens, sign pens, marking pens, and the like. It contains ink for writing implements such as aqueous or oily liquid inks and gel-like inks.
次に、 本発明 （第 1発明及び第 2発明） の筆記具用インキ収容部材の具体的 な実施形態を第 1図〜第 5図により更に詳しく説明する。  Next, specific embodiments of the ink storage member for a writing implement of the present invention (the first and second inventions) will be described in more detail with reference to FIGS.
第 1図 （a) 、 (b) 及び第 2図は、 本発明の筆記具用インキ収容部材をポ 一ルペンにおけるインキ収容管 （リフィ一ル） に適用した場合である。  FIGS. 1 (a), 1 (b) and 2 show the case where the ink storage member for a writing instrument of the present invention is applied to an ink storage tube (refill) of a pollen.
本実施形態の筆記具用インキ収容部材 Aは、 先端にポールペン型チップ 10 を具備したインキ収容管 11を有している。 なお、 12はインキ収容管に充填 されているポールペン用インキ、 13はペン先部とインキ収容管との継ぎ手部 材であり、 14はインキ追従体である。  The ink storage member A for a writing implement of the present embodiment has an ink storage tube 11 provided with a pole pen type tip 10 at the tip. Reference numeral 12 denotes pole pen ink filled in the ink storage tube, 13 denotes a joint member between the pen tip and the ink storage tube, and 14 denotes an ink follower.
このインキ収容管 11は、 第 1図 （b) に示すように、 上述の各種の有機高 分子、 本形態では PPからなる本体部 1 1 a (厚さ 0. 7mm) と、 該本体部 11 aの外側表面部 （外周面部） に酸素透過係数が 25°CDr yで 10— 1G ( c c · cm/cm2 · s e c · cmHg) 以下となるコート層 （本形態では、 EVOHからなるコート層厚さ 1. 0 m、 エチレンモル比率 38mo 1 %) 11 bとから構成されている （第 1発明） 。 As shown in FIG. 1 (b), the ink storage tube 11 has a main body 11a (0.7 mm in thickness) made of the above-mentioned various organic polymers, in this embodiment, PP, and a main body 11a. On the outer surface (aperipheral surface) of a, a coat layer with an oxygen permeability coefficient of 10-1 G (cc · cm / cm 2 · sec · cmHg) or less at 25 ° C Cry (in this embodiment, the thickness of the coat layer made of EVOH) 1.0 m, ethylene molar ratio 38mo 1%) 11b (first invention).
また、 上記本体部 11 aの外側表面部 （外周面部） に酸素透過係数が 25°C D ryで 10— 10 (c c · cm/ cm2 - s e c - cmHg) 以下となる有機 Further, the main body portion 11 the outer surface of a (outer peripheral surface) in the oxygen permeability coefficient at 25 ° CD ry 10- 10 (cc · cm / cm 2 - sec - cmHg) or less and comprising organic
7 高分子 （本形態では、 E V OHでエチレンモル比率 3 8 m o 1 %) 中に平板状 無機微粒子 （本形態では、 合成雲母、 含有量 1重量％) が分散されたコート層7 Coat layer in which flat inorganic fine particles (in this embodiment, synthetic mica, content 1% by weight) are dispersed in a polymer (in this embodiment, EVOH is ethylene mole ratio of 38 mo 1%)
(厚さ 1 1 bとする構成であってもよい （第 2発明） 。 (The configuration may be such that the thickness is 11b (second invention).
なお、 本体部 1 1 aの外側表面部を上記①の粗面部から構成して平滑面がな い構造とする、 または、 上記②のオゾン処理、 プラズマ処理、 コロナ処理、 紫 外線照射処理、 高圧放電処理及び酸処理から選ばれる少なくとも 1種の活性化 処理を施す、 更に上記③の石油樹脂又はその誘導体を配合した材質で構成した もの、 並びに、 これらの①〜③を組合わせた 4種の本体部であってもよい （第 3図以下の実施形態も同様） 。  The outer surface of the main body 11a is composed of the rough surface of (1) above to have a structure without a smooth surface, or the ozone treatment, plasma treatment, corona treatment, ultraviolet irradiation treatment, and high pressure described in (2) above At least one type of activation treatment selected from discharge treatment and acid treatment is applied, and furthermore, a material composed of a material blended with petroleum resin or its derivative described in (3) above, and four types combining these (1) to (3) It may be a main body (the same applies to the embodiments shown in FIG. 3 and thereafter).
この筆記具用インキ収容部材 Aは、 第 2図に示すように、 ポールペン用軸体 As shown in FIG. 2, the ink storage member A for a writing instrument includes a pole pen shaft
1 5に装着してポールペンとして用いられる。 なお、 1 6は尾栓、 1 7はキヤ ップ体、 1 8はシールゴムである。 Used as a pole pen when attached to 15. 16 is a tail plug, 17 is a cap body, and 18 is a seal rubber.
第 3図は、 本発明の筆記具用ィンキ収容部材をコレクタ一構造を備えた直液 式筆記具におけるインキを直接貯溜する軸体 （インキ容器） となるインキタン ク部  FIG. 3 shows an ink tank portion serving as a shaft (ink container) for directly storing ink in a direct liquid type writing instrument having a collector-type structure in which the ink container for a writing instrument according to the present invention is provided.
に適用したものである。 It is applied to
本実施形態の.筆記具用ィンキ収容部材 Bは、 インキ 2 0を中綿等に吸蔵させ ないで直接貯溜する軸体となるィンキ夕ンク部 2 1から構成されるものである なお、 インキタンク部 2 1の前部には、 インキタンク部 2 1内の空気が温度 上昇等によって膨張した場合にインキタンク 2 1から押し出されるインキ 2 0 をペン先や空気孔からポ夕落ちさせないために一時的に保溜するインキ保溜体 (コレクタ一部材） 2 2が内蔵され、 コレクタ一部材 2 2の先端部には繊維芯 からなるペン先 2 3が設けられた構成となっている。  The ink container B for writing implements of the present embodiment is composed of an ink container 21 serving as a shaft for directly storing the ink 20 without absorbing the ink 20 into a batting or the like. The front of 1 is temporarily stopped to prevent the ink 20 pushed out from the ink tank 21 from dropping from the pen tip or air hole when the air in the ink tank 21 expands due to temperature rise etc. An ink reservoir (collector member) 22 for storage is built in, and a pen tip 23 made of a fiber core is provided at the tip of the collector member 22.
インキタンク部 2 1からペン先 2 3へのインキ導出は、 コレクタ一部材 2 2 の中心孔に付設されたインキ流路 2 2 aを設けた中継芯 2 4を介してインキ夕  The ink is drawn out from the ink tank section 21 to the pen tip 23 via an intermediate core 24 provided with an ink flow path 22 a provided in the center hole of the collector member 22.
8 ンク部 21からインキ 20をペン先 23に導出することにより行われる。 なお、 第 3図中の 25はホルダ一部材であり、 26はインキタンク部 11の 後部に固着される後部軸体であり、 27はキャップである。 また、 中継芯 24 を介在させることなく、 ペン先 23の後部をインキタンク部 21内に直接配置 してインキの導出を行ってもよい。 8 This is performed by leading the ink 20 from the ink section 21 to the pen tip 23. In FIG. 3, reference numeral 25 denotes a holder member, reference numeral 26 denotes a rear shaft fixed to the rear of the ink tank 11, and reference numeral 27 denotes a cap. Also, the ink may be led out by disposing the rear portion of the pen tip 23 directly in the ink tank 21 without the intermediary of the relay core 24.
このインキ収容容器となるインキタンク部 21は、 ポリプロピレンからなる 本体部 （厚さ 1. Omm) と、 該本体部の外側表面部 （外周面部） に酸素透過 係数が 25°CD r yで 10-1Q (c c · cm/cm2 - s e c - cmHg) 以 下となるホウ素による耐水化処理が施された PV Aからなるコート層 （厚さ 1 . 2 urn) とから構成されている （第 1発明） 。 The ink tank 21 serving as the ink container has a main body (thickness of 1. Omm) made of polypropylene and an outer surface (outer peripheral surface) of the main body having an oxygen transmission coefficient of 10-1Q at 25 ° C dry. (cc · cm / cm 2 -sec-cmHg) and a coat layer (thickness: 1.2 urn) made of PVA that has been subjected to a water-resistant treatment with boron, which is less than or equal to (the first invention). .
また、 上記本体部の外側表面部 （外周面部） に酸素透過係数が 25°CDr y で 10— 10 (c c · cm/ cm2 - s e c - cmHg) 以下となる有機高分子 (本形態では、 ？ 八でケン化度99%) 中に平板状無機微粒子 （本形態では 、 モンモリロナイト、 含有量 5重量％) が分散されたコート層 （厚さ 2 m) とから構成してもよい （第 2発明） 。 Further, the oxygen permeation coefficient on the outer surface portion of the body portion (outer peripheral surface) is 25 ° CDr y at 10- 10 (cc · cm / cm 2 - cmHg - sec) in the organic polymer (this embodiment equal to or less than? And a coat layer (thickness: 2 m) in which tabular inorganic fine particles (in this embodiment, montmorillonite, content: 5% by weight) are dispersed. ).
なお、 ポリプロピレンからなる後部軸体 26にも上記ホウ素による耐水化処 理が施された PVAからなるコート層 （厚さ 7 m) を施しても良いもの である。  The rear shaft 26 made of polypropylene may be provided with a coat layer (thickness: 7 m) made of PVA that has been subjected to the above-mentioned water resistance treatment with boron.
第 4図は、 本発明の筆記具用インキ収容部材を、 撹拌ボールを内蔵したバル ブ機構部を有するバルブ式筆記具におけるインキを直接貯溜する軸体 （インキ 容器） となるインキタンク部に適用したものである。  FIG. 4 shows a case where the ink storage member for a writing implement of the present invention is applied to an ink tank portion serving as a shaft (ink container) for directly storing ink in a valve-type writing implement having a valve mechanism section containing a stirring ball. It is.
本実施形態の筆記具用ィンキ収容部材 Cは、 インキ 30を中綿等に吸蔵させ ないで直接貯溜する軸体となるインキタンク部 31から構成されるものである なお、 この筆記具には、 インクタンク部 31内にバルブ機構部 32を介在し て繊維芯からなるペン先 33へインキが供給される構成となっている。 なお、  The ink-ink storage member C for a writing implement according to the present embodiment includes an ink tank 31 serving as a shaft that directly stores the ink 30 without absorbing the ink into a batting or the like. Ink is supplied to a nib 33 made of a fiber core via a valve mechanism 32 in 31. In addition,
9 第 3図中の 34はホルダ一部材であり、 35はバルブ機構部 32とホルダー部 材 34間に介在し、 ペン先 33の後部を保持する保持部材であり、 36はキヤ ップであり、 37は撹拌ポールである。 また、 本実施形態は、 中継芯を介さな いでインキをペン先へ供給するものであるが、 中継芯を設け、 インキタンク部 31からバルブ機構部 32、 中継芯を介在して繊維芯からなるペン先 33ヘイ ンキを供給する構成にしてもよい。 9 In FIG. 3, reference numeral 34 denotes a holder member, reference numeral 35 denotes a holding member interposed between the valve mechanism 32 and the holder member 34, and holds a rear portion of the pen tip 33, and reference numeral 36 denotes a cap. 37 is a stirring pole. In this embodiment, the ink is supplied to the pen tip without passing through the relay core. However, the relay core is provided, and the ink tank part 31 is composed of the fiber mechanism through the valve mechanism part 32 and the relay core. A configuration may be adopted in which 33 nibs are supplied.
