JP2023030910A - Liquid storage member for applicator - Google Patents

Abstract

To provide a liquid storage member for an applicator that improves liquid scraping performance and prevents liquid leakage and backflow when the applicator is placed facing upward by treating the inner surface of the liquid storage member made of paper with a specific treatment agent.SOLUTION: The liquid storage member for an applicator includes at least three layers formed of a paper base laminate including an inner layer of a paper base material, and an intermediate layer formed on the outer surface side of the inner layer and being a metal layer or a silica deposited layer, and an outer layer made of a paper base material formed on the outer surface side of the intermediate layer. The liquid storage has a structure in which the paper base laminate is spirally wound, and a structure in which the outer layer made of the paper base material is spirally wound on the outer surface side of the intermediate layer. Further, it has an adhesive layer containing a polyolefin resin between at least one of the inner layer and the intermediate layer and between the intermediate layer and the outer layer. The inner surface of the inner layer is innerwall-treated with at least one treatment agent selected from the group consisting of silicone oil, fluorosurfactant, and olefinic polymer.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a liquid container member for an applicator using a paper material.

Conventionally, transparent or translucent plastics such as polypropylene have been used for ink storage members for writing instruments such as ballpoint pens. Proposals have also been made that focus on eliminating plastics for each part that constitutes the .

For example, Patent Document 1 discloses a writing instrument equipped with a spiral-molded barrel using a composite material in which a synthetic resin having a barrier property or a metal such as aluminum is laminated on a paper base material. . In order to improve the water resistance and gas barrier properties of the barrel used in this writing instrument, from the outer side of the barrel, after stacking two layers of aluminum foil label paper and liner paper with the back side made of kraft paper, the inner surface It has a structure in which a polyethylene layer is laminated, followed by a polyester film having an aluminum deposition film on the outside.

Patent Literature 2 discloses an aqueous ink containing member using an ink containing tube having a multi-layered structure in which one or more layers of other resin are formed inside a containing tube base body made of a biodegradable resin. ing. In the water-based ink storage member, since the storage tube base body is formed of a biodegradable resin, it does not swell with water-based ink to cause a dimensional change, and is biodegraded over time, so it can be discarded. It can contribute to the reduction of the amount.

However, when a shaft cylinder or a storage tube made of such a paper material is filled with ink and then filled with an ink follower, a phenomenon is observed in which the inner wall of the shaft cylinder or storage tube is stained with ink or the like. This dyed surface tends to reduce the ink scraping performance, and when the follower moves to the dyed surface after the start of use, the ink that flows between the inner wall and the follower remains, and when the writing instrument is left standing upward Ink leakage or backflow may occur through the remaining ink between the inner wall and the follower.

In order to solve such problems, it has been studied to impart water and oil repellency to the paper base material to improve the performance of the barrel or housing tube. For example, in a tubular casting manufacturing part used as a runner or the like when manufacturing castings, a water-repellent paper tube layer made of kraft paper is provided as the outermost layer, and inside the water-repellent paper tube layer , a heat-resistant paper tube layer containing inorganic fibers, organic fibers, and thermosetting resin (Patent Document 3). In addition, Patent Document 4 describes a retort-processed paper container made of a laminated material in which an outermost layer, a paper substrate having a silicone-based water-repellent coating film on its surface, a barrier layer, and an innermost layer are successively laminated. It is

JP-A-62-70097 JP-A-2001-146091 JP 2007-152357 A JP-A-2004-17991

The present invention forms a liquid-repellent film on the inner surface of the liquid containing member by treating the inner surface of the liquid containing member using a paper material with a specific treatment agent, thereby improving the liquid scraping performance. SUMMARY OF THE INVENTION It is an object of the present invention to provide a liquid container for an applicator that can prevent liquid from leaking or flowing back when the applicator is placed facing upward.

