JP2003266986A - Ink housing member for writing instrument - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink housing member for a writing instrument, which can prevent an ink from being deteriorated by making oxygen in air permeate the ink housing member for writing instrument, such as an ink housing container for the writing instrument and an ink housing pipe, for housing the ink for the writing instrument, for example, a liquid ink such as a water-based or oil-based ink, or a gelatinous ink, and which can prevent blowoff of the ink. <P>SOLUTION: This ink housing member A for the writing instrument, which is composed of an organic polymer so as to house the ink for the writing instrument, is characterized in that a coated layer 11b of which the oxygen permeability coefficient is 10<SP>-10</SP>(cc.cm/cm<SP>2</SP>.sec.cmHg) or less in a dry state at 25°C, is formed in an outside surface part of the ink housing member 11a for the writing instrument. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink container for a writing instrument, such as an ink container for a writing instrument, which contains ink for a writing instrument such as a water-based or oil-based liquid ink or a gel ink, and more specifically, to an ink containing member for a writing instrument. The present invention relates to an ink accommodating member for a writing instrument, which can prevent deterioration of the ink due to permeation of oxygen in the air into the ink accommodating member for a writing instrument, improve the aroma retaining property of the perfume-containing ink, and prevent the ink from blowing out.

[0002]

2. Description of the Related Art Conventionally, a wide variety of writing instruments are known, but generally, a direct liquid writing instrument having a collector structure,
The role of the ink storage container for the batting type writing implements and the ink storage tube (ink tube, refill) of the ballpoint pen is to store and compose the ink for writing implements such as water-based or oil-based liquid ink and gel ink. The main purpose is to prevent volatilization of the solvent.

Usually, these ink containers and ink containers for writing instruments are composed of organic polymers (synthetic resins, etc.) such as polypropylene in view of chemical stability, solvent resistance, economy, productivity and the like. It is what However, according to the research and knowledge of the present inventors, when viewed over time, air, particularly oxygen permeates into the ink container and the ink container to enter the ink container and the ink container, It has been found that there is a problem that the ink is oxidized and accelerates the deterioration of the ink such as thickening of the ink and the decrease of the concentration of the coloring material, and the problems such as the ink jetting are accelerated and the life of the writing instrument is shortened. .

On the other hand, Japanese Unexamined Patent Publication No. 8-133346 discloses a packaging method of stationery such as a writing instrument containing an antibacterial agent, in which a deoxidizer is incorporated in the packaging material to minimize contact with oxygen and moisture in the air. Disclosed is a method of packaging stationery containing an antibacterial agent, which can prevent discoloration of stationery by suppressing it. However, the technology disclosed in this publication prevents discoloration due to oxidation of stationery items such as writing instruments containing antibacterial agents when they are left on display on shelves or the like in stores for a long period of time (after manufacturing to consumers). Is what
The purpose, action, and configuration (technical idea) of the present invention are different from those of the present invention.

Further, as a measure for preventing the oxidative deterioration of the ink due to air (oxygen) mixed in the ink taken in when the ink is prepared or filled, the ink is reacted or absorbed with vitamin C, vitamin E and other oxygen. Techniques for adding components are also known. However, these techniques have a problem that the function is lost in a relatively short period of time because the amount added to the ink is naturally limited and an extremely small amount is added. In addition, in the above technology,
There is no recognition of problems such as oxidative deterioration of the ink caused by the permeation of oxygen in the ink containing member, and the blowing property of the ink from the pen tip.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art and the present situation, and is intended to solve the problems. An ink for writing instruments such as water-based or oil-based liquid ink and gel ink is provided. Prevents deterioration of ink due to the permeation of oxygen in the air into the ink storage member for writing instruments, such as the ink storage container for writing instruments and ink storage tube, and improves the aroma retention of perfume-containing ink, and further blows out the ink. An object is to provide an ink containing member for a writing instrument that can be prevented for a long period of time.

[0007]

Means for Solving the Problems The present inventors
As a result of repeated intensive studies on technical issues
An ink for a writing instrument composed of an organic polymer containing ink
The outer surface (outer peripheral surface) of the tank housing member has
By forming a coating layer, the writing instrument
Completing the present invention by finding that a container member can be obtained
It came to the end. That is, the writing instrument in of the present invention
The accommodating member exists in the following (1) to (11). (1) Composed of an organic polymer that contains ink for writing instruments
An ink containing member for a writing instrument, comprising:
Oxygen permeability coefficient of 25 ℃ Dry on the outer surface of the container
10^-Ten(Cc · cm / cm²・ Sec ・ cmHg) or less
For writing instruments, characterized in that a coat layer of
Ink storage member. (2) The ink container for writing instruments is an ink container for writing instruments.
Or (1) above, which is an ink storage tube
Ink storage member for writing instruments. (3) The coating layer is a polyvinyl alcohol layer, ethylene vinyl
The above characterized in that it is a nyl alcohol copolymer layer
The ink containing member for a writing instrument according to (1) or (2). (4) The coat layer is a coat layer that has been treated to be water resistant.
According to any one of (1) to (3) above, characterized in that
Ink storage member for writing instruments. (5) The outer surface of the ink container for writing instruments is rough
Any of the above (1) to (4) characterized by not being smooth
The ink containing member for a writing instrument as described in 1. (6) On the outer surface of the ink container for writing instruments, ozone
Treatment, plasma treatment, corona treatment, UV irradiation treatment, high
At least one type of activity selected from pressure discharge treatment and acid treatment
The above (1) to (5) characterized by having been subjected to a sexualizing treatment
An ink containing member for a writing instrument as described in any one of 1. (7) The ink container for writing instruments is made of thermoplastic organic polymer.
What is described in (1) to (6) above, which is characterized in that
The ink containing member for a writing instrument as described in any one of them. (8) The outer surface of the ink container for writing instruments should be
Being composed of fin-based thermoplastic organic polymer
For the writing instrument as described in any one of (1) to (7) above
Ink storage member. (9) Polyolefin-based thermoplastic organic polymers include
For 100 parts by weight of the reffin-based thermoplastic organic polymer,
5 to 40 parts by weight of petroleum resin or its derivative is blended
Ink storage for a writing instrument as described in (8) above
Element. (10) Combine the thickness of the ink containing member for a writing instrument with the coat layer.
The combined total thickness is 0.5 to 5.0 mm, and the thickness of the coat layer
Is 0.1 to 2000 μm
(1) ~ (9) according to any one of the ink container for writing instruments
Material. (11) The thickness of the ink containing member for writing instruments is L1, oxygen permeability
Coefficient is P1, coat layer thickness is L2, oxygen permeability coefficient
Is set to P2, and the coat layer of the ink containing member for a writing instrument is formed.
Assuming that the overall oxygen permeability coefficient is P,
When the permeation coefficient P is defined by the following formula (I), this total acid
Elementary transmission coefficient P is 10^-9(Cc · cm / cm ²・ Sec ・
cmHg) or less, above (1) to (10)
An ink containing member for a writing instrument as described in any one of 1.       (L1 + L2) / P = L1 / P1 + L2 / P2 ... (I)

