WO2003076208A1

WO2003076208A1 - Ink holding member for writing material

Info

Publication number: WO2003076208A1
Application number: PCT/JP2003/003024
Authority: WO
Inventors: Takao Koyama; Toshimi Kamitani; Yasuaki Ogiwara
Original assignee: Mitsubishi Pencil Kabushiki Kaisha
Priority date: 2002-03-14
Filing date: 2003-03-13
Publication date: 2003-09-18
Also published as: AU2003220897A1

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

Description Ink storage components for writing instruments Technical field

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

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.

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.

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.

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.

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.

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.

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.

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

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.

That is, the ink storage member for a writing instrument of the present invention resides in the following (1) to (16).

(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). 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) 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) 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) 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) 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) 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) 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) 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) 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) 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) 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) 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) 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) 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 + 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).

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.

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. 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

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.

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

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

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.

Hereinafter, 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. 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.

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.

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.

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.

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) 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) 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) 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.

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.

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.

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.

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.

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. 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

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.

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 is there.

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.

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.

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.

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%.

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.

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.

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

Two At least one kind (each alone or a mixture of two or more kinds) selected from titanium oxide is exemplified.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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 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.

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.

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.

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, and 14 denotes an ink follower.

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).

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 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%)

(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).

As shown in FIG. 2, the ink storage member A for a writing instrument includes a pole pen shaft

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.

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.

It is applied to

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.

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.

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). .

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. ).

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 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 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.

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 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). .

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, and 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. 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)).

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.

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

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.

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.

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.

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

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.

(Examples 1 to 9 and Comparative Examples 1 and 2, the first invention)

By the following method, a writing implement including the ink container for a writing implement according to the first invention was produced.

(Example 1, direct liquid type pen)

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.

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).

Using this PP ink container, a direct liquid type felt-tip pen shown in Fig. 3 was assembled.

(Example 2, direct liquid type felt pen)

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.

(Example 3, direct liquid type felt pen)

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)

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. '

(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).

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.

(Example 6)

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.

Using the PP ink container, a direct liquid type water-based felt-tip pen shown in Fig. 3 was assembled.

(Example 7, direct liquid type felt pen)

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.

(Example 8, pole pen)

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.

Overall oxygen permeability coefficient P of the PP-made refill was about ^{9. 8 X 10- 11 (cc •} cm / cm 2 'sec' cmHg).

(Example 9, pole pen)

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)

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.

Using this PP ink container, a direct liquid type sign-in as shown in Fig. 3 was assembled.

(Comparative Example 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 0.5mm, 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. .

The results are shown in Tables 1 to 4 below.

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.

(Ink composition for direct liquid writing implement, 100% by weight)

C.I.Direct Black-154 4.5

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

(Ink composition fragrance type for direct liquid writing instrument, 100% by weight)

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

(Ink composition for pole pen, 100% by weight)

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

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

(Evaluation method of blow-out characteristics of ink)

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.

Evaluation criteria:

A: There is no ink jetting.

〇: Ink blowout can be confirmed with the naked eye, but there is no practical problem. △: Ink blowout is slightly.

X: There is a jet of ink.

(Evaluation method of fragrance retention)

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: The fragrance is slightly weaker than in the initial stage (before storage), but there is no problem in practical use.

Δ: Slightly weak scent.

X: Almost no scent. table 1

In addition, “one” in the table means that it was not evaluated.

* 1: Since it blew out in the third month, it was not evaluated thereafter.

n: 1 within Chikaratsuki, because it was the balloon already, were not evaluated after the _c

Table 2

40 ° C-35% environment

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

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.

(Examples 10 to 20 and Reference Examples 1 and 2)

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].

(Example 10, direct liquid type felt pen)

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_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).

(Example 11, direct liquid type felt pen)

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.

(Example 12, direct liquid type pen)

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.

(Example 13, direct liquid type felt pen)

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.

(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.

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).

(Example 15, direct liquid type felt pen)

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.

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).

(Example 16, direct liquid type felt pen)

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).

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.

(Example 17, direct liquid type felt pen)

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).

(Example 18, direct liquid type pen)

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).

Using this PP ink container, a direct liquid felt-tip pen shown in Fig. 3 was assembled. (Example 19, pole pen)

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 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).

The pole pen shown in FIG. 1 was assembled using this PP container. (Example 20, pole pen)

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.

[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).

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.

··· 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.

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.

The results are shown in Tables 5 to 9 below.

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.

(Evaluation method for scratch resistance)

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.

Evaluation criteria:

A: No change at all. 〇: Scratches but no peeling _c

Δ: Partial peeling occurred.

X: Full peeling. Five

Table 6

35 ° C · 30% environment

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

Table 8

Scent retention

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

In addition, "one" in the above table means

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

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.

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.

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

The scope of the claims

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. 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. 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. 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. 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. 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. 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. 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. 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.

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. 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:

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. 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. 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. 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. 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)