このインキ収容容器となるインキタンク部 3 1は、 環状ポリオレフインから なる本体部 （厚さ 2. Omm) と、 該本体部の外側表面部 （外周面部） に酸素 透過係数が 2 5°CD r yで 10_1Q (c c · cm/ cm2 - s e c - c mH g ) 以下となる EVOHからなるコート層 （厚さ 1. 0 fim) とから構成されて いる。 The ink tank 31 serving as the ink container has a main body (annular thickness of 2. Omm) made of a cyclic polyolefin and an oxygen transmission coefficient of 25 ° C dry on the outer surface (outer peripheral surface) of the main body. It is composed of a coat layer (thickness: 1.0 fim) made of EVOH that is less than 10 _1Q (cc · cm / cm 2 -sec-cmHg ).
また、 上記本体部の外側表面部 （外周面部） に、 酸素透過係数が 25°CD r yで 10— 10 (c c · cm/ cm2 - s e c - cmHg) 以下となる有機高分 子 （本形態では、 ？ 八でケン化度99%) 中に平板状無機微粒子 （本形態で は、 モンモリロナイト、 含有量 5重量％) が分散されたコート層 （厚さ 2 m ) としてもよい （第 2発明） 。 The outer surface portion of the body portion (outer peripheral surface), the oxygen permeability coefficient at 25 ° CD ry 10- 10 (cc · cm / cm 2 - sec - cmHg) or less and comprising organic high partial element (in this embodiment A coating layer (2 m in thickness) in which flat inorganic fine particles (in this embodiment, montmorillonite, content 5% by weight) are dispersed in the saponification degree 99% (second invention). .
第 5図は、 本発明の筆記具用インキ収容部材を、 インキを中綿等のインキ吸 蔵体に吸蔵させた筆記具のインキタンク部に適用したものである。  FIG. 5 shows a case where the ink storage member for a writing implement of the present invention is applied to an ink tank portion of a writing implement in which ink is occluded in an ink storage body such as batting.
本実施形態の筆記具用ィンキ収容部材 Dは、 ィンキを中綿等に吸蔵させたィ ンキ吸蔵体 40を収容する軸体となるインキタンク部 41から構成されるもの である。  The ink storage member D for a writing implement of the present embodiment is configured by an ink tank portion 41 serving as a shaft that stores an ink storage body 40 in which the ink is stored in a batting or the like.
このインキ吸蔵体 40の前部には繊維芯からなるペン先 42の後端部 42 a が当接されることにより、 ィンキ吸蔵体 40のィンキがペン先 42へ供給され る構成となっている。 43は、 先軸部材、 44は軸本体 41の後端部に固着さ れた尾栓、 45は、 キャップである。  The rear end portion 42a of the pen tip 42 made of a fiber core abuts on the front portion of the ink occluding body 40, so that the ink of the ink occluding body 40 is supplied to the pen tip 42. . 43 is a front shaft member, 44 is a tail plug fixed to the rear end of the shaft body 41, and 45 is a cap.
このインキ収容容器となるインキタンク部 41は、 ポリプロピレンからなる 本体部 （厚さ l. 0 mm) と、 該本体部の外側表面部 （外周面部） に酸素透過 係数が 25°CD r yで 10-1() (c c · cm/ cm2 · s e c · cmHg) 以 下となる EVOHからなるコート層 （厚さ 1. 0 urn) とから構成されている また、 上記本体部の外側表面部 （外周面部） に、 酸素透過係数が 25°CDr yで 10— 10 (c c · cm/ cm2 - s e c - cmHg) 以下となる有機高分 子 （本形態では EVOHでエチレンモル比率 38mo 1 %) 中に平板状無機微 粒子 （本形態では、 モンモリロナイト、 含有量 5重量％) が分散されたコート 層 （厚さ を構成してもよい （第 2発明） 。 The ink tank 41 serving as the ink container is made of polypropylene. The main body (thickness of l. 0 mm) and, 10 1 the outer surface portion of the body portion (outer peripheral surface) in the oxygen permeability coefficient at 25 ° CD ry () (cc · cm / cm 2 · sec · cmHg) coating layer made of EVOH to be hereinafter also is constructed from (a thickness of 1. 0 urn) and an outer surface portion of the body portion (outer peripheral surface), 10-10 oxygen permeability coefficient at 25 ° CDr y (cc · cm / cm 2 -sec-cmHg) Inorganic polymer (in this embodiment, EVOH ethylene molar ratio 38mo 1%) less than or equal to tabular inorganic fine particles (in this embodiment, montmorillonite, content 5% by weight) ) Is dispersed in the coating layer (the thickness may be constituted (second invention)).
このように構成される本発明では、 水性又は油性の液状インキ、 ゲル状イン キなどの筆記具用インキを収容するコレクター構造を有する直液筆記具、 中綿 式筆記具等のィンキ収容容器やポールペンのィンキ収容管 （ポールペンリフィ ール） 等の筆記具用インキ収容部材の外側表面部に、 第 1発明では、 酸素透過 係数が 25°CD ryで 10— 1( (c c · cm/cm2 · s e c · cmHg) 以 下のコート層 （第 1発明） が形成されているので、 筆記具用インキ収容部材に 空気中の酸素が透過することがなくなり、 インキの劣化防止、 並びに香料入り ィンキの保香性向上、 更にはィンキの吹き出しを長期間防止することができる 筆記具用ィンキ収容部材が得られることとなる。 In the present invention configured as described above, ink storage containers such as water-based or oil-based liquid ink, and inks for writing implements such as gel inks, and a collector container structure for accommodating ink for writing implements, batting-type writing implements, etc. tube outer surface portion of the (pole pen refill Lumpur) like ink for a writing instrument housing member, in the first invention, the oxygen permeability coefficient at 25 ° CD ry 10- 1 (( cc · cm / cm 2 · sec · cmHg) Since the following coat layer (first invention) is formed, oxygen in the air does not pass through the ink storage member for writing implements, preventing deterioration of the ink and improving the scent retention of the ink containing fragrance. Thus, a writing instrument accommodating member that can prevent blowout of the ink for a long period of time can be obtained.
また、 第 2発明では、 筆記具用インキ収容部材の外側表面部に、 酸素透過係 数が 25t D ryで 10— 10 (c c · cm/cm2 · s e c · cmHg) 以下 の有機高分子中に平板状無機微粒子が分散されているコート層が形成されてい るので、 コート層の機械的強度が更に向上し、 耐擦過性が更に向上するのでピ ンホールなどが発生し難くなり、 また、 筆記具用インキ収容部材に空気中の酸 素が透過することがなくなり、 インキの劣化防止、 香料インキの保香性向上、 並びに、 インキの吹き出しを長期間防止することができる筆記具用インキ収容 部材が得られることとなる。 In the second invention, the outer surface portion of the writing instrument ink containing member, the oxygen permeability coefficient is at 25t D ry 10- 10 (cc · cm / cm 2 · sec · cmHg) or less of the plate in the organic polymer Since the coating layer in which the inorganic fine particles are dispersed is formed, the mechanical strength of the coating layer is further improved, and the abrasion resistance is further improved, so that pinholes and the like hardly occur. Oxygen in the air does not permeate into the housing member, and an ink housing member for writing implements that can prevent deterioration of the ink, improve the fragrance retention of the fragrance ink, and prevent the ejection of the ink for a long time can be obtained. Becomes
2 また、 上記特性のコート層を形成する前の筆記具用ィンキ収容部材の外側表 面を①粗面部から構成して平滑面がない構造としたり、 ②オゾン処理、 プラズ マ処理、 コロナ処理、 紫外線照射処理、 高圧放電処理及び酸処理から選ばれる 少なくとも 1種の活性化処理を施したり、 ③筆記具用インキ収容部材をポリオ レフィン系熱可塑性有機高分子 100重量部に対して、 石油樹脂又はその誘導 体が 5〜40重量部配合されたものにより構成したもの、 または、 これらの① 〜③を組合わせた 4種の筆記具用インキ収容部材によりなるものでは、 更にコ ート層との密着性が向上し、 更に酸素が透過することがなくなり、 インキの劣 化防止、 インキの吹き出しを更に長期間防止することができるものとなる。 また、 本発明の筆記具用インキ収容部材では、 該筆記具用インキ収容部材の 外側表面部に酸素透過係数が 25t D r yで 10— 1Q (c c · cm/cm2■ s e c - cmHg) 以下のコート層 （第 1発明） が形成されている構造 （第 1 発明） 、 または、 酸素透過係数が 25°CD r yで 10— 10 (c c * cm/cm 2 · s e c · cmHg) 以下の有機高分子中に平板状無機微粒子が分散されて いるコート層が形成されている構造 （第 2発明） からなるものであるが、 筆記 具用ィンキ収容部材等においては窒素ガスよりも酸素ガスの方が透過しやすい ので、 該酸素透過係数を上記特性値以下にすることにより、 窒素ガスの透過も 更に抑制できるものとなる。 従って、 空気及び加圧筆記具に用いる窒素ガスの 透過も抑制できるものとなる。 よって、 加圧ポールペン等の窒素ガスなどの加 圧気体による加圧式筆記具用の筆記具用インキ収容部材においても、 インキ収 容容器内の窒素ガスなどの加圧気体が容器外に透過することが防止できるもの となるので、 インキ収容容器内の内圧低下による筆記不良を長期間防止するこ とができるものとなる。 Two In addition, the outer surface of the ink container for writing implements before the formation of the coating layer having the above-mentioned characteristics may be composed of a rough surface to have no smooth surface, or ozone treatment, plasma treatment, corona treatment, and ultraviolet irradiation. Treatment, high-pressure discharge treatment, or acid treatment, or at least one activation treatment. ③ The ink storage member for writing implements is made of petroleum resin or its derivative with respect to 100 parts by weight of a polyolefin-based thermoplastic organic polymer. 5 to 40 parts by weight, or four kinds of ink storage members for writing implements combining these ① to ③, further improve the adhesion to the coat layer In addition, oxygen is no longer permeated, so that deterioration of the ink can be prevented, and ejection of the ink can be prevented for a longer period of time. Further, in the ink storage member for writing implement of the present invention, the coat layer having an oxygen permeability coefficient of 10-1 Q (cc · cm / cm 2 ■ sec-cmHg) at 25 t Dry on the outer surface portion of the ink storage member for writing implement. (first invention) is formed structure (first invention), or the oxygen permeability coefficient at 25 ° CD ry 10- 10 (cc * cm / cm 2 · sec · cmHg) in the following organic polymers It has a structure in which a coat layer in which plate-like inorganic fine particles are dispersed is formed (second invention). However, in an ink container for a writing instrument, etc., oxygen gas is more easily permeated than nitrogen gas. Therefore, by setting the oxygen permeation coefficient to be equal to or less than the above characteristic value, permeation of nitrogen gas can be further suppressed. Therefore, permeation of air and nitrogen gas used for the pressurized writing instrument can be suppressed. Therefore, even in an ink storage member for a writing instrument for a pressurized writing instrument using a pressurized gas such as a nitrogen gas such as a pressurized pole pen, the pressurized gas such as a nitrogen gas in the ink storage container is prevented from permeating outside the container. As a result, poor writing due to a decrease in the internal pressure of the ink container can be prevented for a long period of time.