The present invention (including examples described later)
“Oxygen permeability coefficient” (unit: cc · cm / cm ²
-Sec-cmHg) means a value calculated by the following formula (II). Oxygen permeability coefficient = oxygen permeability × test piece thickness (II) In the above formula (II), oxygen permeability (oxygen permeability, unit: cc)
/ M ² · 24 hr · atm) means the volume of oxygen that permeates a test piece having a unit area per unit time with a partial pressure difference, and by measuring the amount of oxygen permeating the test piece at a certain time, the following formula Required by. Oxygen permeability = oxygen permeation amount / [(high-pressure side partial pressure−low-pressure side partial pressure) × permeation area × time] The “oxygen permeation coefficient” defined in the present invention is the oxygen permeation rate as defined above. It is calculated by multiplying the test piece thickness by the thickness of the test piece and converted into the permeation amount per unit thickness. It becomes clear that it is necessary to select a coat layer having a thickness of just that. Further, "25 ° C Dry" defined in the present invention means 0% humidity (including a humidity of less than 1% which is infinitely close to 0% humidity) in an environment of 25 ° C, and "50 ° C Dry". Is 0% humidity in an environment of 50 ° C (humidity of 1% which is infinitely close to 0%).
Including less than%).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below with reference to the drawings. The ink containing member for a writing instrument of the present invention is an ink containing member for a writing instrument composed of an organic polymer that contains ink for a writing instrument, specifically,
Oxygen permeation coefficient is 10 at 25 ° C Dry on the outer surface (outer peripheral surface) of the ink container or the ink container for writing instruments.
It is characterized in that a coat layer of ^-10 (cc · cm / cm ² · sec · cmHg) or less is formed.

As the structure of the ink containing member for a writing instrument of the present invention, for example, the ink containing tube (refill) in the ballpoint pen shown in FIGS. 1 and 2 and the ink in the direct liquid writing instrument having the collector structure shown in FIG. 3 are directly stored. Ink tank part that becomes the shaft body (ink container), Fig. 4
An ink tank part which is a shaft (ink container) for directly storing ink in a writing instrument having a valve mechanism in
Examples include an ink storage unit that stores the ink in the batting type writing instrument in FIG.
There is no particular limitation as long as it is a storage member that stores the ink for writing instruments.

These ink containing members for writing instruments are made of polypropylene (PP), polyethylene (PE), cyclic polyolefin, polymethylpentene, polyethylene terephthalate (PET), polybutylene terephthalate (P).
BT), polystyrene (PS), polycarbonate (P
C), a silicone elastomer, an acrylonitrile-butadiene-styrene copolymer (ABS), nylon (polyamide), polyimide, polyvinyl chloride (PVC) or the like, and is preferably composed of an organic polymer. A plastic organic polymer, more preferably a polyolefin-based thermoplastic organic polymer such as polypropylene (PP), polyethylene (PE), cyclic polyolefin, or polymethylpentene in view of solvent resistance, economy, productivity, etc. Things are desirable.

According to the present invention, a coating layer having an oxygen transmission coefficient having the above characteristics is formed on the outer surface portion (outer peripheral surface portion) of the ink containing member for a writing instrument to substantially coat the ink containing member with the main body (layer) + coat. Although the structure has two or more layers, the main body (layer) of the ink containing member may be formed in multiple layers by using other different organic polymer layers. Also,
In the present invention, the main body of the ink storage member for a writing instrument is described in any one of the following items from the point that the adhesiveness between the ink storage member for a writing instrument (main body) and the coat layer can be made more reliable and the effect of the present invention can be further improved. It is preferable to use one having a structure or the like. A structure is used in which the outer surface portion of the main body of the ink containing member for a writing instrument is composed of a rough surface portion so that there is no smooth surface. At least one selected from ozone treatment, plasma treatment, corona treatment, ultraviolet irradiation treatment, high-pressure discharge treatment and acid treatment for the outer surface of the main body of the ink containing member for a writing instrument.
The one having a structure in which the seeds are activated is used. As a material for the main body of the ink containing member for a writing instrument, a material formed by mixing 5 to 40 parts by weight of a petroleum resin or a derivative thereof with 100 parts by weight of the above-mentioned polyolefin-based thermoplastic organic polymer is used.

As a method of forming the outer surface portion of the main body portion from a rough surface portion so as to have a structure without a smooth surface, for example, the outside of an ink container for a writing instrument or an ink storage tube which becomes an ink accommodation member for a writing instrument. It can be carried out by subjecting the surface to sandblasting, roughening the surface of the mold, and the like to roughening treatment such as satinizing.

