JP7746065B2 - Liquid storage member for applicator - Google Patents

Description

The present invention relates to a liquid container for an applicator made of paper.

Traditionally, transparent or translucent plastics such as polypropylene have been used for the ink containers of writing instruments such as ballpoint pens. However, in recent years, there has been growing momentum to address global environmental issues, such as reducing the use of plastic, and proposals have been made to eliminate plastic for the various parts that make up writing instruments.

For example, Patent Document 1 discloses a writing instrument equipped with a barrel formed by spiral molding using a composite material made by laminating a synthetic resin with barrier properties and a metal such as aluminum onto a paper base. To improve water resistance and gas barrier properties, the barrel used in this writing instrument has a structure in which, from the exterior side of the barrel, two layers of aluminum foil label paper with a kraft paper backing and liner paper are layered, followed by a polyethylene layer on the inner surface and then a polyester film with an aluminum vapor-deposited film on the outside.

Patent Document 2 discloses an aqueous ink storage member that uses an ink storage tube with a multilayer structure, in which one or more layers of another resin are formed inside a storage tube base molded from a biodegradable resin. Because the storage tube base of this aqueous ink storage member is molded from a biodegradable resin, it does not swell with aqueous ink and undergo dimensional changes, and it biodegrades over time, contributing to a reduction in the amount of waste disposal.

However, when ink is filled into a barrel or housing tube made of these paper materials and then an ink follower is added, the ink can stain the inner walls of the barrel or housing tube. The ink scraping ability of this stained surface is easily reduced, and when the follower moves toward the stained surface after use, ink remains between the inner wall and the follower, and when the writing instrument is placed face up, ink can leak or flow back along the ink remaining between the inner wall and the follower.

To solve these problems, efforts are being made to improve the performance of barrels or housing tubes by imparting water- and oil-repellent properties to paper substrates. For example, Patent Document 3 describes a tubular casting manufacturing component used as a runner or other such component in the production of castings, which has a water-repellent paper tube layer made of kraft paper as its outermost layer, and a heat-resistant paper tube layer containing inorganic fibers, organic fibers, and a thermosetting resin inside the water-repellent paper tube layer. Patent Document 4 also describes a retort-processable paper container made from a laminated material that is sequentially laminated with an outermost layer, a paper substrate with a silicone-based water-repellent coating on its surface, a barrier layer, and an innermost layer.

Japanese Unexamined Patent Publication No. 62-70097 Japanese Patent Application Laid-Open No. 2001-146091 Japanese Patent Application Laid-Open No. 2007-152357 Japanese Patent Application Laid-Open No. 2004-17991

The present invention aims to provide a liquid container for an applicator that uses a paper material and treats the inner surface of the liquid container with a specific treatment agent to form a liquid-repellent film on the inner surface of the liquid container, improving the liquid scraping performance and preventing leakage or backflow of liquid when the applicator is placed face up.

The liquid container for an applicator of the present invention has at least three layers: an inner layer made of a paper substrate; a paper substrate laminate having an intermediate layer that is a metal layer or a silica-deposited layer formed on the outer surface side of the inner layer; and an outer layer made of a paper substrate formed on the outer surface side of the intermediate layer; the paper substrate laminate has a spirally wound structure; and the outer layer made of the paper substrate has a spirally wound structure on the outer surface side of the intermediate layer; the liquid container for an applicator has a layer of adhesive containing a polyolefin resin at least either between the inner layer and the intermediate layer or between the intermediate layer and the outer layer; and the inner surface of the inner layer is treated with at least one treating agent selected from the group consisting of silicone oil, fluorine-based surfactants, and olefin-based polymers.

According to the present invention, by treating the inner surface of a paper-made liquid containing member with a specific treatment agent, an ink-repellent film is formed on the inner surface of the liquid containing member, improving ink scraping performance. Furthermore, improved ink scraping performance (reducing the amount of ink remaining on the refill's inner wall) means that even after starting to use the writing instrument and the follower moves to the ink-stained surface, ink is less likely to flow and remain between the inner wall and the follower, maintaining close contact between the inner wall and the follower. Even when the tip of the writing part is placed facing upward, ink leakage from the rear end of the refill can be prevented.