本発明の筆記具用ィンキ収容部材は、 上記実施形態に限定されるものでなく 、 本発明の要旨を変更しない範囲で種々の形態に変更できることはいうまでも ない。 本発明の筆記具用ィンキ収容部材は、 第 1発明で筆記具用ィンキを収容する 有機高分子から構成される筆記具用ィンキ収容部材の外側表面部に酸素透過係 数が 2 r yで 10— 10 (c c · cmZcm2 · s e c · cmHg) 以下 のコート層を形成すること、 または、 第 2発明で筆記具用インキを収容する有 機高分子から構成される筆記具用ィンキ収容部材の外側表面部に酸素透過係数 が 25" D ryで 10_10 (c c · cm/ cm2 · s e c · cmHg) 以下の 有機高分子中に平板状無機微粒子が分散されているコート層が形成することを 要旨とするので、 本発明を各種筆記具に用いた場合には、 上記筆記具用インキ 収容部材以外の構造は特に限定されるものではなく、 ポールペン、 サインペン 、 マ一キングペンなどの各種筆記具の構造が適用されるものである。 The ink container for a writing instrument according to the present invention is not limited to the above embodiment, and it goes without saying that it can be changed to various forms without changing the gist of the present invention. Writing instruments Inki receiving member of the present invention, the first oxygen permeability coefficient in the outer surface portion of the writing instrument Inki housing member comprised of an organic polymer which houses a writing instrument for Inki with invention in 2 ry 10- 10 (cc · CmZcm 2 · sec · cmHg) The following coating layer is formed, or the oxygen permeation coefficient is applied to the outer surface of the ink container for writing implements composed of an organic polymer that contains the ink for writing implements in the second invention. There since summarized in that the coating layer in which the tabular inorganic fine particles are dispersed is formed in the organic polymer 10_ 10 (cc · cm / cm 2 · sec · cmHg) or less at 25 "D ry, the present invention When is used for various writing tools, the structure other than the ink storage member for writing tools is not particularly limited, and the structure of various writing tools such as a pole pen, a felt-tip pen, and a marking pen is applied.
また、 筆記具用インキを修正液、 塗布液、 化粧品等の液状ィ匕粧料等とした塗 布具の塗布液の収容部材にも適用できるものである。  Further, the present invention is also applicable to a member for storing a coating liquid of a coating implement, such as a correction liquid, a coating liquid, or a liquid cosmetic such as cosmetics, in which a writing implement ink is used.
なお、 筆記具用インキ収容部材を酸素透過係数の少ない材質、 例えば、 ェチ レン，ビニルアルコール共重合体 （EVOH) 等により構成した場合には、 酸 素透過が少なくなるが、 加湿雰囲気等の環境下にすると、 樹脂が空気中の水蒸 気で膨潤し、 ガスバリア性が低下し、 寸法変化等が起こることとなり、 本発明 の効果を発揮できるものではないものである。 実施例  When the ink storage member for writing implements is made of a material having a low oxygen permeability coefficient, for example, ethylene, vinyl alcohol copolymer (EVOH), etc., oxygen permeation is reduced, but the environment such as humidified atmosphere is reduced. When the resin is lowered, the resin swells due to water vapor in the air, the gas barrier property is reduced, and dimensional changes occur, so that the effects of the present invention cannot be exhibited. Example
次に、 本発明を実施例及び比較例に基づき更に詳細に説明するが、 本発明は 下記実施例に限定される ¾のではない。  Next, the present invention will be described in more detail based on examples and comparative examples, but the present invention is not limited to the following examples.
〔実施例 1〜 9及び比較例 1〜 2、 第 1発明〕  (Examples 1 to 9 and Comparative Examples 1 and 2, the first invention)
下記方法により第 1発明等となる各筆記具用ィンキ収容部材を備えた筆記具 を作製した。  By the following method, a writing implement including the ink container for a writing implement according to the first invention was produced.
(実施例 1、 直液式サインペン）  (Example 1, direct liquid type pen)
射出成形により直液式サインペン用の P P製ィンキ収容容器を作製した。 こ の PP製インキ収容容器は第 3図の図示符号 21に準拠するものであり、 肉厚 1. Omm、 内径 7. Omm、 長さ 5 Ommである。 PPの酸素透過係数は、 25T:D r yで約 5 X 10— 9 ( c c · c mZ c m2 · s e c · c mH g) であ つた。 An INK container made of PP for a direct liquid type felt pen was manufactured by injection molding. This The PP ink container conforms to the reference numeral 21 in FIG. 3, and has a thickness of 1. Omm, an inner diameter of 7. Omm, and a length of 5 Omm. Oxygen permeability coefficient of the PP, 25T: D ry about 5 X 10- 9 (cc · c mZ cm 2 · sec · c mH g) der ivy.
この P P製ィンキ収容容器の外側表面部全体を金型上で成形時に梨地化処理 し、 次いで、 該表面部全体を空気存在下グロ一放電によりプラズマ処理した。 この梨地化処理、 プラズマ処理した P P製ィンキ収容容器の外側表面部全体に 酸素透過係数が 25°CD r yで約 1 X 10— 13 (c c · cm/ cm2 - s e c • cmHg) の EVOH (エチレンモル比率 38 %) を平均厚約 1. 0 mに なるように、 塗布液粘度と EVOH固形分を調整した塗布液を用いてコーティ ング処理し、 本体層とコート層の総厚 1001. O mにした。 また、 この P P製インキ収容容器の全体の酸素透過係数 Pは約 9. 8X 10— 11 (c c · c m cm2 ' s e c ' c mH g) であった。 The entire outer surface of the PP ink container was matted during molding on a mold, and then the entire surface was plasma-treated by glow discharge in the presence of air. The entire outer surface of the matte-treated and plasma-treated PP ink container has an oxygen permeation coefficient of about 1 X 10-13 (cc · cm / cm 2 -sec • cmHg) of EVOH (ethylene mole) at 25 ° C dry. (38% ratio) to an average thickness of about 1.0 m, using a coating solution with the coating solution viscosity and EVOH solid content adjusted to achieve a total thickness of 1001. did. Further, the whole of the oxygen permeability coefficient P of the PP-made ink container was about 9. 8X 10- 11 (cc · cm cm 2 'sec' c mH g).
この P P製ィンキ収容容器を用いて第 3図に示す直液式サインペンを組み立 た。  Using this PP ink container, a direct liquid type felt-tip pen shown in Fig. 3 was assembled.
(実施例 2、 直液式サインペン）  (Example 2, direct liquid type felt pen)
上記実施例 1において、 プラズマ処理のみを除いた実施例 1と同様の直液式 サインペンを組み立た。 なお、 各酸素透過係数は実施例 1と同様であった。  In Example 1, a direct liquid type pen similar to Example 1 except for the plasma treatment was assembled. The respective oxygen permeability coefficients were the same as in Example 1.
(実施例 3、 直液式サインペン）  (Example 3, direct liquid type felt pen)
上記実施例 1において、 梨地化処理のみを除いた実施例 1と同様の直液式サ インペンを組み立た。 なお、 各酸素透過係数は実施例 1と同様であった。 (実施例 4、 直液式サインペン）  In Example 1, a direct liquid-type sign pen similar to Example 1 except for the satin finish treatment was assembled. The respective oxygen permeability coefficients were the same as in Example 1. (Example 4, direct liquid type pen)
上記実施例 1において、 梨地化処理、 プラズマ処理の両方を除き実施例 1と 同様の直液式サインペンを組み立た。 なお、 各酸素透過係数は実施例 1と同様 であった。 '  In Example 1 above, a direct liquid type felt-tip pen similar to that of Example 1 was assembled except for both the satin finish treatment and the plasma treatment. The respective oxygen permeability coefficients were the same as in Example 1. '
(実施例 5、 直液式サインペン） 上記実施例 1において、 インキ収容容器用材料として、 PP樹脂 （J 226 E、 三井石油化学社製） 100重量部に対して石油樹脂 （アルコン P— 100 、 荒川化学工業社製） 20重量部を配合した樹脂組成物を用いて PP製インキ 収容容器を実施例 1と同寸法のものを作製した。 この P P製ィンキ収容容器の 酸素透過係数は、 25t:D r yで約 10-9 (c c ' cmZcm2 ' s e c ' c mHg) であった。 (Example 5, direct liquid type felt pen) In Example 1 described above, 20 parts by weight of a petroleum resin (Alcon P-100, manufactured by Arakawa Chemical Industries) was used as the ink container material for 100 parts by weight of PP resin (J226E, manufactured by Mitsui Petrochemical Co., Ltd.). A PP ink container having the same dimensions as in Example 1 was produced using the compounded resin composition. Oxygen permeability coefficient of the PP made Inki accommodating container, 25t: was about at D ry 10- 9 (cc 'cmZcm 2' sec 'c mHg).
この PP製インキ収容容器を用いて （梨地化処理、 プラズマ処理せず） 、 上 記実施例 1と同様にして EVOHコートを作製した。 また、 この PP製インキ 収容容器の全体の酸素透過係数 Pは約 9. 8 X 10- 11 (c c · cm/ cm2 - s e c - cmHg) であった。 An EVOH coat was produced in the same manner as in Example 1 above using this PP ink container (without satin finish treatment or plasma treatment). Further, the whole of the oxygen permeability coefficient P of the PP-made ink container about 9. 8 X 10- 11 (cc · cm / cm 2 - cmHg - sec) was.
この P P製ィンキ収容容器を用いて実施例 1と同様にして直液式サインペン を組み立た。  A direct liquid type felt-tip pen was assembled in the same manner as in Example 1 using this PP ink container.