In the above ozone treatment, the outer surface of the ink containing member for a writing instrument is brought into contact with ozone molecules to introduce a functional group such as a hydroxyperoxy group, a hydroxyl group or a carbonyl group. This is performed by exposing the ink containing member to ozone. Examples of the exposure method include, but are not particularly limited to, a method of holding in an atmosphere in which ozone is present for a predetermined time and a method of exposing in an ozone stream for a predetermined time. As the plasma treatment, the ink containing member for a writing instrument is air, oxygen, nitrogen,
It is placed in a container containing carbon dioxide, argon, neon, etc., and exposed to plasma generated by glow discharge, and the carboxylic acid group containing oxygen, nitrogen, etc. on the outer surface of the ink containing member for a writing instrument, a carbonyl group, an amino group. For the purpose of introducing a functional group such as, plasma discharge forms include direct current discharge, low frequency discharge, radio frequency discharge, and microwave discharge, but are not particularly limited.

As the corona treatment, the outer surface of the ink containing member for a writing implement can be activated by passing the ink containing member for a writing implement through an electric field in which corona discharge occurs. The above-mentioned ultraviolet irradiation treatment is a method of irradiating the outer surface of the ink containing member for a writing instrument with ultraviolet light, and when the outer surface of the ink containing member for a writing instrument is irradiated with ultraviolet light, two surface areas of the ink containing member for a writing instrument are exposed. The purpose is to introduce a carbonyl group, a carboxyl group, etc. obtained by the absorption of ultraviolet rays into the chemical structure such as a heavy bond, the chemical bond being cut by the absorbed energy, and the oxygen in the air being bonded 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 above-mentioned high-voltage discharge treatment is a method in which a high voltage of several hundred thousand volts is applied between electrodes provided with a large number of ink accommodating members for writing utensils, and discharge is performed in the air to treat oxygen in the air. The surface of the ink containing member for a writing instrument is activated, oxygen is taken into the surface, and a polar group is introduced, whereby the outer surface of the ink containing member for a writing instrument can be activated. The above-mentioned acid treatment can be carried out by directly immersing the ink accommodating member for a writing instrument in a chromium mixed acid solution, sodium hypochlorite / hydrochloric acid / water system, chlorate-sulfuric acid system, sulfuric acid or the like.

Examples of the above petroleum resin or its derivative include a hydrogenated petroleum resin containing a hydroxyl group or its derivative. Specifically, commercially available Hiletz G-1
00 (manufactured by Mitsui Petrochemical Co., Ltd.), Petrosin # 100 (manufactured by Mitsui Petrochemical Co., Ltd.), Alcon P-100 (manufactured by Arakawa Chemical Industry Co., Ltd.) and the like. If the amount of the petroleum resin used is less than 5 parts by weight, the adhesion to the coat layer will not be improved, while if it exceeds 40 parts by weight, the effect will not change.
There is a problem that the mechanical strength of the ink containing member for a writing instrument is lowered, which is not preferable. By using the ink containing member (main body) for a writing instrument described above in (1), particularly when the above-mentioned treatments (1) are performed using a polyolefin resin typified by PP, polyvinyl alcohol (P
VA), ethylene-vinyl alcohol copolymer (EVO
It is possible to further improve the adhesiveness of the coat layer having a predetermined oxygen transmission coefficient composed of H) or the like. the above~
The ink containing member (main body) for the writing instrument may be used individually, but, if necessary, a combination of the above and, and, and above (total 4). Species) may be used.

In the present invention, the coat layer formed on the outer surface portion (outer peripheral surface portion) of the ink containing member for a writing instrument having the above structure has an oxygen permeability coefficient of 10 at 25 ° C. Dry.
It is necessary to be ^-10 (cc · cm / cm ² · sec · cmHg) or less, preferably 10 ⁻¹¹ (cc · c)
m / cm ² · sec · cmHg) or less, more preferably 10 ⁻¹² to 10 ⁻¹⁵ (cc · cm / cm ² ·
sec · cmHg) is desirable. In the present invention, the oxygen permeability coefficient is 10 ^-10 (cc · c at 25 ° C Dry).
In the coating layer having a thickness of more than m / cm ² · sec · cmHg), the effect of the present invention, that is, prevention of ink deterioration due to permeation of oxygen in the air into the ink container for a writing instrument that contains the ink for a writing instrument, and The effect of preventing ink ejection for a long time cannot be achieved.

The coat layer in the present invention has an oxygen permeability coefficient of 10 ⁻¹⁰ (cc · cm / cm ² · sec at 25 ° C. Dry).
It is not particularly limited as long as it is less than or equal to cmHg), and examples thereof include a layer made of an organic polymer having a low oxygen permeability, a metal layer, an inorganic layer obtained by hydrolyzing an organometallic compound, and the like. To be Preferably,
Excellent oxygen permeation resistance, manufacturability, economy even with thin films, especially
PVA and EVOH with a low ethylene molar ratio can be dissolved in water and the coating / drying equipment can be non-explosion proof equipment when coating to obtain a coating layer. (PVA)
Layer, ethylene vinyl alcohol copolymer (EVOH)
What is a layer is desirable. Above all, P from the point of low hygroscopicity
In the case of VA, those having a saponification degree of 50% or more are more preferable, and in the case of EVOH, those having an ethylene molar ratio of 80% or less are more preferable. The resin coating layers such as the PVA layer and the EVOH layer are formed by dissolving the ink containing member for a writing instrument in a predetermined solvent by dissolving a polymer having a low oxygen permeability such as PVA or EVOH by a dipping method or the like. The gas barrier coat layer can be formed by an extrusion method or a blow molding method. The metal layer can be formed by vapor deposition, electroless plating, or the like. The inorganic layer is formed by immersing the ink containing member for a writing instrument in a solution containing an organometallic compound capable of undergoing a hydrolysis reaction or by coating the solution on the surface of the member, and through hydrolysis, a polycondensation reaction such as dehydration condensation to form an inorganic layer. it can.