FIG. 1 shows an example of the configuration of a refill including a liquid containing member for an applicator of the present invention, where FIG. 1(a) is a front view of the appearance of the refill, and FIG. 1(b) is a cross-sectional view of the refill taken along the A-A' arrow. Fig. 2 shows the three-layer structure of an inner layer, an intermediate layer, and an outer layer that constitutes a liquid containing member for an applicator of the present invention. Fig. 2(a) shows a configuration in which an adhesive layer is provided between the inner layer and the intermediate layer, Fig. 2(b) shows a configuration in which an adhesive layer is provided between the intermediate layer and the outer layer, and Fig. 2(c) shows a configuration in which adhesive layers are provided between the inner layer, the intermediate layer, and the outer layer.

The liquid containing member for an applicator of the present invention will be described in detail with reference to the drawings.
FIG. 1 shows an example of the configuration of a refill including a liquid containing member 10 for an applicator of the present invention, where FIG. 1(a) shows a front view of the appearance of the refill, and FIG. 1(b) shows a cross-sectional view of the refill taken along the line A-A'.
In Figure 1, for example, a refill housed in the barrel of a ballpoint pen comprises a liquid container 10 for an applicator (hereinafter simply referred to as "liquid container 10"), which is a long, thin, cylindrical ink container tube made of paper and containing ink (not shown), a joint 11 attached to the tip of this liquid container 10, and a ballpoint pen tip 12 attached to the tip of the joint 11 as a writing member.

Specifically, the joint 11 has a cylindrical rear end portion that joins with the liquid container 10, and a cylindrical front end portion with a larger outer diameter than the rear end portion, with the ballpoint pen tip 12 attached to this front end portion. Furthermore, an adhesive is applied in advance to the rear end portion of the joint 11 to ensure a certain level of bonding strength at the joint with the liquid container 10, and in this state, the rear end portion of the joint 11 is press-fitted into the front end of the liquid container 10 to join the joint 11 and the liquid container 10. This connects the liquid container 10 and the ballpoint pen tip 12 via the joint 11, allowing ink to flow through.

The liquid containing member 10 of the present invention has at least three layers: an inner layer 1 made of a paper substrate; a paper substrate laminate including an intermediate layer 2 formed on the outer surface of the inner layer 1 and being a metal layer or a silica-vapor-deposited layer; and an outer layer 3 made of a paper substrate formed on the outer surface of the intermediate layer 2. The liquid containing member 10 has a structure in which the paper substrate laminate is spirally wound, and a structure in which the outer layer 3 made of the paper substrate is spirally wound around the outer surface of the intermediate layer 2. Additionally, the liquid containing member 10 has an adhesive layer 5 (hereinafter simply referred to as "adhesive layer 5") containing a polyolefin resin at least either between the inner layer 1 and the intermediate layer 2 or between the intermediate layer 2 and the outer layer 3, and the inner surface of the inner layer 1 is treated with at least one treating agent selected from the group consisting of silicone oil, fluorine-based surfactants, and olefin-based polymers.

The paper substrate that constitutes the inner layer 1 can be any of a variety of known materials, such as fine paper, medium-quality paper, one-side glossy paper, kraft paper, one-side glossy kraft paper, bleached kraft paper, paperboard, white paperboard, liner, lightly coated paper, coated paper, art paper, cast-coated paper, glassine paper, parchment paper, and vulcanized fiber.
The density of these paper substrates is preferably 0.8 g/cm ³ or more. By using a paper substrate with a density of 0.8 g/cm ³ or more, sufficient water resistance and oil resistance can be imparted.
The paper substrate constituting the inner layer 1 is preferably glassine paper, parchment paper or vulcanized fiber, and more preferably has a density of 0.8 g/cm ³ or more.

Glassine paper is a high-density, highly transparent paper made by extensively beating virgin pulp to increase its specific surface area, and then treating the paper with a supercalender to densify it and strengthen the bonds between the cellulose fibers. In the present invention, glassine paper with a basis weight of 20 to 50 g/ ^m2 is used. Using glassine paper as the paper substrate constituting the inner layer 1 facilitates imparting water resistance and oil resistance. Alternatively, glassine paper with a basis weight of 20 to 50 g/ ^m2 may be used as the base paper, with one or both sides coated with a coating liquid such as an aqueous polyvinyl alcohol solution. The thickness of the glassine paper is typically 20 to 50 μm, preferably 20 to 30 μm.