(実施例 6 )  (Example 6)
上記実施例 1において、 実施例 1と同様に梨地化処理、 プラズマ処理した P P製ィンキ収容容器の外側表面部全体に酸素透過係数が 25 °C D r yで約 5 X 10— 14 (c c · cm/ cm2 - s e c - cmHg) の PVA (ケン化度 99 %) を平均厚約 2. 0 mになるように、 デイツピング法を用いてコーティン グ処理し、 本体層とコート層の総厚 1002. 0 mにした。 また、 この PP 製インキ収容容器の全体の酸素透過係数 Pは約 2. 4X 10— 11 (c c · cm /cm2 - s e c - cmHg) である。 In the first embodiment, in the same manner as in Example 1 satin treatment, a plasma treatment was made of PP Inki oxygen permeability coefficient across outer surface portion of the container is 25 ° in CD ry about 5 X 10- 14 (cc · cm / cm 2 - sec - average PVA (99% degree of saponification) of cmHg) thickness of about 2 so that 0 m, and Kotin grayed processed using Deitsupingu method, 1002. the total thickness of the body layer and the coat layer 0 m. Further, the whole of the oxygen permeability coefficient P of the PP-made ink container about 2. 4X 10- 11 (cc · cm / cm 2 - cmHg - sec) is.
この P P製ィンキ収容容器を用いて第 3図に示す直液式水性サインペンを組 み立た。  Using the PP ink container, a direct liquid type water-based felt-tip pen shown in Fig. 3 was assembled.
(実施例 7、 直液式サインペン）  (Example 7, direct liquid type felt pen)
上記実施例 1において、 実施例 1と同様に梨地化処理、 プラズマ処理した P P製ィンキ収容容器の外側表面部全体に酸素透過係数が 25 °C D r yで約 5 X 10— 14 (c c · cm/cm2 - s e c - cmHg) の完全ケン化の PVAを ホウ素とコンプレックスを形成させたものを平均厚約 1. 0 mになるように 、 デイツビング法を用いてコーティング処理し、 本体層とコート層の総厚 10 01. Ο ΠΙにした。 また、 この Ρ Ρ製インキ収容容器の全体の酸素透過係数 Ρは約 4. 8 X 10— 11 (c c · cm/ cm2 - s e c - cmHg) であった この P P製ィンキ収容容器を用いて第 3図に示す直液式サインペンを組み立 た。 In the first embodiment, in the same manner as in Example 1 satin treatment, a plasma treatment was made of PP Inki oxygen permeability coefficient across outer surface portion of the container is 25 ° in CD ry about 5 X 10- 14 (cc · cm / the cmHg PVA of complete saponification of) - cm 2 - sec The complex formed with boron was subjected to a coating treatment by a dive method so as to have an average thickness of about 1.0 m, and the total thickness of the main body layer and the coat layer was set to 100. 1. Moreover, this Ρ is Ρ overall oxygen permeability coefficient of Ρ manufactured ink container about 4. 8 X 10- 11 (cc · cm / cm 2 - cmHg - sec) first with a which was the PP made Inki container The direct liquid type felt pen shown in Fig. 3 was assembled.
(実施例 8、 ポールペン）  (Example 8, pole pen)
射出成形により直液筆記具用の PP製インキチューブ （リフィール） を作製 した。 この PP製インキリフィールは第 1図 （a) の図示符号 Aに準拠するも のであり、 肉厚 0. 5mm、 内径 4mm、 長さ 120mmである。 PPの酸素 透過係数は、 25°CD r yで約 5 X 10-9 (c c · cm/ cm2 · s e c · c mHg) であった,。 PP ink tubes (refills) for direct liquid writing instruments were manufactured by injection molding. This PP ink refill conforms to the reference symbol A in Fig. 1 (a), and has a wall thickness of 0.5mm, an inner diameter of 4mm, and a length of 120mm. The oxygen permeability coefficient of PP was about 5 × 10 −9 (cc · cm / cm 2 · sec · cmHg) at 25 ° C. dry.
この P P製ィンキ収容容器の外側表面部全体を空気存在下グロ一放電により プラズマ処理した。 このプラズマ処理した PP製インキ収容容器の外側表面部 全体に酸素透過係数が 25°CD r yで約 1 X 10— 13 (c c · cm/cm2 · s e c - cmHg) の EVOH (エチレンモル比率 20%) を平均厚約 1. 0 mになるように、 デイツピング法によりコーティング処理し、 本体層とコ一 ト層の総厚 1001. 0 mにした第 1図 （a) に示すポールペン用リフィ一 ルを作製した。 The entire outer surface of the PP ink container was plasma-treated by glow discharge in the presence of air. The plasma-treated PP-made ink container about 1 oxygen permeability coefficient across outer surface portion 25 ° CD ry of X 10- 13 (cc · cm / cm 2 · sec - cmHg) of EVOH (ethylene mole ratio 20%) The coating was applied by dipping to an average thickness of about 1.0 m, and the total thickness of the main body layer and the coating layer was 1001.0 m. Produced.
この PP製リフィールの全体の酸素透過係数 Pは約 9. 8 X 10— 11 (c c • cm/ cm2 ' s e c ' cmHg) であった。 Overall oxygen permeability coefficient P of the PP-made refill was about 9. 8 X 10- 11 (cc • cm / cm 2 'sec' cmHg).
(実施例 9、 ポールペン）  (Example 9, pole pen)
上記実施例 8において、 プラズマ処理を除いた実施例 9と同様のポールペン 用リフィールを組み立てた。 なお、 各酸素透過係数は、 実施例 9と同様であつ た。 (比較例 1 ) In Example 8, a refill for a pole pen similar to Example 9 except for the plasma treatment was assembled. The respective oxygen permeability coefficients were the same as in Example 9. (Comparative Example 1)
射出成形により直液筆記具用の P P製ィンキ収容容器を作製した。 この P P 製インキ収容容器は第 3図の図示符号 21に準拠するものであり、 肉厚 1. 0 mm、 内径 7mm、 長さ 5 Ommである。 PPの酸素透過係数は、 25°CDr yで約 5 X 10— 9 (c c · cm/ cm2 - s ec - cmHg) であった。 A PP ink container for a direct liquid writing instrument was manufactured by injection molding. This PP ink container complies with the reference numeral 21 in FIG. 3, and has a thickness of 1.0 mm, an inner diameter of 7 mm, and a length of 5 Omm. Oxygen permeability coefficient of the PP, 25 ° CDr y about 5 X 10- 9 (cc · cm / cm 2 - s ec - cmHg) was.
この P P製ィンキ収容容器を用いて第 3図に示す直液式サインぺンを組み立 た。  Using this PP ink container, a direct liquid type sign-in as shown in Fig. 3 was assembled.
(比較例 2 )  (Comparative Example 2)
射出成形により直液筆記具用の PP製インキチューブ （リフィール） を作製 した。 この PP製インキリフィールは第 1図 （a) の図示符号 Aに準拠するも のであり、 肉厚 0. 5mm、 内径 4mm、 長さ 120mmである。 PPの酸素 透過係数は、 25 D r yで約 5 X 10— 9 (c c · cm/cm2 · s e c · c mHg) であった。 PP ink tubes (refills) for direct liquid writing instruments were manufactured by injection molding. This PP ink refill conforms to the reference symbol A in Fig. 1 (a), and has a wall thickness of 0.5mm, an inner diameter of 4mm, and a length of 120mm. Oxygen permeability coefficient of the PP was 25 D ry about 5 X 10- 9 (cc · cm / cm 2 · sec · c mHg).
得られた各筆記具等について、 下記各組成のインキを充填し、 各直液式サイ ンペン、 第 2図に示すポールペンを作製した後、 下記方法によりインキの吹き 出し性、 保香性について評価した。  Each of the writing implements was filled with the ink of the following composition to prepare each direct liquid type pen and the pole pen shown in Fig. 2, and then evaluated for the ink blowing property and fragrance retention by the following methods. .
これらの結果を下記表 1〜 4に示す。  The results are shown in Tables 1 to 4 below.
上記実施例 1〜 7及び比較例 1は下記直液筆記具用ィンキ組成、 直液筆記具 用インキ組成 （香料タイプ） 各 lgを充填した。 また、 上記実施例 8〜 9及び 比較例 2は、 下記ポールペン用インキ組成物、 ポールペン用インキ組成物 （香 料タイプ） 各 1 gを充填した。  In the above Examples 1 to 7 and Comparative Example 1, the following ink compositions for a direct liquid writing instrument and ink compositions for a direct liquid writing instrument (perfume type) were filled with each lg. In Examples 8 to 9 and Comparative Example 2, 1 g each of the following ink composition for pole pen and pole pen ink composition (fragrance type) was filled.