In the present invention, the effect of the present invention can be exhibited by forming the coat layer having the above-mentioned characteristics. However, from the viewpoint of reduction of surface tackiness and further low hygroscopicity, organic polymer is used. The coat layer made of may be a coat layer that has been further subjected to water resistance treatment. As the water resistance treatment, for example, by reacting with the hydroxyl groups of the organic polymer forming the coat layer to substantially reduce the number of hydroxyl groups, specifically, heat treatment at 100 ° C. or higher (frame treatment) , Cross-linking reaction with hydroxyl groups by aldehydes, cross-linking reaction with methylol compounds, cross-linking reaction with epoxy compounds, cross-linking reaction with esters, cross-linking reaction with diisocyanate, copper, boron (boron compounds such as borax and sodium borate) (Including also), aluminum, titanium, zirconium, tin, vanadium and the like, and complex formation with a metal compound can reduce the number of hydroxyl groups to carry out water resistance treatment. For example, when a coating layer such as the 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 dimethylol urea or the like. It can be carried out by partially eliminating the hydroxyl group by the crosslinking reaction of.

In the present invention, the total thickness (total thickness of the main body portion + thickness of the coat layer) of the thickness of the ink containing member for the writing instrument (main body portion) and the coat layer is the kind of ink to be contained, It depends on the organic polymer species of the main body used, but is preferably 0.5 to 5.0 mm, more preferably
The thickness of the coat layer is preferably 1 to 3 mm, and the thickness of the coat layer is preferably 0.1 to 2000 μm, more preferably 0.5 to 1500 μm. By setting the total thickness to 0.5 to 5.0 mm and the thickness of the coat layer to 0.1 to 2000 μm, oxygen can be more reliably generated without causing a problem in moldability and mechanical strength. By preventing the permeation, it is possible to prevent the deterioration of the ink and the ejection of the ink. If the total thickness is less than 0.5 mm, defects may occur in terms of moldability and the strength of the ink containing member, and the total thickness may be 5.
When the thickness is more than 0 mm, the oxygen permeation resistance is improved, but the visibility is inferior for the member having the visibility (the remaining amount of the ink is visually recognized), and further, the degree of freedom in design is reduced. Will be invited. In addition, the thickness of the coat layer is 0.
When the thickness is 1 μm, the mechanical strength of the film is lowered and the oxygen permeation resistance is lowered, and when the thickness of the coat layer exceeds 2000 μm, the oxygen permeation resistance is improved, but the visibility is improved. In order to use a member having (a visual check of the remaining amount of ink, etc.), the visibility will be inferior, and the degree of freedom in design will be reduced.

According to the present invention, a writing instrument in-line having the above-mentioned structure is used.
The coating of the above physical properties on the outer surface (outer peripheral surface) of the housing member.
Oxygen in the air can be transmitted by forming
To prevent the deterioration of ink and retain the fragrance of perfume ink
Improving and preventing ink blowout for a long time
It is possible to improve these effects.
Therefore, preferably, as shown in FIG. 1, ink for writing instruments
Let L1 be the wall thickness of the containing member and P1 be the oxygen permeability coefficient.
The thickness of the layer is L2 and the oxygen permeability coefficient is P2.
When the coat layer of the ink containing member is formed, the oxygen permeability of the entire
When the excess coefficient is P, the total oxygen transmission coefficient P is
When defined in (I), this total oxygen permeability coefficient P is 10
^-9(Cc · cm / cm²・ Sec ・ cmHg) or less
Is desirable.       (L1 + L2) / P = L1 / P1 + L2 / P2 ... (I) In addition, FIG. 1 illustrates a refill.
However, in FIG.
Part), the total oxygen permeability coefficient P is 10
^-9(Cc · cm / cm²・ Sec ・ cmHg) or less
Is desirable. Total oxygen permeability P of 10^-9(Cc ・
cm / cm²・ Sec · cmHg) or less
Oxygen in the air permeates through the ink container for writing instruments.
Prevent further deterioration of ink due to
Items that can further prevent blowout
Becomes

The ink contained in the ink containing member for a writing instrument of the present invention is not particularly limited as long as it is a commonly used ink for a writing instrument, and it is water-based or oil-based for ballpoint pens, felt-tip pens, marking pens, etc. It contains ink for writing instruments such as liquid ink and gel ink.

Next, a concrete embodiment of the ink containing member for a writing instrument of the present invention will be described in more detail with reference to FIGS. 1 (a), 1 (b) and 2 show the case where the ink containing member for a writing instrument of the present invention is applied to an ink containing tube (refill) in a ballpoint pen. The ink accommodating member A for a writing instrument of this embodiment has a ball-point pen type tip 10 at the tip.
It has an ink containing tube 11 equipped with. 12
Is the ink for the ball-point pen filled in the ink containing tube,
13 is a joint member between the pen tip portion and the ink containing tube,
14 is an ink follower. This ink containing tube 11 is
As shown in FIG. 1B, the main body 11a (0.7 mm thick) made of the above-mentioned various organic polymers, PP in this embodiment.
And an oxygen permeation coefficient of 10 ⁻¹⁰ (cc · cm / cm ² ···) at 25 ° C. Dry on the outer surface (outer peripheral surface) of the main body 11a.
sec · cmHg) or less (in this embodiment, a coat layer
The coating layer is made of EVOH and has a thickness of 1.0 μm and an ethylene molar ratio of 38 mol%) 11b. In addition, the outer surface of the main body 11a is composed of the above rough surface to have a structure without a smooth surface, or the above ozone treatment, plasma treatment, corona treatment, ultraviolet irradiation treatment,
At least one kind of activation treatment selected from high-pressure discharge treatment and acid treatment, which is made of a material mixed with the above petroleum resin or its derivative, and four types of main body parts combining these (The same applies to the embodiments of FIG. 3 and subsequent figures). This ink containing member A for writing instruments
2, is used as a ballpoint pen by being attached to the shaft body 15 for a ballpoint pen. In addition, 16 is a tail plug, 1
Reference numeral 7 is a cap body, and 18 is a seal rubber.