Parchment paper and vulcanized fiber are made by treating them with concentrated sulfuric acid or zinc chloride solution during the manufacturing process, which strengthens the direct bonds between the cellulose fibers, i.e., increases the density of cellulose hydrogen bonds between the cellulose fibers. Therefore, using parchment paper or vulcanized fiber as the paper base material that makes up the inner layer 1 can effectively suppress the generation of paper dust.

The parchment paper used has a basis weight of, for example, 20 to 100 g/ ^m² , and preferably has enhanced oil resistance so that the oil absorption is 13 g/ ^m² or less when mineral oil is used instead of water in accordance with the water absorption test method for paper and paperboard (Cobb method). The thickness of the parchment paper is usually 20 to 100 µm, and preferably 20 to 60 µm.

Due to differences in reactivity during the manufacturing process, vulcanized fiber can be made thicker than parchment paper. Therefore, it is suitable for cases where thick cardboard is required as the paper substrate. The thickness of vulcanized fiber is typically 0.08 to 1 mm, preferably 0.1 to 0.5 mm, taking into consideration the compressive strength of the paper tube portion after the liquid containing member 10 is formed and ease of handling during manufacturing. Furthermore, the density of vulcanized fiber is higher than that of general paper tube base paper, typically 0.8 to 1.4 g/cm ^3. In the present invention, a density of 0.8 to 1.3 g/cm ³ is preferred, taking into consideration the strength of the paper tube portion and ease of availability.

Parchment paper and vulcanized fiber may also be subjected to resin impregnation or glass coating. This treatment further strengthens the bonds between the cellulose fibers, and when these papers are used as the paper base material that makes up the inner layer 1, the generation of paper dust can be reduced.

The intermediate layer 2 is a metal layer or a silica vapor deposition layer. The metal layer may be formed by adhering a metal foil such as aluminum foil to one side of the paper substrate with an adhesive containing a polyolefin resin, or by depositing aluminum or an alloy of aluminum and zinc by electron beam deposition under vacuum.
In the present invention, a paper substrate laminate consisting of an inner layer 1 and an intermediate layer 2 is generally used as a composite material in which a metal layer or a silica vapor deposition layer is laminated on the surface of a paper substrate.

In the present invention, to prevent ink and other liquids from being absorbed into the inner layer 1, the side of the inner wall 1 that comes into contact with the liquid is treated with a treatment agent selected from silicone oil, fluorochemical surfactants, and olefin polymers. The treatment agent serves to prevent ink and other liquids from adhering to the wall surface of the liquid containing tube.

Examples of silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, and hydrogenpolysiloxane (e.g., methylhydrogenpolysiloxane). These may be modified polysiloxanes such as alkyl-modified, polyether-modified, higher fatty acid amide-modified, higher fatty acid ester-modified, or fluorine-modified (fluorosilicone). Specific examples include the TSF451 series, TSF456 series, and TSF458 series (all manufactured by Toshiba Silicone Co., Ltd.).
The silicone oils may be used alone or in combination of two or more.

Fluorine-based surfactants have the role of imparting water-resistant adhesion to paper while maintaining the wettability of liquids such as ink to the paper. Examples of fluorine-based surfactants include perfluoroalkyl group adducts, perfluoroalkenylethylene oxide adducts, and perfluorobutanesulfonic acid group adducts, and high-molecular-weight polymers. Specific examples include polymers of ( _CF3 ) _2CF2C =C(F) _CF3 having a double bond and a branched perfluoroalkenyl structure in the molecule (Ftergent 100, _100C , 110, 140A, 150, 150CH, A-K, 501, 250, 251, 222F, 300, 310, and 400SW, all manufactured by Neos Co., Ltd.), and those having a perfluorobutanesulfonic acid group (FC-4430 and FC-4432, manufactured by 3M Japan Ltd.).
The fluorosurfactants may be used alone or in combination of two or more.