(直液筆記具用インキ組成、 全量 100重量％)  (Ink composition for direct liquid writing implement, 100% by weight)
C.I. Direct Black-154 4. 5 C.I.Direct Black-154 4.5
C. I. Direct Black— 19 1. 5 エチレングリコール 10. 0 グリセリン 10. 0 PH調整剤 0. 3 防腐剤 （プロキセル GXL) 0. 5 固着性樹脂 （スチレンアクリル酸樹脂、 アンモニア中和） 3. 0 界面活性剤 （インゲン P、 第一製薬工業社製） 0. 2 CI Direct Black— 19 1.5 Ethylene glycol 10.0 Glycerin 10.0 PH adjuster 0.3 Preservative (Proxel GXL) 0.5 Sticking resin (styrene acrylic acid resin, ammonia neutralization) 3.0 Surfactant (Ingen P, Daiichi Pharmaceutical) 0.2
(直液筆記具用ィンキ組成香料タイプ、 全量 100重量％) (Ink composition fragrance type for direct liquid writing instrument, 100% by weight)
C. I. Direct Black-154 4. 5 C. I. Direct Black- 19 1. 5 プロピレングリコール 10. 0 グリセリン 10. 0 香料 （1—メントール） 1. 3 PH調整剤 0. 3 防腐剤 （プロキセル GXL) 0. 5 固着性樹脂 （スチレンアクリル酸樹脂、 アンモニア中和） 3. 0 界面活性剤 （インゲン P、 第一製薬工業社製） 0. 2 CI Direct Black-154 4.5 CI Direct Black- 19 1.5 Propylene glycol 10.0 Glycerin 10.0 Perfume (1-menthol) 1.3 PH regulator 0.3 Preservative (Proxel GXL) 0.5 Adhesion Resin (styrene acrylic acid resin, neutralized with ammonia) 3.0 Surfactant (Ingen P, manufactured by Daiichi Pharmaceutical Co., Ltd.) 0.2
(ポールペン用インキ組成、 全量 100重量％) (Ink composition for pole pen, 100% by weight)
C. I. Direct Black-154 4. 5 C. I. Direct Black-19 1. 5 エチレングリコール 0 0 グリセリン 0 0 ゲル化剤 （キサンタンガム） 0 3 防腐剤 （プロキセル GXL) 0 5 固着性樹脂 （スチレンアクリル酸樹脂、 アンモニア中和） 3 0 界面活性剤 （インゲン P、 第一製薬工業社製） 0 2 (ポールペン用インキ組成香料タイプ、 全量 1 0 0重量％) C. I. Direct Black - 154 4 5 CI Direct Black-154 4.5 CI Direct Black-19 1.5 Ethylene glycol 0 0 Glycerin 0 0 Gelling agent (Xanthan gum) 0 3 Preservative (Proxel GXL) 0 5 Sticking resin (Styrene acrylic resin, in ammonia) Sum) 30 surfactant (green bean P, manufactured by Daiichi Pharmaceutical) 0 2 (Perfume ink composition for pole pen, 100% by weight) CI Direct Black-154 4 5
C. I. Direc t Black- 19 5 プロピレングリコール 0 0 グリセリン 0 0 香料 （1—メントール） 3 ゲル化剤 （キサンタンガム） 0 3 防腐剤 （プロキセル G X L) 0 5 固着性樹脂 （スチレンアクリル酸樹脂、 アンモニア中和） 3 0 界面活性剤 （インゲン P、 第一製薬工業社製） 0 2 精製水 CI Direc t Black- 19 5 Propylene glycol 0 0 Glycerin 0 0 Fragrance (1-menthol) 3 Gelling agent (Xanthan gum) 0 3 Preservative (Proxel GXL) 0 5 Sticking resin (Styrene acrylic acid resin, ammonia neutralization) 3 0 Surfactant (Bean P, manufactured by Daiichi Pharmaceutical) 0 2 Purified water
(ィンキの吹き出し性の評価法）  (Evaluation method of blow-out characteristics of ink)
5 0 °CD r y環境下、 3 5 °C ·湿度 3 0 %環境下、 4 0 °C ·湿度 3 5 %環境 下で、 キャップした状態でペン先を下向き保存し、 1力月、 3力月、 6力月保 存したときのペンの状態を下記評価基準にて評価した。  In a 50 ° C cry environment, 35 ° C · humidity of 30% environment, 40 ° C · humidity of 35% environment, save the pen tip downward with the cap on, 1 month, 3 power The state of the pen when stored for 6 months and 6 months was evaluated according to the following evaluation criteria.
評価基準：  Evaluation criteria:
◎：インキの吹き出しが全くない。  A: There is no ink jetting.
〇：ィンキの吹き出しがやつと肉眼で確認できるが、 実用上問題ない △：インキの吹き出しがややある。  〇: Ink blowout can be confirmed with the naked eye, but there is no practical problem. △: Ink blowout is slightly.
X ：インキの吹き出しがある。  X: There is a jet of ink.
(保香性の評価法）  (Evaluation method of fragrance retention)
5 0 °CD r y環境下で、 キャップした状態でペン先を下向き保存し、 1力月 、 3力月、 6力月保存したものを筆記して描線のメントールの香りを下記評価 基準にて評価した。 ◎ :初期 （保存前） と全く変わらない香りがする。 In a 50 ° C CDry environment, store the pen tip downward with the cap capped, write on the first, third, and sixth months and write the scent of menthol on the drawing line according to the following evaluation criteria. did. ◎: The scent is the same as the initial one (before storage).
〇：初期 （保存前） に較べやや香りが弱くなつているが実用上全く問 題ない。  〇: The fragrance is slightly weaker than in the initial stage (before storage), but there is no problem in practical use.
△：香りがやや弱っている。  Δ: Slightly weak scent.
X：殆ど香りがない。 表 1  X: Almost no scent. table 1
Figure imgf000032_0001
Figure imgf000032_0001
なお、 表中の 「一」 は、 評価しなかったことを意味する。  In addition, “one” in the table means that it was not evaluated.
*1 : 3力月目で吹き出したので、 以降評価しなかった。  * 1: Since it blew out in the third month, it was not evaluated thereafter.
n： 1力月以内で、 すでに吹き出していたので、 以降評価しなかった c n: 1 within Chikaratsuki, because it was the balloon already, were not evaluated after the c
表 2 Table 2
Figure imgf000033_0001
Figure imgf000033_0001
4 0 °C - 3 5 %環境下のインキ吹き出し性40 ° C-35% environment
1力月 3力月 6力月 実施例 1 ◎ ◎ ◎ 実施例 2 ◎ ◎ ◎ 実施例 3 ◎ ◎ ◎ 実施例 4 ◎ ◎ ◎ 実施例 5 ◎ ◎ ◎ 実施例 6 ◎ ◎ ◎ 実施例 7 ◎ ◎ ◎ 実施例 8 ◎ ◎ ◎ 実施例 9 ◎ ◎ ◎ 比較例 1 〇 〇〜△ △〜X 比較例 2 〇〜△ △ X 表 4 1 month 3 months 6 months Example 1 ◎ ◎ ◎ Example 2 ◎ ◎ ◎ Example 3 ◎ ◎ ◎ Example 4 ◎ ◎ ◎ Example 5 ◎ ◎ ◎ Example 6 ◎ ◎ ◎ Example 7 ◎ ◎ ◎ Example 8 ◎ ◎ ◎ Example 9 ◎ ◎ ◎ Comparative Example 1 〇 〇 to △ △ to X Comparative Example 2 〇 to △ △ X Table 4
Figure imgf000034_0001
上記表 1〜 4の結果から明らかなように、 本発明範囲となる実施例 1〜 9は 、 本発明の範囲外となる比較例 1〜2に較べ、 筆記具用インキ収容部材に空気 中の酸素が透過することがなくなるので、 インキの吹き出しを長期間防止する ことができるとともに、 香料入りィンキの保香性を向上することができる筆記 具用ィンキ収容部材 （筆記具用ィンキを収容するコレクター構造を有する直液 筆記具、 ポールペンのインキ収容管） であることが判明した。
Figure imgf000034_0001
As is clear from the results of Tables 1 to 4 above, Examples 1 to 9 that are included in the scope of the present invention are compared with Comparative Examples 1 and 2 that are not included in the scope of the present invention. Since ink does not pass through, ink blowing can be prevented for a long period of time, and the ink holding member for writing implements that can improve the scent retention of the scented ink can be used. It has been found that it is a direct liquid writing instrument and a pole pen ink storage tube.
〔実施例 10〜 20及び参考例 1、 第 2発明〕  (Examples 10 to 20 and Reference Examples 1 and 2)
下記方法により第 2発明 〔筆記具用インキ収容部材の外側表面部に酸素透過 係数が 25 :Dryで 10— 10 (c c · cm/ cm2 ' s e c · cmHg) 以 下の有機高分子中に平板状無機微粒子が分散されているコート層を形成〕 の各 筆記具用ィンキ収容部材を備えた筆記具を作製した。 Oxygen permeation coefficient on the outer surface of the second invention [ink for a writing instrument accommodating member by the following method is 25: in Dry 10- 10 (cc · cm / cm 2 'sec · cmHg) tabular the organic polymer follows Forming a coating layer in which inorganic fine particles are dispersed].
(実施例 10、 直液式サインペン）  (Example 10, direct liquid type felt pen)
射出成形により直液式サインペン用の PP製インキ収容容器を作製した。 こ の PP製インキ収容容器は第 3図の図示符号 21に準拠するものであり、 肉厚 1. 0mm、 内径 6. 4mm, 長さ 120mmである。 PPの酸素透過係数は 、 25°CD r yで約 10—9 (c c · cm/ cm2 - s ec · cmHg) であつ た。 An ink container made of PP for a direct liquid type felt pen was manufactured by injection molding. This PP ink container complies with the reference numeral 21 in FIG. 3, and has a thickness of 1.0 mm, an inner diameter of 6.4 mm, and a length of 120 mm. Oxygen permeability coefficient of the PP is about 10-9 at 25 ° CD ry (cc · cm / cm 2 - s ec · cmHg) filed by Was.
この P P製ィンキ収容容器の外側表面部全体を金型により梨地化処理し、 次 いで、 該表面部全体をグロ一放電によりプラズマ処理した。 この梨地化処理、 プラズマ処理した P P製ィンキ収容容器の外側表面部全体に酸素透過係数が 2 5°CD r yで約 5 X 10— 14 (c c · cm/ cm2 - s e c - cmHg) の E V〇H (エチレンモル比率 38mo 1 %) 中に平板状無機微粒子としてマイ力 (ME— 100、 コープケミカル社製） を EVOHに対して 5重量％分散させ たものを平均厚約 0. 1 mになるように、 デイツビング法を用いてコ一ティ ング処理し、 本体層とコート層の総厚 1000. l mにした。 また、 この P P製インキ収容容器の全体の酸素透過係数 Pは約 9. 8 X 10"11 (c c · c m/cm2 ' s e c ' cmHg) であった。 The entire outer surface of the PP ink container was matted using a mold, and then the entire surface was plasma-treated by glow discharge. The satin treatment, plasma treatment and oxygen permeability coefficient across outer surface portion of the PP made Inki container is 2 5 ° CD ry about 5 X 10- 14 (cc · cm / cm 2 - sec - cmHg) EV_〇 of 5% by weight of EVOH (ME-100, manufactured by Corp Chemical) dispersed as flat inorganic fine particles in H (38 mol 1% ethylene mole ratio) so as to have an average thickness of about 0.1 m Then, a coating treatment was performed using a dating method to make the total thickness of the main body layer and the coat layer 1000.lm. The oxygen permeability coefficient P of the PP ink container was about 9.8 × 10 ″ 11 (cc · cm / cm 2 ′ sec′cmHg).
この P P製ィンキ収容容器を用いて第 3図に示す直液式サインぺンを組み立 た。  Using this PP ink container, a direct liquid type sign-in as shown in Fig. 3 was assembled.
(実施例 11、 直液式サインペン）  (Example 11, direct liquid type felt pen)
上記実施例 10において、 プラズマ処理のみを除いた実施例 10と同様の直 液式サインペンを組み立た。 なお、 各酸素透過係数は実施例 10と同様であつ た。  In Example 10, a direct-type felt-tip pen similar to Example 10 except for the plasma treatment was assembled. The respective oxygen permeability coefficients were the same as in Example 10.
(実施例 12、 直液式サインペン）  (Example 12, direct liquid type pen)
上記実施例 10において、 梨地化処理のみを除いた実施例 10と同様の直液 式サインペンを組み立た。 なお、 各酸素透過係数は実施例 10と同様であった  In Example 10 described above, a direct liquid type felt pen similar to Example 10 except for the matte finish treatment was assembled. The respective oxygen permeability coefficients were the same as in Example 10.