FIG. 3 shows an application of the ink accommodating member for a writing instrument of the present invention to an ink tank portion which is a shaft (ink container) for directly storing ink in a direct liquid type writing instrument having a collector structure. The ink accommodating member B for a writing instrument of the present embodiment is composed of an ink tank portion 21 which serves as a shaft body for directly storing the ink 20 without occluding the ink 20 in the batting or the like. In addition, in the front part of the ink tank portion 21,
Ink 2 pushed out from the ink tank 21 when the air in the ink tank portion 21 expands due to temperature rise or the like.
An ink reservoir (collector member) 22 that temporarily retains 0 in order to prevent it from dropping from the pen tip or air hole is built in, and a pen tip 23 made of a fiber core is provided at the tip of the collector member 22. It has been configured. Ink is drawn from the ink tank portion 21 to the pen tip 23 through the relay core 24 provided with an ink flow path 22a attached to the center hole of the collector member 22 and the ink 2 is discharged from the ink tank portion 21.
This is performed by deriving 0 to the pen tip 23. In addition,
In FIG. 3, reference numeral 25 is a holder member, 26 is a rear shaft member fixed to the rear portion of the ink tank portion 11, and 27 is a cap. In addition, the rear portion of the pen tip 23 may be directly arranged in the ink tank portion 21 without the intermediary of the relay core 24 to lead out the ink. The ink tank portion 21 serving as the ink storage container has a main body portion (thickness 1.0 mm) made of polypropylene and an oxygen permeation coefficient of 10 ⁻¹⁰ at an outer surface portion (outer peripheral surface portion) of the main body portion at 25 ° C. Dry.
It is composed of a coating layer (thickness: 1.2 μm) made of PVA that has been subjected to a water resistance treatment with boron so as to have a (cc · cm / cm ² · sec · cmHg) or less. In addition,
The rear shaft 26 made of polypropylene may also be provided with a coat layer (thickness 0.7 μm) made of PVA that has been subjected to the water resistance treatment with boron.

FIG. 4 shows that the ink containing member for a writing instrument of the present invention is applied to an ink tank section which is a shaft (ink container) for directly storing ink in a valve type writing instrument having a valve mechanism section having a stirring ball built therein. It is a thing. The ink accommodating member C for a writing instrument of the present embodiment is composed of an ink tank portion 31 which serves as a shaft body for directly storing the ink 30 without occluding the ink 30 in the batting or the like. In addition, in this writing instrument, ink is supplied to the pen tip 33 formed of a fiber core through the valve mechanism portion 32 in the ink tank portion 31. Reference numeral 34 in FIG. 3 is a holder member, 35 is a holding member that is interposed between the valve mechanism portion 32 and the holder member 34 and holds the rear portion of the pen tip 33, 36 is a cap, and 37 is an agitator. It's a ball.
In addition, in the present 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 portion 31 includes the valve mechanism portion 32 and the fiber core with the relay core interposed. The ink may be supplied to the pen tip 33. Ink tank portion 31 that serves as this ink container
Is a main body made of cyclic polyolefin (thickness: 2.0 m
m) and the outer surface (outer peripheral surface) of the main body has an oxygen permeability coefficient of 10 ⁻¹⁰ (cc · cm / cm ² · s) at 25 ° C. Dry.
ec · cmHg) or less and a coating layer (thickness 1.0 μm) made of EVOH.

FIG. 5 shows the ink containing member for a writing instrument of the present invention applied to an ink tank portion of a writing instrument in which ink is occluded in an ink occluding body such as batting. The ink accommodating member D for a writing instrument of the present embodiment is composed of an ink tank portion 41 which serves as a shaft for accommodating an ink occlusion body 40 in which ink is occluded in a batting or the like. The front end of the ink occlusion body 40 has a rear end portion 42 formed of a fiber core and a rear end portion 42.
The ink of the ink occlusion body 40 is supplied to the pen tip 42 when a is abutted. 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 portion 41 serving as the ink container is a main body portion (thickness 1.0 mm) made of polypropylene, and the outer surface portion (outer peripheral surface portion) of the main body portion has an oxygen transmission coefficient of 10 ⁻¹⁰ (25 ° C. Dry). cc
・ Cm / cm ²・ sec ・ cmHg) or less
And a coat layer made of H (thickness 1.0 μm).

In the present invention thus constructed, an aqueous or
Is an ink for writing instruments such as oily liquid ink and gel ink.
Direct liquid writing instrument, batting that has a collector structure to accommodate ki
Ink container for ballpoint pens and ink container for writing instruments
Ink storage part for writing instruments such as tubes (ballpoint pen refills)
Oxygen permeability coefficient of the outer surface of the material is 10 at 25 ° C Dry
^-Ten(Cc · cm / cm²・ Sec ・ cmHg) or less
Since the coating layer is formed, an ink containing member for a writing instrument
The oxygen in the air does not permeate through the
To prevent odorization, improve the fragrance retention of perfume-containing ink, and
For writing instruments that can prevent blowout of ink for a long time
An ink containing member will be obtained. In addition, the above characteristics
Outside the ink containing member for writing instruments before forming the coat layer of
The side surface was made up of rough surface to make it a structure without smooth surface.
, Ozone treatment, plasma treatment, corona treatment, ultraviolet light
Less selected from irradiation treatment, high pressure discharge treatment and acid treatment
Both have been subjected to one type of activation treatment and ink collection for writing instruments.
Polyolefin thermoplastic organic polymer 100 weight
5 to 40 parts by weight of petroleum resin or its derivative with respect to parts by weight
Part made up of parts that have been mixed, or these
4 types of ink container for writing instruments
In the case of, the adhesion with the coat layer is further improved,
Furthermore, oxygen does not permeate, preventing ink deterioration.
Stopping, improving the fragrance retention of inks containing fragrance, and further ink
It is possible to prevent the blowout of
It