An olefin-based polymer is a polymer composed of one or more olefin monomers. The olefin-based polymer may be a copolymer of at least one olefin monomer selected from the group consisting of α-olefins, cycloolefins, conjugated dienes, and non-conjugated dienes, or a copolymer of the olefin monomer with an α,β-unsaturated carboxylic acid (e.g., (meth)acrylic acid), an α,β-unsaturated carboxylic acid ester (e.g., (meth)acrylic acid ester), vinyl alcohol, styrene, or the like.

As the olefin-based polymer, a propylene-based polymer is preferred because the paper material has excellent flexibility even after coating. The propylene-based polymer is a propylene homopolymer, or a block copolymer or random copolymer of propylene and an α-olefin having 2 to 20 carbon atoms, containing 50 mol% or more of monomer units derived from propylene. Specific examples include polypropylene, propylene-ethylene random copolymer, and propylene-ethylene-1-butene random copolymer.
The olefin polymers may be used alone or in combination of two or more.

The application method used in the present invention is not particularly limited and may be selected as needed. Examples include spraying, dipping, brush coating, roller coating, roll coating, gravure coating, flexography, and inkjet coating. After the inner wall treatment agent is applied to the paper substrate using one of the above methods, a drying process is performed to allow the inner wall treatment agent to be fixed to the paper substrate.

The amount of the inner wall coating agent to be applied is preferably in the range of 100 to 1000 mg/m ² , and more preferably in the range of 200 to 800 mg/m ² .

Next, we will explain the adhesive used between the inner layer 1 and the intermediate layer 2, and/or between the intermediate layer 2 and the outer layer 3. The adhesive used in the present invention may be an adhesive made from one or more polyolefin resins, or it may be an adhesive made by mixing the polyolefin resin with other resins.

Specific examples of polyolefin resins include polyethylene ionomers, polypropylene ionomers, polypropylene elastomers, polyethylene elastomers, high-density polyethylene, and low-density polyethylene, as well as modified polyolefin resins such as maleic anhydride-modified polypropylene. Of these, polypropylene ionomers and maleic anhydride-modified polypropylene are preferred.

Specific examples of other resins include acrylic acid copolymers, ethylene-vinyl alcohol copolymers (EVOH), ethylene-acrylic acid copolymers (EAA), ethylene-methacrylic acid copolymers (EMAA), epoxy resins, carbodiimide crosslinkers, ethylene-vinyl acetate copolymers, and polyvinyl alcohol.

When polyolefin resin is mixed with other resins, the proportion of polyolefin resin in the total adhesive is approximately 60 to 97% by weight, preferably 90 to 97% by weight. Furthermore, the proportion of polyolefin resin in the total of polyolefin resin and other resins is approximately 68 to 98% by weight, preferably 93 to 98% by weight.

Adhesives containing polyolefin resins are used in the form of dispersion or emulsion resin liquids, with polyolefin resins or mixtures of polyolefin resins and other resins as the base polymer. Additives such as silane coupling agents may be added to the resin liquid as needed. Of these, dispersion-type adhesives such as polypropylene ionomers and maleic anhydride-modified polypropylenes are preferred due to their excellent adhesive properties and ease of handling.

The adhesive containing polyolefin resin is applied between the inner layer 1 and the intermediate layer 2, or between the intermediate layer 2 and the outer layer 3. That is, as shown in FIG. 2, an adhesive layer 5 may be provided between the inner layer 1 and the intermediate layer 2 (FIG. 2a), between the intermediate layer 2 and the outer layer 3 (FIG. 2b), or between both the inner layer 1 and the intermediate layer 2 and between the intermediate layer 2 and the outer layer 3 (FIG. 2c). By applying an adhesive containing polyolefin resin, which has excellent adhesion to paper and ink resistance, the inner layer 1, the intermediate layer 2, and the outer layer 3 of the liquid containing member 10 are tightly adhered to each other, preventing ink leakage to the outside of the liquid containing member 10. Ink resistance refers to the degree to which the elution of adhesive resin components into ink can be suppressed. When an adhesive containing polyolefin resin is used, the polyolefin resin has low compatibility with ink, so it does not dissolve in the ink, and these effects on ink resistance can be expected.