(実施例 13、 直液式サインペン） (Example 13, direct liquid type felt pen)
上記実施例 10において、 梨地化処理、 プラズマ処理の両方を除き実施例 1 0と同様の直液式サインペンを組み立た。 なお、 各酸素透過係数は実施例 10 と同様であった。  In Example 10 described above, a direct liquid type felt-tip pen similar to that of Example 10 was assembled except for both the satin finish treatment and the plasma treatment. The respective oxygen permeability coefficients were the same as in Example 10.
(実施例 14、 直液式サインペン） 上記実施例 10において、 マイ力に代え平板状無機微粒子として合成マイ力 (MK— 100、 コープケミカル社製） を EVOHに対して 5重量％分散させ たものを平均厚約 0. 1 mになるように、 デイツビング法を用いてコーティ ング処理し、 上記実施例 10と同様にして本体層とコート層の総厚 1000. 1 にして実施例 10と同様の直液式サインペンを組み立た。 (Example 14, direct liquid type felt pen) In Example 10, the average thickness is about 0.1 m obtained by dispersing 5% by weight of synthetic My power (MK-100, manufactured by Corp Chemical) as EVOH as flat inorganic fine particles instead of My power. As described above, the coating treatment was performed using the dive method, and the total thickness of the main body layer and the coat layer was set to 1000.1 in the same manner as in Example 10 to assemble the direct liquid type pen as in Example 10.
また、 この PP製インキ収容容器の全体の酸素透過係数 Pは約 4. 5X 10 一10 (c c · cm/ cm2 - s e c - cmH ) であった。 Further, the oxygen permeability coefficient P of the whole ink container made of PP was about 4.5 × 10 10 (cc · cm / cm 2 -sec-cmH).
(実施例 15、 直液式サインペン）  (Example 15, direct liquid type felt pen)
上記実施例 10において、 マイ力に代え平板状無機微粒子としてモンモリロ ナイト （クニピア F、 クニミネ工業社製） を EVOHに対して 5重量％分散さ せたものを平均厚約 0. 1 mになるように、 デイツピング法を用いてコーテ イング処理し、 上記実施例 10と同様にして本体層とコート層の総厚 1000 . 1 mにして実施例 10と同様の直液式サインペンを組み立た。  In Example 10 above, montmorillonite (Kunipia F, manufactured by Kunimine Industries Co., Ltd.) as tabular inorganic fine particles instead of my force was dispersed at 5% by weight in EVOH so as to have an average thickness of about 0.1 m. Then, a coating process was performed using a dipping method, and a direct liquid type pen as in Example 10 was assembled in the same manner as in Example 10 except that the total thickness of the main body layer and the coat layer was set to 1000.
また、 この PP製インキ収容容器の全体の酸素透過係数 Pは約 4. 0X 10 — 10 、c c · cm/ cm2 · s e c · cmHg) であった。 Further, the whole of the oxygen permeability coefficient P of the PP-made ink container about 4. 0X 10 - was 10, cc · cm / cm 2 · sec · cmHg).
(実施例 16、 直液式サインペン）  (Example 16, direct liquid type felt pen)
上記実施例 10において、 インキ収容容器用材料として、 PP樹脂 （J 22 6E、 三井石油化学社製） 100重量部に対して石油樹脂 （アルコン P— 10 0、 荒川化学工業社製） 20重量部を配合した樹脂組成物を用いて PP製イン キ収容容器を実施例 1と同寸法のものを作製した。 この PP製インキ収容容器 の酸素透過係数は、 25°CD r yで約 10— 9 (c c · cm/cm2. s e c * cmHg) であった。 In Example 10 described above, 20 parts by weight of petroleum resin (Alcon P-100, Arakawa Chemical Industries) was used as the ink container material for 100 parts by weight of PP resin (J226E, manufactured by Mitsui Petrochemical Co., Ltd.). A PP ink container having the same dimensions as in Example 1 was prepared using a resin composition containing the same. Oxygen permeability coefficient of the PP-made ink container was about 10 9 25 ° CD ry (cc · cm / cm 2. Sec * cmHg).
この PP製インキ収容容器を用いて （梨地化処理、 プラズマ処理せず） 、 上 記実施例 10と同様にして EVOH+平板状無機微粒子分散のコート層を作製 した。 また、 この PP製インキ収容容器の全体の酸素透過係数 Pは約 4. 5X 10— 10 (c c · cm/ cm2 - s e c - cmHg) であった。 この P P製ィンキ収容容器を用いて実施例 10と同様にして直液式サインぺ ンを組み立た。 Using this PP ink container (without satin finish treatment or plasma treatment), a coat layer of EVOH + flat inorganic fine particle dispersion was produced in the same manner as in Example 10 above. Further, the whole of the oxygen permeability coefficient P of the PP-made ink container about 4. 5X 10- 10 (cc · cm / cm 2 - cmHg - sec) was. Using this PP ink container, a direct liquid signin was assembled in the same manner as in Example 10.
(実施例 17、 直液式サインペン）  (Example 17, direct liquid type felt pen)
上記実施例 10において、 実施例 10と同様に梨地化処理、 プラズマ処理し た P P製ィンキ収容容器の外側表面部全体に酸素透過係数が 25 °C D r yで約 10— 13 (c c · cm/ cm2 - s e c - cmHg) の PVA (ケン化度 98 %) 中に平板状無機微粒子として合成スメク夕イト （スメクトン SA、 クニミ ネ工業社製） を PVAに対して 1重量％分散させたものを平均厚約 0. l m になるように、 デイツピング法を用いてコーティング処理し、 本体層とコート 層の総厚 1000. 1 mにした。 また、 この PP製インキ収容容器の全体の 酸素透過係数 Pは約 4. 0 X 10-10 (c c · cm/ cm2 - s e c - c mH g) であった。 In the above-described Example 10, the oxygen permeation coefficient is about 10-13 (cc · cm / cm) at 25 ° An average of 1% by weight of synthetic smectite (Smecton SA, manufactured by Kunimine Industries, Ltd.) as tabular inorganic fine particles dispersed in PVA ( 2 -sec-cmHg) at a saponification degree of 98% was dispersed in PVA. Coating was applied by dipping to a thickness of about 0.1 lm, and the total thickness of the main body layer and the coat layer was 100.1 m. The oxygen permeability coefficient P of the PP ink container was about 4.0 × 10 −10 (cc · cm / cm 2 -sec-cmHg).
この P P製ィンキ収容容器を用いて第 3図に示す直液式サインペンを組み立 た。  Using this PP ink container, a direct liquid type felt-tip pen shown in Fig. 3 was assembled.
(実施例 18、 直液式サインペン）  (Example 18, direct liquid type pen)
上記実施例 10において、 実施例 10と同様に梨地化処理、 プラズマ処理し た P P製ィンキ収容容器の外側表面部全体に酸素透過係数が 25 X D r yで約 5 X 10— 14 (c c · cm/ cm2 · s e c · cmHg) の完全ケン化 PVA 中に平板状無機微粒子として合成マイ力 （MK— 100、 コープケミカル社製 ) を PVAに対して 5重量％分散せしめ、 完全ゲン化の PVAを硼酸中の硼素 とコンプレックスを形成させたものを平均厚約 0. 1 mになるように、 ディ ッピング法を用いてコーティング処理し、 本体層とコート層の総厚 1000. l mにした。 また、 この PP製インキ収容容器の全体の酸素透過係数 Pは約 4. 8X 10一11 (c c - cmZcm2 - s e c * cmHg) であった。 In the above Example 10, Example 10 and likewise satin treatment, a plasma treatment was made of PP Inki oxygen permeability coefficient across outer surface portion of the container is 25 XD ry about 5 X 10- 14 (cc · cm / cm 2 · sec · cmHg) tabular inorganic particles as synthesized My force in completely saponified PVA of (MK-100, manufactured by Co-op Chemical Co., Ltd.) dispersion allowed 5 wt% with respect to PVA, boric acid PVA fully Gen of The complex formed with the boron in it was coated by dipping so as to have an average thickness of about 0.1 m, so that the total thickness of the main body layer and the coat layer was 1000. lm. Further, the whole of the oxygen permeability coefficient P of the PP-made ink container about 4. 8X 10 one 11 was (cc - sec * cmHg - cmZcm 2).
この P P製ィンキ収容容器を用いて第 3図に示す直液式サインペンを組み立 た。 (実施例 19、 ポールペン） Using this PP ink container, a direct liquid felt-tip pen shown in Fig. 3 was assembled. (Example 19, pole pen)
射出成形により直液筆記具用の PP製インキチューブ （リフィール） を作製 した。 この PP製インキリフィ一ルは第 1図 （a) の図示符号 Aに準拠するも のであり、 肉厚 0. 8mm、 内径 6. 4mm、 長さ 12 Ommである。 PPの 酸素透過係数は、 25°CD r yで約 5 X 10— 9 (c c · cm/cm2 · s e c • cmHg) であった。 PP ink tubes (refills) for direct liquid writing instruments were manufactured by injection molding. This PP ink refill conforms to the reference symbol A in Fig. 1 (a), and has a wall thickness of 0.8mm, an inner diameter of 6.4mm, and a length of 12 Omm. Oxygen permeability coefficient of the PP was about 5 X 10- 9 at 25 ° CD ry (cc · cm / cm 2 · sec • cmHg).
この P P製ィンキ収容容器の外側表面部全体を金型により梨地化処理し、 次 いで、 該表面部全体をグロ一放電によりプラズマ処理した。 この梨地化処理、 プラズマ処理した P P製ィンキ収容容器の外側表面部全体に酸素透過係数が 2 5t:D r yで約 5X 10— 13 (c c - cm/ cm2 - s e c - cmH ) の P VA (ケン化度 98%) 中に平板状無機微粒子として合成マイ力 （MK— 10 0、 コープケミカル社製） を PVAに対して 5重量％分散させたものを平均厚 約 0. 1 mになるように、 デイツピング法を用いてコ一ティング処理し、 本 体層とコート層の総厚 1000. 1 mにした。 また、 この PP製インキ収容 容器の全体の酸素透過係数 Pは約 4. 0 X 10— 1G (c c · cm/cm2 · s e c · cmHg) であった。 The entire outer surface of the PP ink container was matted using a mold, and then the entire surface was plasma-treated by glow discharge. The satin treatment, a plasma treatment was made of PP Inki container outer surface portion across the oxygen permeability coefficient of 2 5t: about at D ry 5X 10- 13 (cc - cm / cm 2 - sec - cmH) of P VA ( 5% by weight of PVA with synthetic My power (MK-100, manufactured by Coop Chemical Co., Ltd.) dispersed as tabular inorganic fine particles in a saponification degree of 98%) so as to have an average thickness of about 0.1 m Then, a coating treatment was performed using a dipping method to make the total thickness of the main body layer and the coat layer 1000.l m. The oxygen permeability coefficient P of the whole ink container made of PP was about 4.0 × 10-1 G (cc · cm / cm 2 · sec · cmHg).