Needless to say, the ink accommodating member for a writing instrument of the present invention is not limited to the above-mentioned embodiment, and can be modified into various forms without changing the gist of the present invention. The ink containing member for a writing instrument of the present invention has an oxygen transmission coefficient of 25 ° C. Dry on the outer surface portion of the ink containing member for a writing instrument that is composed of an organic polymer that contains the ink for a writing instrument.
Since the gist of the invention is to form a coat layer of 10 ⁻¹⁰ (cc · cm / cm ² · sec · cmHg) or less, when the present invention is applied to various writing instruments, other than the ink containing member for the writing instruments described above, The structure is not particularly limited, and various writing instruments such as ballpoint pens, felt-tip pens, and marking pens are applied. It can also be applied to a member for containing a coating liquid of an applicator, such as a correction liquid, a coating liquid, a liquid cosmetic such as a cosmetic, etc. In addition, the ink containing member for a writing instrument is made of a material having a small oxygen permeability coefficient, for example, an ethylene / vinyl alcohol copolymer (E
VOH) and the like reduce oxygen permeation, but under an environment such as a humidified atmosphere, the resin swells with water vapor in the air, the gas barrier property deteriorates, and dimensional change occurs, The effect of the present invention cannot be exerted.

[0030]

EXAMPLES 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] A writing instrument provided with an ink containing member for each writing instrument was produced by the following method. (Example 1, direct liquid type felt-tip pen) An ink container made of PP for a direct liquid type felt-tip pen was produced by injection molding. This PP ink container conforms to the reference numeral 21 in FIG. 3, and has a wall thickness of 1.0 mm, an inner diameter of 7.0 mm, and a length of 5
It is 0 mm. The oxygen permeability coefficient of PP is about 5 × 10 ⁻⁹ (cc · cm / cm ² · sec · cmH at 25 ° C. Dry.
g). The entire outer surface of the PP ink container was satinized at the time of 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 25 ° C.
About 1 × 10 ^-13 (cc · cm / cm ² · sec · cmH
g) EVOH (ethylene molar ratio 20%) was coated with a coating solution having a coating solution viscosity and EVOH solid content adjusted so that the average thickness was about 1.0 μm, and the total thickness of the main body layer and the coating layer was 1001. It was set to 0.0 μm. The oxygen permeability coefficient P of the PP ink container is about 9.
8 × 10 ^-11 (cc · cm / cm ² · sec · cmHg)
Met. A direct liquid type felt-tip pen shown in FIG. 3 was assembled using this PP ink container.

(Example 2, direct liquid type felt-tip pen) A direct liquid type felt-tip pen similar to that of Example 1 except for the plasma treatment was assembled. The oxygen transmission coefficients were the same as in Example 1. (Example 3, direct liquid type felt-tip pen) In the above-mentioned Example 1, the same direct liquid type felt-tip pen as in Example 1 except for the satinizing treatment was assembled. The oxygen transmission coefficients are shown in Example 1.
Was similar to. (Example 4, direct liquid type felt-tip pen) In Example 1, the same direct liquid type felt-tip pen as in Example 1 was assembled except for both the satinizing treatment and the plasma treatment. The oxygen transmission coefficients were the same as in Example 1.

(Embodiment 5: Direct liquid type felt-tip pen) In the above Embodiment 1, as a material for the ink container, 100 parts by weight of PP resin (J226E, manufactured by Mitsui Petrochemical Co., Ltd.) was used for petroleum resin (Alcon P-100). Manufactured by Arakawa Chemical Industry Co., Ltd.)
A PP ink container having the same dimensions as in Example 1 was prepared using a resin composition containing 20 parts by weight. This P
The oxygen permeability coefficient of the ink container made of P was about 10 ⁻⁹ (cc · cm / cm ² · sec · cmHg) at 25 ° C. Dry. Using this PP ink container (without satinizing treatment or plasma treatment), the same procedure as in Example 1 was performed.
A VOH coat was made. The oxygen permeability coefficient P of the PP ink container is about 9.8 × 10 ⁻¹¹ (c
It was c · cm / cm ² · sec · cmHg). A direct liquid type felt-tip pen was assembled using the PP ink container in the same manner as in Example 1.

(Embodiment 6) The embodiment 1 is carried out.
A PP ingot that has been treated with satin finish and plasma treatment in the same manner as in Example 1.
O Oxygen permeation coefficient of 25 ° C on the entire outer surface of the container
about 5 × 10 in ry ^-14(Cc · cm / cm²・ Sec ・ c
mHg) PVA (saponification degree 99%) average thickness about 2.0
coating using the dipping method so that
Processed to a total thickness of 1002.0 μm for the main layer and coat layer
did. Also, the oxygen permeation of the entire PP ink container is
Over coefficient P is about 2.4 × 10^-11(Cc · cm / cm²・ S
ec · cmHg). This PP ink container
The direct liquid type water-based felt-tip pen shown in FIG.