In the present invention, any one of the inner layer 1, intermediate layer 2, and outer layer 3 may be bonded together using an adhesive containing a polyolefin resin, and other adhesives, such as general-purpose adhesives based on vinyl acetate resin, acrylic resin, and polyvinyl alcohol, may also be used in combination.

The adhesive containing polyolefin resin is applied in a mound near the center of the inner layer 1 or intermediate layer 2. Next, the inner layer 1 and intermediate layer 2 are pressed together, spreading the adhesive over the entire bonding surface, bonding the two layers together without leaving any air bubbles or adhesive defects. After bonding the inner layer 1 and intermediate layer 2 together, they are pressed together and fixed in place until the adhesive hardens.

The adhesive containing polyolefin resin is applied to the inner layer 1 or intermediate layer 2 in an amount of about 5 to 50 g/m ² , preferably 5 to 25 g/m ² .

The inner layer 1 and the intermediate layer 2 of the liquid containing member 10 may be formed of a paper substrate laminate using a paper substrate and a metal layer or a silica vapor deposition layer of the same thickness, or may be formed by appropriately combining paper substrate laminates using paper substrates and metal layers or silica vapor deposition layers of different thicknesses.
In the paper substrate laminate, the ratio of the thickness of the paper substrate to the thickness of the metal layer or silica vapor deposition layer is about 2/1 to 1200/1.

After adhering the intermediate layer 2 to the inner layer 1, cutting using a bobbin slitter or similar tool produces a strip-shaped sheet of paper substrate laminate. The paper substrate laminate is then spirally wound around a mandrel (paper tube manufacturing machine) used to process the liquid containing member 10, with the inner layer 1 facing inward. An appropriate amount of the treatment agent may be applied to the surface of the mandrel beforehand, and the inner layer 1 may be subjected to an inner wall treatment during winding. An adhesive containing a polyolefin resin or similar is then applied to the outer intermediate layer 2 to adhere the outer layer 3.

The paper substrate laminate is typically a strip-shaped sheet cut to a width of 4 to 20 mm, preferably 5 to 15 mm. By spirally winding such a wide paper substrate laminate, the required length of the liquid containing member 10 can be achieved without multiple windings. As a result, the number of contact surfaces between the paper substrates, i.e., the number of seams 4, is reduced, and leakage of the liquid contained within the liquid containing member 10 can be suppressed.

A paper base material is further spirally wound around the outside of the intermediate layer 2 to form the outer layer 3. The outer layer 3 is also preferably formed using a paper base material having a width of 4 to 20 mm, specifically 6 to 15 mm. As with the paper base material laminate, this is because reducing the number of seams 4' can prevent leakage of the liquid inside the liquid containing member 10.
The paper base material constituting the outer layer 3 can be the same as the paper base material constituting the inner layer 1. Alternatively, an adhesive containing the polyolefin resin may be used to attach the outer layer 3 to the intermediate layer 2. The application method and amount of the adhesive containing the polyolefin resin in this case are similar to those for the inner layer 1 or the intermediate layer 2.

The ratio of the thicknesses (μm) of the inner layer 1, intermediate layer 2, and outer layer 3 is typically 20-60:0.025-12:50-200, and preferably 20-30:0.025-12:50-200.

As described above, the liquid containing member 10 has a structure in which the paper base laminate is wound in a spiral shape along the longitudinal direction of the liquid containing member 10, with adjacent surfaces in contact and not overlapping. Even if adjacent surfaces overlap at the contact point between the paper base laminates, i.e., at seam 4, the overlap width is limited to a maximum of 1 mm. By ensuring that seam 4 is in contact and not overlapping, or by limiting the overlap width to a maximum of 1 mm, leakage of liquid from seam 4 can be suppressed. If the overlap width at seam 4 exceeds 1 mm, a step will occur at the overlapping portion, which may lead to liquid leakage.

Similar to the paper base laminate, the outer layer 3 is preferably wound with its adjacent surfaces in contact. The seams 4' between the outer layers 3 and the seams 4 between the paper base laminates are preferably spaced apart along the longitudinal direction of the liquid container for an applicator by a distance of 1 mm or more and half the width of the paper base laminate or the outer layer 3, and more preferably 3 mm or more and half the width of the paper base laminate or the outer layer 3. Even if the seams 4' between the outer layers 3 overlap slightly, this does not pose a problem of liquid leakage.