この P P製ィンキ収容容器を用いて第 1図に示すポールペンを組み立た。 (実施例 20、 ポールペン）  The pole pen shown in FIG. 1 was assembled using this PP container. (Example 20, pole pen)
上記実施例 19において、 プラズマ処理のみを除いた実施例 19と同様のポ 一ルペン用リフィールを組み立た。 なお、 各酸素透過係数は実施例 19と同様 であった。  In Example 19, a refill for a polpen similar to Example 19 except for the plasma treatment was assembled. The respective oxygen permeability coefficients were the same as in Example 19.
〔参考例 1 (実施例 1) 、 平板状無機微粒子が分散しないコート層〕 上述の実施例 1の直液式サインペンを用いた。 すなわち、 射出成形により直 液式サインペン用の P P製ィンキ収容容器を作製した。 この P P製ィンキ収容 容器は第 3図の図示符号 21に準拠するものであり、 肉厚 1. 0mm、 内径 7 . 0mm, 長さ 50mmである。 PPの酸素透過係数は、 25°CD ryで約 5 x 1 O—9 (c c · cmZcm2 ' s ec ' c mH g) であった。 [Reference Example 1 (Example 1), Coating Layer in which Flat Inorganic Fine Particles Are Not Dispersed] The direct liquid type pen of Example 1 described above was used. In other words, a PP ink container for a direct liquid type felt pen was manufactured by injection molding. This PP ink container conforms to the reference symbol 21 in FIG. 3, and has a thickness of 1.0 mm, an inner diameter of 7.0 mm, and a length of 50 mm. The oxygen permeability coefficient of PP is about 5 at 25 ° C dry. x 1 O— 9 (cc · cmZcm 2 'sec'cmHg).
この P P製ィンキ収容容器の外側表面部全体を金型上で成形時に梨地化処理 し、 次いで、 該表面部全体を空気存在下グロ一放電によりプラズマ処理した。 この梨地化処理、 プラズマ処理した P P製ィンキ収容容器の外側表面部全体に 酸素透過係数が 2 r yで約 1 X 10— 13 (c c - cm/cm2 - s e cThe entire outer surface of the PP ink container was matted during molding on a mold, and then the entire surface was plasma-treated by glow discharge in the presence of air. The oxygen permeation coefficient is about 1 X 10—13 (cc-cm / cm 2 -sec at 2 ry) over the entire outer surface of the matte-treated and plasma-treated PP ink container.
·· cmHg) の EVOH (エチレンモル比率 38 mo 1 %) を平均厚約 1. 0 mになるように、 塗布液粘度と EVOH固形分を調整した塗布液を用いてコ —ティング処理し、 本体層とコート層の総厚 1001. 0 zmにした。 また、 この PP製インキ収容容器の全体の酸素透過係数 Pは約 9. 8X10— 11 (c c · cm/cm2 ' s e c ' c mH であった。 ··· cmHg) EVOH (ethylene mole ratio 38 mo 1%) is coated using a coating solution that has been adjusted for coating solution viscosity and EVOH solids so that the average thickness is about 1.0 m. And the total thickness of the coating layer was 1001.0 zm. Further, the whole of the oxygen permeability coefficient P of the PP-made ink container was about 9. 8X10- 11 (cc · cm / cm 2 'sec' c mH.
この P P製ィンキ収容容器を用いて第 3図に示す直液式サインペンを組み立 た。  Using this PP ink container, a direct liquid type felt-tip pen shown in Fig. 3 was assembled.
得られた各筆記具等について、 上記第 1発明での実施例 1等で用いた核組成 のインキを充填し、 各直液式サインペン、 第 2図に示すポールペンを作製した 後、 上述の各方法によりインキの吹き出し性、 保香性を評価すると共に、 下記 方法により、 耐擦過性について更に評価した。  Each of the obtained writing implements is filled with the ink having the nucleus composition used in Example 1 of the first invention, etc., and each of the direct liquid type pens and the pole pens shown in FIG. 2 is manufactured. The ink blowing performance and fragrance retention were evaluated by the following method, and the rub resistance was further evaluated by the following method.
これらの結果を下記表 5〜 9に示す。  The results are shown in Tables 5 to 9 below.
上記実施例 10〜 18及び参考例 1は上述の直液筆記具用ィンキ組成、 直液 筆記具用インキ組成 （香料タイプ） 各 l gを充填した。 また、 上記実施例 19 〜20は、 上述の実施例 8等で用いたのポ一ルペン用インキ組成物、 ポールべ ン用インキ組成物 （香料タイプ） 各 lgを充填した。  In Examples 10 to 18 and Reference Example 1, each of the above-described ink composition for a direct liquid writing instrument and the ink composition for a direct liquid writing instrument (fragrance type) was filled with each 1 g. In each of Examples 19 to 20, the ink compositions for the pole pens and the pole pens (perfume types) used in Example 8 and the like were filled with lg.
(耐擦過性の評価法）  (Evaluation method for scratch resistance)
得られた各筆記具のコ一卜層を爪で引つかくことにより、 コート層の剥離の 状態を下記評価基準にて評価した。  The coating layer of each of the writing instruments thus obtained was gripped with a nail, and the state of peeling of the coating layer was evaluated according to the following evaluation criteria.
評価基準：  Evaluation criteria:
◎：全く変化なし。 〇：傷がつくが剥離なし c A: No change at all. 〇: Scratches but no peeling c
△ :部分的な剥離あり。  Δ: Partial peeling occurred.
X：全面剥離。 5  X: Full peeling. Five
Figure imgf000040_0001
Figure imgf000040_0001
表 6 Table 6
3 5 °C · 3 0 %環境下のインキ吹き出し性 35 ° C · 30% environment
1力月 3力月 6力月 実施例 1 0 ◎ ◎ ◎ 実施例 1 1 ◎ ◎ ◎ 実施例 1 2 ◎ ◎ ◎ 実施例 1 3 ◎ ◎ ◎ 実施例 1 4 ◎ ◎ ◎ 実施例 1 5 ◎ ◎ ◎ 実施例 1 6 ◎ ◎ ◎ 実施例 1 7 ◎ ◎ ◎ 実施例 1 8 ◎ ◎ ◎ 実施例 1 9 ◎ ◎ ◎ 実施例 2 0 ◎ ◎ ◎ 表 7 1 month 3 months 6 months Example 1 0 ◎ ◎ ◎ Example 1 1 ◎ ◎ ◎ Example 1 2 ◎ ◎ ◎ Example 1 3 ◎ ◎ ◎ Example 1 4 ◎ ◎ ◎ Example 1 5 ◎ ◎ ◎ Example 1 6 ◎ ◎ ◎ Example 1 7 ◎ ◎ ◎ Example 1 8 ◎ ◎ ◎ Example 1 9 ◎ ◎ ◎ Example 2 0 ◎ ◎ ◎ Table 7
Figure imgf000041_0001
Figure imgf000041_0001
表 8 Table 8
保香性  Scent retention
1力月 3力月 6力月 実施例 1 0 ◎ ◎ ◎ 実施例 1 1 ◎ ◎ ◎ 実施例 1 2 ◎ ◎ ◎ 実施例 1 3 ◎ ◎ ◎ 実施例 1 4 ◎ ◎ ◎ 実施例 1 5 ◎ ◎ ◎ 実施例 1 6 ◎ ◎ ◎ 実施例 1 7 ◎ ◎ ◎ 実施例 1 8 ◎ ◎ ◎ 実施例 1 9 ◎ ◎ ◎ 実施例 2 0 ◎ ◎ ◎ 表 9 1 month 3 months 6 months Example 1 0 ◎ ◎ ◎ Example 1 1 ◎ ◎ ◎ Example 1 2 ◎ ◎ ◎ Example 1 3 ◎ ◎ ◎ Example 1 4 ◎ ◎ ◎ Example 1 5 ◎ ◎ ◎ Example 1 6 ◎ ◎ ◎ Example 1 7 ◎ ◎ ◎ Example 1 8 ◎ ◎ ◎ Example 1 9 ◎ ◎ ◎ Example 2 0 ◎ ◎ ◎ Table 9
Figure imgf000042_0001
Figure imgf000042_0001
なお、 上記表中の 「一」 は、  In addition, "one" in the above table means
評価しなかったことを意味する t 上記表 5〜9の結果から明らかなように、 本発明範囲となる実施例 1 0〜2 0は、 筆記具用ィンキ収容部材に空気中の酸素が透過することがなくなるので 、 インキの吹き出しを長期間防止することができるとともに、 香料入りインキ の保香性を向上することができ、 しかも、 平板状無機微粒子が分散しないコー ト層の参考例 1 (実施例 1 ) に較べ、 機械的強度にも更に優れる筆記具用イン キ収容部材 （筆記具用ィンキを収容するコレクター構造を有する直液筆記具、 ボールペンのインキ収容管） であることが判明した。 産業上の利用可能性 As apparent from the results of t Table 5-9, which means that not evaluated, Example 1 0-2 0 as the range of the present invention, the oxygen in the air passes through the Inki housing member for a writing instrument As a result, it is possible to prevent the ejection of the ink for a long period of time, to improve the scent retention of the scented ink, and to obtain a coating layer in which the flat inorganic fine particles are not dispersed. Compared to 1), it was found that the ink storage member for writing implements (a direct liquid writing implement having a collector structure for accommodating ink for writing implements, and an ink storage tube for a ballpoint pen) was also superior in mechanical strength. Industrial applicability
以上のように、 本発明によれば、 筆記具用インキ収容部材に空気中の酸素が 透過することがなくなり、 インキの劣化防止、 並びに香料入りインキの保香性 向上、 更にはィンキの吹き出しを長期間防止することができる筆記具用ィンキ 収容部材が提供される。 As described above, according to the present invention, oxygen in the air does not pass through the ink storage member for writing implements, preventing deterioration of the ink, improving the scent retention of the scented ink, and extending the discharge of the ink. Ink for writing implements that can prevent the period A receiving member is provided.
また、 酸素透過係数が 2 5 °CD r yで 1 0— 1 0 ( c c · c m/ c m2 · s e c - c mH g) 以下の有機高分子中に平板状無機微粒子が分散されているコー ト層を形成したものでは、 更に、 コート層の機械的強度が向上し、 耐擦過性に 優れる筆記具用ィンキ収容部材が提供される。 The oxygen permeability coefficient of 1 2 5 ° CD ry 0- 1 0 (cc · cm / cm 2 · sec - c mH g) Coat layer tabular inorganic fine particles are dispersed in the following organic polymers In addition, the present invention provides an ink container for writing implements, in which the mechanical strength of the coat layer is improved and the scratch resistance is excellent.