(Embodiment 7: Direct liquid type felt-tip pen) The above implementation
In Example 1, as in Example 1, satinized treatment, plasma
Oxygen is applied to the entire outer surface of the treated PP ink container.
Permeability coefficient is about 5 × 10 at 25 ℃ Dry ^-14(Cc · cm
/ Cm²・ Completely saponified PVA (sec ・ cmHg)
The average thickness of the complex formed with boron
Coat using dipping method so that it becomes 1.0 μm.
Total thickness of body layer and coat layer 1001.0
μm. In addition, the entire PP ink container
Oxygen permeability coefficient P is about 4.8 × 10^-11(Cc · cm / c
m²-Sec-cmHg). This PP ink
Assemble the direct liquid type felt-tip pen shown in Fig. 3 using the container.
It was

(Example 8, Ballpoint Pen) A PP ink tube (refill) for a direct liquid writing instrument was produced by injection molding. This PP ink refill is based on the reference symbol A in FIG. 1A, and has a wall thickness of 0.5 mm, an inner diameter of 4 mm, and a length of 120 mm. The oxygen permeability coefficient of PP is about 5 × 10 ⁻⁹ (cc · cm / cm ² at 25 ° C. Dry).
-Sec-cmHg). The entire outer surface of the PP ink container was plasma treated by glow discharge in the presence of air. The oxygen permeation coefficient was 25 ° C. Dry on the entire outer surface of the plasma-treated PP ink container.
About 1 × 10 ^-13 (cc · cm / cm ² · sec · cmH
g) EVOH (ethylene molar ratio 20%) was coated by a dipping method so that the average thickness was about 1.0 μm, and the total thickness of the main body layer and the coat layer was 1001.0 μm.
A refill for a ball-point pen shown in FIG. The overall oxygen permeability coefficient P of this PP refill
Is about 9.8 × 10 ^-11 (cc · cm / cm ² · sec · c
mHg).

Example 9, Ballpoint Pen A refill for a ballpoint pen similar to that of Example 9 except for the plasma treatment in Example 8 was assembled. In addition, each oxygen permeability coefficient was the same as that in Example 9.

(Comparative Example 1) A PP ink container for a direct writing instrument was prepared by injection molding. This PP ink container conforms to the reference numeral 21 in FIG.
The thickness is 1.0 mm, the inner diameter is 7 mm, and the length is 50 mm. P
The oxygen permeability coefficient of P is about 5 × 10 ^-9 (c
It was c · cm / cm ² · sec · cmHg). A direct liquid type felt-tip pen shown in FIG. 3 was assembled using this PP ink container.

(Comparative Example 2) A PP ink tube (refill) for a direct liquid writing instrument was produced by injection molding. This PP ink refill is based on the reference symbol A in FIG. 1A, and has a wall thickness of 0.5 mm, an inner diameter of 4 mm, and a length of 120 mm. Oxygen permeability coefficient of PP is 25 ℃ D
ry about 5 × 10 ^-9 (cc · cm / cm ² · sec · c
mHg).

Each of the obtained writing utensils and the like was filled with an ink having the following composition, and each direct liquid type felt-tip pen and the ball-point pen shown in FIG. 2 were produced, and then the ink jetting property and the aroma retaining property were evaluated by the following methods. . The results are shown in Tables 1 to 4 below.

In Examples 1 to 7 and Comparative Example 1 described above, 1 g each of the following ink composition for direct liquid writing instruments and ink composition for direct liquid writing instruments (fragrance type) was filled. In Examples 8 to 9 and Comparative Example 2 described above, 1 g each of the following ballpoint pen ink composition and ballpoint pen ink composition (fragrance type) was filled. (Ink composition for direct liquid writing instrument, total amount 100% by weight) CIDirect Black-154 4.5 CIDirect Black-19 1.5 Ethylene glycol 10.0 Glycerin 10.0 pH adjuster 0.3 Preservative (Proxel GXL) 0. 5 Adhesive Resin (Styrene Acrylic Acid Resin, Ammonia Neutralization) 3.0 Surfactant (Green Bean P, Daiichi Pharmaceutical Co., Ltd.) 0.2 Purified Water Remainder

[0042] (Ink composition for direct liquid writing instruments, fragrance type, total amount 100% by weight) C.I.Direct Black-154 4.5 C.I.Direct Black-19 1.5 Propylene glycol 10.0 Glycerin 10.0 Fragrance (1-menthol) 1.3 pH adjuster 0.3 Preservative (Proxel GXL) 0.5 Adhesive resin (styrene acrylic acid resin, ammonia neutralization) 3.0 Surfactant (green beans P, manufactured by Daiichi Pharmaceutical Co., Ltd.) 0.2 Purified water balance

[0043] (Ink composition for ballpoint pens, total amount 100% by weight) C.I.Direct Black-154 4.5 C.I.Direct Black-19 1.5 Ethylene glycol 10.0 Glycerin 10.0 Gelling agent (xanthan gum) 0.3 Preservative (Proxel GXL) 0.5 Adhesive resin (styrene acrylic acid resin, ammonia neutralization) 3.0 Surfactant (green beans P, manufactured by Daiichi Pharmaceutical Co., Ltd.) 0.2 Purified water balance

[0044] (Ballpoint pen ink composition fragrance type, 100% by weight total) C.I.Direct Black-154 4.5 C.I.Direct Black-19 1.5 Propylene glycol 10.0 Glycerin 10.0 Fragrance (1-menthol) 1.3 Gelling agent (xanthan gum) 0.3 Preservative (Proxel GXL) 0.5 Adhesive resin (styrene acrylic acid resin, ammonia neutralization) 3.0 Surfactant (green beans P, manufactured by Daiichi Pharmaceutical Co., Ltd.) 0.2 Purified water balance

(Evaluation method of ink jetting property) 50 ° C. D
In a ry environment, under a temperature of 35 ° C./humidity of 30%, and under a temperature of 40 ° C./humidity of 35%, the pen tip is stored face down in a capped state, and the state of the pen when stored for one month, three months, or six months It evaluated by the following evaluation criteria. Evaluation criteria: ⊚: No ink is blown out. ○: The ink ejection can be confirmed with the naked eye, but there is no problem in practical use. Δ: There is some ink ejection. X: Ink is blown out.