After forming the inner layer 1, intermediate layer 2, and outer layer 3, the liquid containing member 10 manufactured as described above is completed by removing the mandrel and cutting the cylindrical molded body to the specified length required for the liquid containing member 10 for the applicator, and then drying it for several hours at appropriate temperature and humidity.

The resulting liquid containing member 10 has a smaller diameter than a typical paper tube, and its outer diameter is typically 20 mm or less, preferably 15 mm or less, and more preferably 10 mm or less, with the lower limit of the outer diameter typically being 1 mm or more, and preferably 2 mm or more. Such small-diameter liquid containing members require strict dimensional accuracy. Therefore, the smaller the outer diameter of the liquid containing member 10, the more preferably it is preferable that, when winding the paper substrate laminate and the outer layer made of paper substrate in a spiral shape, the paper substrate laminate be brought into contact with adjacent surfaces so as not to overlap, and that the outer layers made of paper substrate be brought into contact with adjacent surfaces.

The tube thickness of the liquid containing member 10 is typically 0.07 to 0.6 mm, specifically 0.2 to 0.4 mm. By keeping the tube thickness of the liquid containing member 10 within this range, it is possible to contain a sufficient amount of liquid, while improving barrier properties and making it easier to prevent liquid leakage and deterioration.

The applicator of the present invention is not limited to any particular type as long as it is equipped with the liquid containing member 10, and may be a padded or direct-fill type writing instrument, or a cosmetic tool such as eyeliner, mascara, or concealer, but is preferably a writing instrument.

In the case of writing implements, the pen tip may be any of brush bristles, soft pens, and hard pens. Specific examples of writing implements include fountain pens, ballpoint pens, marking pens, felt-tip pens, correction tools, and brush pens. In this case, the ink contained in the liquid containing member 10 may be either water-based (gel) ink or oil-based ink, and depending on the type of pen, ink for ballpoint pens, pressurized ballpoint pens, or marking pens may be used.

The liquid containing members used in the examples and comparative examples were manufactured and evaluated as follows.
[Production Example 1]
A 25 μm thick glassine paper (basis weight 25 g/ ^m2 , density 1.0 g/ ^cm3 ) and a 6.5 μm thick aluminum foil were bonded together with a polyolefin resin-containing adhesive (Chemipearl S500, manufactured by Mitsui Chemicals, Inc.) to form a 6.5 μm thick adhesive layer, resulting in a total thickness of 38 μm. The laminate was then cut into 13 mm widths using a bobbin slitter.
Silicone oil (KF-415, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to the surface on the glassine paper side at 500 mg/m ² .
The adhesive containing the polyolefin resin was applied to the aluminum foil side, which was the outer layer of the strip-shaped adhesive paper, at 12 g/ ^m2 using a roll-type applicator, and the adhesive was spirally wound in a single layer around the outer periphery of the mandrel of a paper tube manufacturing machine (Langston) with the glassine paper facing inward.
Next, a 66 μm thick coated paper (basis weight 85 g/m ² ) cut to a width of 13 mm using a bobbin slitter was spirally wound in a single layer on the aluminum foil which was the outer layer of the paper laminate.
At this time, the adhesive paper and the coated paper were wound so that their adjacent surfaces abutted against each other without overlapping, and the adhesive paper and the coated paper were wound so that the contact points between the adhesive paper and the coated paper were 3 mm apart in the longitudinal direction.
The obtained spiral tube was cut to a length of 89.3 mm to obtain a liquid-containing tube (paper tube 1) with an inner diameter of 3.8 mm.

[Production Example 2]
A liquid containing tube (paper tube 2) was obtained in the same manner as in Production Example 1, except that a fluorine-based surfactant (Surflon S-211, manufactured by AGC) was applied to the surface of the glassine paper instead of the silicone oil (KF-415, manufactured by Shin-Etsu Chemical Co., Ltd.) in Production Example 1.