更に、 筆記具用ィンキ収容部材の外側表面を粗面部から構成して平滑面がな い構造としたり、 オゾン処理、 プラズマ処理、 コロナ処理、 紫外線照射処理、 高圧放電処理及び酸処理から選ばれる少なくとも 1種の活性化処理を施したり 、 また、 筆記具用インキ収容部材をポリオレフイン系熱可塑性有機高分子 1 0 0重量部に対して、 石油樹脂及び/又はその誘導体が 5〜4 0重量部配合され たものにより構成したものでは、 更にコート層との密着性が向上し、 更に酸素 が透過することがなくなり、 耐擦過性に優れると共に、 インキの劣化防止、 並 びに香料入りインキの保香性向上、 更にはインキの吹き出しを更に長期間防止 することができるものとなる。  Further, the outer surface of the writing instrument ink storage member is made of a rough surface to have a structure without a smooth surface, or at least one selected from ozone treatment, plasma treatment, corona treatment, ultraviolet irradiation treatment, high pressure discharge treatment, and acid treatment. Various kinds of activation treatments were performed, and a petroleum resin and / or a derivative thereof was blended in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the polyolefin-based thermoplastic organic polymer in the ink storage member for writing implements. In the case where the ink is composed of an ink, the adhesion to the coat layer is further improved, oxygen is not transmitted, and the abrasion resistance is improved, and the ink is prevented from deteriorating. Furthermore, it is possible to prevent the ejection of ink for a longer period of time.

Claims

請求の範囲 The scope of the claims
1. 筆記具用ィンキを収容する有機高分子から構成される筆記具用ィンキ収容 部材であって、 該筆記具用インキ収容部材の外側表面部に酸素透過係数が 25 °CD r yで 10— 10 (c c ' cm/ cm2 - s e c - cmHg) 以下のコート 層が形成されていることを特徴とする筆記具用インキ収容部材。 1. A Inki housing member for a writing instrument constructed of an organic polymer which accommodates the writing instrument Inki, the oxygen permeability coefficient in the outer surface portion of the writing instrument ink containing member is at 25 ° CD ry 10- 10 (cc ' cm / cm 2 -sec-cmHg) An ink storage member for a writing implement, wherein a coating layer of the following is formed.
2. 筆記具用ィンキを収容する有機高分子から構成される筆記具用ィンキ収容 部材であって、 該筆記具用インキ収容部材の外側表面部に酸素透過係数が 25 °CD r yで 10— 1() (c c · cm/ cm2 - s e c - cmHg) 以下の有機高 分子中に平板状無機微粒子が分散されているコ一ト層が形成されていることを 特徴とする筆記具用ィンキ収容部材。 2. An ink container for a writing instrument comprising an organic polymer for accommodating an ink for a writing instrument, the outer surface of the ink container for a writing instrument having an oxygen transmission coefficient of 10-1 () at 25 ° C. (c · cm / cm 2 -sec-cmHg) An ink container for writing implements, characterized in that a coating layer in which tabular inorganic fine particles are dispersed in an organic polymer having a density of not more than an organic polymer is formed.
3. 筆記具用ィンキ収容部材が筆記具用ィンキ収容容器又はィンキ収容管であ ることを特徴とする請求の範囲第 1項又は第 2項記載の筆記具用ィンキ収容部 材。  3. The ink container for a writing instrument according to claim 1 or 2, wherein the ink container for a writing instrument is an ink container or a tube for a writing instrument.
4. 平板状無機微粒子が天然粘土鉱物類、 合成粘土鉱物類から選ばれる薄い層 構造を有する平板層状無機物であることを特徴とする請求の範囲第 2項又は第 3項記載の筆記具用ィンキ収容部材。 4. The ink container for a writing instrument according to claim 2 or 3, wherein the flat inorganic fine particles are a flat layer inorganic material having a thin layer structure selected from natural clay minerals and synthetic clay minerals. Element.
5. 平板層状無機物の層間が陽イオン交換能を有する又は有機処理されている ことを特徴とする請求の範囲第 4項記載の筆記具用インキ収容部材。  5. The ink storage member for a writing instrument according to claim 4, wherein the interlayer of the flat layered inorganic substance has a cation exchange ability or is organically treated.
6. 平板状無機微粒子の含有量が有機高分子中に 0. 1〜25重量％分散され ていることを特徴とする請求の範囲第 2項〜第 5項の何れか一つに記載の筆記 具用インキ収容部材。 6. The writing according to any one of claims 2 to 5, wherein the content of the tabular inorganic fine particles is 0.1 to 25% by weight dispersed in the organic polymer. Ink storage member for ingredients.
7. コート層がポリビニルアルコール層、 エチレン 'ビニルアルコール共重合 体層、 ポリアミド層の少なくとも一つから構成されていることを特徴とする請 求の範囲第 1項又は第 3項記載の筆記具用ィンキ収容部材。  7. The writing instrument ink according to claim 1 or 3, wherein the coat layer is composed of at least one of a polyvinyl alcohol layer, an ethylene-vinyl alcohol copolymer layer, and a polyamide layer. Housing member.
8. コート層の有機高分子がポリビニルアルコール、 エチレン ·ビニルアルコ ール共重合体、 ポリアミドの少なくとも一つから構成されていることを特徴と する請求の範囲第 2項〜第 6項の何れか一つに記載の筆記具用ィンキ収容部材 8. The organic polymer of the coating layer is polyvinyl alcohol, ethylene vinyl alcohol 7. The ink container for a writing instrument according to claim 2, wherein the ink container is made of at least one of a cellulose copolymer and a polyamide.
9 . コート層は耐水ィ匕処理が施されているコート層であることを特徴とする請 求の範囲第 1項〜第 8項の何れか一つに記載の筆記具用ィンキ収容部材。9. The ink storage member for a writing instrument according to any one of claims 1 to 8, wherein the coat layer is a coat layer that has been subjected to a water-resistant treatment.
1 0 . 筆記具用インキ収容部材の外側表面部が粗面部からなり平滑でないこと を特徴とする請求の範囲第 1項〜第 9項の何れか一つに記載の筆記具用ィンキ 収容部材。 10. The ink container for a writing instrument according to any one of claims 1 to 9, wherein the outer surface of the ink container for a writing instrument has a rough surface and is not smooth.
1 1 . 筆記具用インキ収容部材の外側表面部には、 オゾン処理、 プラズマ処理 、 コロナ処理、 紫外線照射処理、 高圧放電処理及び酸処理から選ばれる少なく とも 1種の活性化処理が施されていることを特徴とする請求の範囲第 1項〜第 1 0項の何れか一つに記載の筆記具用ィンキ収容部材。  1 1. At least one activation treatment selected from ozone treatment, plasma treatment, corona treatment, ultraviolet irradiation treatment, high-pressure discharge treatment and acid treatment is applied to the outer surface of the ink storage member for writing implements. The ink-ink storage member for a writing instrument according to any one of claims 1 to 10, characterized in that:
1 2. 筆記具用インキ収容部材は、 熱可塑性の有機高分子から構成されている ことを特徴とする請求の範囲第 1項〜第 1 1項の何れか一つに記載の筆記具用 インキ収容部材。  12. The ink storage member for a writing implement according to any one of claims 1 to 11, wherein the ink storage member for a writing implement is composed of a thermoplastic organic polymer. .
1 3. 筆記具用インキ収容部材は、 ポリオレフイン系熱可塑性有機高分子から 構成されていることを特徴とする請求の範囲第 1項〜第 1 2項の何れか一つに 記載の筆記具用ィンキ収容部材。  1 3. The ink container for a writing implement according to any one of claims 1 to 12, wherein the ink storage member for a writing implement is composed of a polyolefin-based thermoplastic organic polymer. Element.
1 4. ポリオレフイン系熱可塑性有機高分子には、 ポリオレフイン系熱可塑性 有機高分子 1 0 0重量部に対して、 石油樹脂及び Z又はその誘導体が 5〜4 0 重量部配合されていることを特徴とする請求の範囲第 1 3項記載の筆記具用ィ ンキ収 部材。  1 4. The polyolefin-based thermoplastic organic polymer is characterized by blending 5 to 40 parts by weight of petroleum resin and Z or its derivative with respect to 100 parts by weight of the polyolefin-based thermoplastic organic polymer. The ink-collecting member for a writing instrument according to claim 13, wherein
1 5. 筆記具用インキ収容部材の肉厚とコート層とを合わせた総厚が 0. 5〜 5 . 0 mmであり、 ート層の厚さが 0. 1〜 2 0 0 0 mであることを特徵 とする請求の範囲第 1項〜第 1 4項の何れか一つに記載の筆記具用インキ収容 部材。 1 5. The total thickness including the thickness of the ink storage member for the writing implement and the coating layer is 0.5 to 5.0 mm, and the thickness of the coating layer is 0.1 to 2000 m. The ink storage member for a writing instrument according to any one of claims 1 to 14, characterized in that:
16. 筆記具用インキ収容部材の肉厚を L 1、 酸素透過係数を P Iとし、 コー ト層の厚さを L 2、 酸素透過係数を P 2とし、 筆記具用インキ収容部材のコ一 ト層を形成した時の全体の酸素透過係数を Pとした場合に、 全酸素透過係数 P を下記式 （I) で定義したときに、 この全酸素透過係数 Pが 10—9 (c c · cm/cm2 - s e c - cmHg) 以下であることを特徴とする請求の範囲第 1項〜第 15項の何れか一つに記載の筆記具用ィンキ収容部材。 16. The thickness of the ink storage member for writing implement is L1, the oxygen permeability coefficient is PI, the thickness of the coating layer is L2, the oxygen permeability coefficient is P2, and the coating layer of the ink storage member for writing implement is the overall oxygen transmission coefficient when the formed when is P, when defining the total oxygen permeability coefficient P by the following formula (I), the total oxygen permeability coefficient P is 10- 9 (cc · cm / cm 2 -sec-cmHg) The ink container for a writing instrument according to any one of claims 1 to 15, wherein the temperature is equal to or less than -sec-cmHg).
(L 1+L2) /P = L 1/P 1 +L 2/P 2 (I)  (L 1 + L2) / P = L 1 / P 1 + L 2 / P 2 (I)
PCT/JP2003/003024 2002-03-14 2003-03-13 Ink holding member for writing material WO2003076208A1 (en)

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JP2002-070291 2002-03-14
JP2002-225123 2002-08-01
JP2002225123A JP2004066476A (en) 2002-08-01 2002-08-01 Ink holding member for writing utensil

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WO2003076208A1 true WO2003076208A1 (en) 2003-09-18

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WO (1) WO2003076208A1 (en)

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CN109383163A (en) * 2017-08-09 2019-02-26 旭化成株式会社 Ink accommodates pipe and writing implement

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CN109383163A (en) * 2017-08-09 2019-02-26 旭化成株式会社 Ink accommodates pipe and writing implement

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