(Evaluation method of aroma retention) In a Dry environment of 50 ° C., the pen tip was stored face down in a capped state, and the scent of menthol drawn as a line was drawn by writing what was stored for 1, 3 or 6 months. It evaluated by the following evaluation criteria. Evaluation Criteria: ⊚: The fragrance is completely the same as the initial (before storage). ◯: The scent is slightly weaker than in the initial stage (before storage), but there is no problem in practical use. Δ: The fragrance is slightly weakened. X: Almost no fragrance.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

[Table 4]

As is clear from the results shown in Tables 1 to 4,
Compared with Comparative Examples 1 and 2 which are outside the scope of the present invention, Examples 1 to 9 which are within the scope of the present invention do not allow oxygen in the air to permeate through the ink containing member for a writing instrument, so that the ink is blown out longer. An ink containing member for a writing instrument (a direct liquid writing instrument having a collector structure for containing the ink for a writing instrument, an ink containing tube for a ballpoint pen) that can prevent the period and improve the aroma retaining property of the ink containing a fragrance. There was found.

[0052]

EFFECTS OF THE INVENTION According to the present invention, oxygen in the air is prevented from permeating the ink containing member for a writing instrument, preventing deterioration of the ink, improving the aroma retaining property of the perfume-containing ink, and further prolonging the jetting of the ink. Provided is an ink containing member for a writing instrument, which can prevent the period. Further, the outer surface of the ink accommodating member for a writing instrument is composed 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. In addition, the ink accommodating member for a writing instrument is composed of a mixture of 5 to 40 parts by weight of a petroleum resin or a derivative thereof with 100 parts by weight of a polyolefin-based thermoplastic organic polymer. Further, the adhesion with the coat layer is further improved, further oxygen is prevented from permeating, the deterioration of the ink can be prevented, the aroma retaining property of the perfume-containing ink can be improved, and further, the blowout of the ink can be prevented for a longer period of time. Will be things.

[Brief description of drawings]

FIG. 1 (a) is a vertical cross-sectional view showing, in a cross-sectional aspect, an example in which the ink containing member for a writing instrument of the present invention is applied to an ink containing tube for a ballpoint pen, and FIG. 1 (b) is a partial cross-section showing a main part thereof. It is a side view.

FIG. 2 is a vertical cross-sectional view of a ballpoint pen including the ink container tube for the ballpoint pen of FIG.

FIG. 3 is a longitudinal sectional view showing an example in which the ink containing member for a writing instrument of the present invention is applied to a direct liquid type felt-tip pen.

FIG. 4 is a cross-sectional view showing an example in which the ink containing member for a writing instrument of the present invention is applied to a writing instrument having a valve mechanism.

FIG. 5 is a cross-sectional view showing an example in which the ink storage member for a writing instrument of the present invention is applied to a writing instrument in which ink is occluded in an ink occluding body such as batting.

[Explanation of symbols]

11 Ink storage tube 11a main body layer 11b coat layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasuaki Ogiwara             1091, Tateishi, Fujioka-shi, Gunma Mitsubishi Pencil Stock Co., Ltd.             Gunma Research and Development Center F-term (reference) 2C350 GA01 GA03 GA04 KC02 KC03                       KC04 KC05 NA05 NA06 NA23                       NC04 NC20 NE01 NE07 NE08

Claims (11)

[Claims] 1. An ink accommodating member for a writing instrument, which is composed of an organic polymer for accommodating an ink for a writing instrument, and has an oxygen transmission coefficient of 25 on the outer surface of the ink accommodating member for a writing instrument.
10 ^-10 (cc · cm / cm ² · sec · cm at ℃ Dry
Hg) An ink accommodating member for a writing instrument, wherein the following coating layers are formed. 2. The ink containing member for a writing instrument according to claim 1, wherein the ink containing member for a writing instrument is an ink containing container for a writing instrument or an ink containing tube. 3. The ink accommodating member for a writing instrument according to claim 1, wherein the coat layer is a polyvinyl alcohol layer or an ethylene / vinyl alcohol copolymer layer. 4. The ink accommodating member for a writing instrument according to claim 1, wherein the coating layer is a coating layer that has been subjected to water resistance treatment. 5. The ink storage member for a writing instrument, wherein the outer surface portion is a rough surface portion and is not smooth.
4. The ink containing member for a writing instrument according to any one of 4 above. 6. The outer surface of the ink containing member for a writing instrument is subjected to at least one activation treatment selected from ozone treatment, plasma treatment, corona treatment, ultraviolet irradiation treatment, high pressure discharge treatment and acid treatment. The ink containing member for a writing instrument according to any one of claims 1 to 5, wherein 7. The ink containing member for a writing instrument according to claim 1, wherein the ink containing member for a writing instrument is made of a thermoplastic organic polymer. 8. The ink accommodating member for a writing instrument according to claim 1, wherein the ink accommodating member for a writing instrument is composed of a polyolefin-based thermoplastic organic polymer. 9. The polyolefin-based thermoplastic organic polymer contains 5 to 40 parts by weight of a petroleum resin or its derivative with respect to 100 parts by weight of the polyolefin-based thermoplastic organic polymer. Item 8. An ink containing member for a writing instrument according to item 8. 10. The total thickness of the ink accommodating member for a writing instrument and the coat layer is 0.5 to 5.0 mm, and the thickness of the coat layer is 0.1 to 2000 μm. The ink containing member for a writing instrument according to any one of claims 1 to 9. 11. The thickness of the ink containing member for a writing instrument is L
1, the oxygen permeability coefficient is P1, the coat layer thickness is L2,
When the oxygen permeability coefficient is P2 and the overall oxygen permeability coefficient when the coat layer of the ink containing member for a writing instrument is formed is P, when the total oxygen permeability coefficient P is defined by the following formula (I), Total oxygen transmission coefficient P is 10 ^-9 (cc · cm / cm
² · sec · cmHg) or less, The ink containing member for a writing instrument according to any one of claims 1 to 10, wherein: (L1 + L2) / P = L1 / P1 + L2 / P2 ... (I)