[Production Example 3]
A liquid containing tube (paper tube 3) was obtained in the same manner as in Production Example 1, except that an olefin polymer (Chemipearl S100, manufactured by Mitsui Chemicals, Inc.) was applied to the surface of the glassine paper instead of the silicone oil (KF-415, manufactured by Shin-Etsu Chemical Co., Ltd.) in Production Example 1.

[Production Example 4]
A liquid containing tube (paper tube 4) was obtained in the same manner as in Production Example 1, except that the strip-shaped adhesive paper was spirally wound twice, instead of once, around the outer peripheral surface of the mandrel of the paper tube manufacturing machine (Langston).

[Production Example 5]
In Manufacturing Example 4, a liquid storage tube (paper tube 5) was obtained in the same manner as Manufacturing Example 4, except that instead of glassine paper, 25 μm thick parchment paper (basis weight 25 g/ ^m2 , density 1.0 g/ ^cm3 ) and 6.5 μm thick aluminum foil were bonded together with an adhesive containing polyolefin resin.

[Production Example 6]
A liquid containing tube (paper tube 6) was obtained in the same manner as in Production Example 4, except that the adhesive paper used was a 25 μm thick glassine paper (basis weight 25 g/ ^m2 , density 1.0 g/ ^cm3 ) on which a 0.4 μm thick silica vapor deposition layer was formed instead of aluminum foil.

[Production Example 7]
A liquid storage tube (paper tube 7) was obtained in the same manner as in Production Example 4, except that the adjacent surfaces of the coated paper were not butted together but were wound with an overlap of 1 mm.

[Production Example 8]
A liquid containing tube (paper tube 8) was obtained in the same manner as in Manufacturing Example 4, except that the distance between the contact points of the laminated papers and the contact points of the coated papers was 5 mm instead of 3 mm.

[Production Example 9]
A liquid containing tube (paper tube 9) was obtained in the same manner as in Production Example 1, except that silicone oil was not applied to the surface of the glassine paper.

The inks used in the examples and comparative examples were prepared according to the following formulations.
<Coating Solution 1> (Total amount 100% by mass)
Spiron Violet C-RH [manufactured by Hodogaya Chemical Co., Ltd.] 8%
Spiron Yellow C-GNH [manufactured by Hodogaya Chemical Co., Ltd.] 5%
Printex #35 [manufactured by Degussa Japan Co., Ltd.] 8%
Polyvinyl butyral BL-1 [Sekisui Chemical Co., Ltd.] 4%
Polyvinyl butyral BH-3 [Sekisui Chemical Co., Ltd.] 0.7%
Hi-Lac 110H [Hitachi Chemical Co., Ltd.] 10%
SOLSPERSE 28000 [manufactured by Lubrizol Japan, Inc.] 1%
(Acid value: 29, weight average molecular weight: approximately 3400)
Benzotriazole 0.5%
3-Methoxy-3-methyl-1-butanol 62.8%

<Coating Solution 2> (Total amount 100% by mass)
FUJI RED 2510 [Fuji Pigment Co., Ltd.] 8%
Joncryl 61J [manufactured by BASF Japan Ltd.] 6%
Xanthan gum KELSAN S [manufactured by Sansho Co., Ltd.] 0.32%
Isopropyl phosphate 0.5%
Bioden 421 [manufactured by Nippon Soda Co., Ltd.] 0.2%
Benzotriazole 0.3%
Triethanolamine 1.4%
Propylene glycol 15%
Ion-exchanged water 68.28%

<Coating Solution 3> (Total amount 100% by mass)
Vinyblan GV5651 [manufactured by Nissin Chemical Industry Co., Ltd.] 80%
(Polyvinyl acetate emulsion; solids content 40%)
Acid dye Red No. 227 0.22%
Yellow No. 4 0.34%
Blue No. 1 0.08%
Purified water 19.36%

[Ink scraping performance]
The liquid containing member filled with ink and ink follower was left in a temperature cycle environment of -10°C to 35°C (continuous operation with a temperature rise time and a temperature fall time of 6 hours each, and a hold time of 6 hours) tilted at a 45°C angle with the pen tip facing upward for two weeks, after which writing was carried out until the ink was gone. After writing, the paper tube was cut along its length, and the amount of ink remaining on the inner wall surface of the paper tube was visually observed according to the following evaluation criteria.
A: No ink remained. B: A small amount of ink remained. C: A large amount of ink remained on the inner wall of the paper tube.

[Ink leakage when left facing up]
The liquid containing member filled with ink and ink follower was left standing for two weeks in a temperature cycle environment of -10°C to 35°C (continuous operation with a temperature rise and fall time of 6 hours each, and a hold time of 6 hours) tilted at a 45°C angle with the pen tip facing upwards, and then after writing 400m, the pen was left standing for one week in an environment of 25°C and 65% humidity with the pen tip facing upwards, with the ink still remaining. The presence or absence of ink leakage was visually observed according to the following evaluation criteria.
A: No ink leakage was observed. B: Slight ink leakage. C: Ink leakage.

[Example 1]
The paper tube 1 was filled with 0.7 g of the coating liquid 1, and polybutene was filled to a length of about 10 mm as an ink follower, and combined with a pen tip consisting of a joint and a tip with a ball diameter of 0.7 mm to form a refill.
The refill was left standing for two weeks in a temperature cycle environment of -10°C to 35°C (continuous operation with a temperature rise time and a temperature fall time of 6 hours each, and a hold time of 6 hours) tilted at 45° with the pen tip facing upward.
After writing until the ink was gone, the ink scraping performance was evaluated.
On the other hand, after writing 400 m, the pen tip was turned upward and left to stand for one week in an environment of 25°C and 65% humidity, and ink leakage was evaluated.
Since the glassine paper was slightly soaked with ink, the ink scraping performance was rated as B, but the ink did not leak even when the paper was placed face up, so the evaluation was A.
The types of treating agents used and the evaluation results are shown in Table 1.

[Example 2]
The paper tube 2 was filled with 0.7 g of the coating liquid 1, and polybutene was filled to a length of about 10 mm as an ink follower, and combined with a pen tip consisting of a joint and a tip with a ball diameter of 0.7 mm to form a refill.
The ink scraping performance and ink leakage when left facing up were evaluated in the same manner as in Example 1. Both the ink scraping performance and ink leakage were evaluated as A.
The types of treating agents used and the evaluation results are shown in Table 1.

[Example 3]
The paper tube 3 was filled with 0.7 g of the coating liquid 1, and polybutene was filled to a length of about 10 mm as an ink follower, and combined with a pen tip consisting of a joint and a tip with a ball diameter of 0.7 mm to form a refill.
The ink scraping performance and ink leakage when left facing up were evaluated in the same manner as in Example 1. Both the ink scraping performance and ink leakage were evaluated as A.
The types of treating agents used and the evaluation results are shown in Table 1.

[Comparative Example 1]
An ink containing member was produced in the same manner as in Example 1, except that the inner wall of the ink containing member was not treated.
The ink scraping performance and ink leakage when left facing up were evaluated in the same manner as in Example 1. A large amount of ink remained on the inner wall, and the ink scraping performance was rated C. Furthermore, when the ink containing member was left facing up, ink leaked, and the evaluation was C.
The types of treating agents used and the evaluation results are shown in Table 1.

REFERENCE SIGNS LIST 10 Liquid storage member for applicator 11 Joint 12 Ballpoint pen tip 1 Inner layer 2 Intermediate layer 3 Outer layer 4, 4' Seam 5 Adhesive layer

Claims (1)

a paper substrate laminate including an inner layer made of a paper substrate which is glassine paper, parchment paper, or vulcanized fiber and has a density of 0.8 g/cm3 or more ^; an intermediate layer which is a metal layer or a silica vapor deposition layer and is formed on the outer surface side of the inner layer; and an outer layer made of a paper substrate and formed on the outer surface side of the intermediate layer,
The paper substrate laminate has a structure in which the paper substrate laminate is spirally wound, and an outer layer made of the paper substrate is spirally wound on the outer surface side of the intermediate layer, and
a layer of an adhesive containing a polyolefin resin is provided at least either between the inner layer and the intermediate layer or between the intermediate layer and the outer layer;
a liquid containing member for an applicator, wherein the inner surface of the inner layer is treated with at least one treating agent selected from the group consisting of silicone oil, a fluorine-based surfactant, and an olefin-based polymer in an amount of 100 to 1,000 mg/m2 ^.