A liquid containing member for an applicator of the present invention is a paper base laminate comprising an inner layer made of a paper base, an intermediate layer formed on the outer surface side of the inner layer and being a metal layer or a silica deposited layer, and A structure having at least three layers consisting of an outer layer made of a paper base material formed on the outer surface side of the intermediate layer, and a structure in which the paper base laminate is spirally wound, and the outer surface side of the intermediate layer. and an adhesive comprising a polyolefin resin between the inner layer and the intermediate layer and/or between the intermediate layer and the outer layer. The inner surface of the inner layer is treated with at least one treatment agent selected from the group consisting of silicone oil, fluorosurfactant, and olefin polymer.

According to the present invention, an ink-repellent film is formed on the inner surface of the liquid containing member by treating the inner surface of the liquid containing member made of paper with a specific treatment agent, thereby improving the ink scraping performance. . In addition, the ink scraping performance is improved (the amount of ink remaining on the inner wall of the refill is reduced). It becomes difficult to remain, and the degree of adhesion between the inner wall and the follower can be maintained. Even when the tip of the writing part is placed upward, ink leakage from the rear end of the refill can be prevented.

1A and 1B are diagrams showing an example of the configuration of a refill including a liquid container for an applicator of the present invention, FIG. 1A is a front view of the appearance of the refill, and FIG. It is an A' arrow directional cross-sectional view. FIG. 2 is a diagram showing a three-layer structure of an inner layer, an intermediate layer and an outer layer that constitute the liquid container member for an applicator of the present invention. FIG. 2(a) shows a form having an adhesive layer between the inner layer and the intermediate layer, FIG. 2(b) shows a form having an adhesive layer between the intermediate layer and the outer layer, and FIG. ) shows a configuration having an adhesive layer between the inner layer, the intermediate layer and the outer layer.

A liquid container member for an applicator according to the present invention will be described in detail with reference to the drawings.
1A and 1B are diagrams showing an example of a configuration of a refill including a liquid container 10 for an applicator according to the present invention, FIG. 1A showing a front view of the appearance of the refill, and FIG. AA' arrow cross-sectional view is shown.
In FIG. 1, for example, a refill housed in a barrel of a ballpoint pen is an applicator liquid containing member 10 (hereinafter simply referred to as ), a joint 11 attached to the tip of the liquid accommodation member 10, and a ballpoint pen tip 12 attached to the tip of the joint 11 as a writing member.

Specifically, the joint 11 is formed with a cylindrical rear end portion that is joined to the liquid containing member 10 and a cylindrical tip portion with a larger outer diameter than the rear end portion. A chip 12 is attached. Adhesive is applied in advance to the rear end portion of the joint 11 in order to give a certain joint strength to the joint portion with the liquid containing member 10. The joint 11 and the liquid containing member 10 are joined by press-fitting into the inside of the tip of the member 10 . As a result, the liquid containing member 10 and the ball-point pen tip 12 are connected via the joint 11 so that ink can flow.

The liquid containing member 10 of the present invention is a paper base laminate comprising an inner layer 1 made of a paper base, and an intermediate layer 2 formed on the outer surface side of the inner layer 1 and being a metal layer or silica deposition layer, A structure having at least three layers consisting of an outer layer 3 made of a paper base material formed on the outer surface side of the intermediate layer 2, and a structure in which the paper base laminate is spirally wound, and the intermediate layer 2 It has a structure in which the outer layer 3 made of the paper base material is spirally wound on the outer surface side of the. In addition, the liquid containing member 10 has an adhesive layer 5 containing a polyolefin resin (hereinafter simply referred to as "adhesive layer") between the inner layer 1 and the intermediate layer 2 and at least one between the intermediate layer 2 and the outer layer 3. The inner surface of the inner layer 1 is treated with at least one treatment agent selected from the group consisting of silicone oil, fluorosurfactant, and olefin polymer.

The paper base material constituting the inner layer 1 includes fine paper, medium quality paper, one-sided glossy paper, kraft paper, one-sided glossy kraft paper, bleached kraft paper, paperboard, white paperboard, liner, lightly coated paper, coated paper, and art paper. Various known materials such as paper, cast-coated paper, glassine paper, parchment paper, and vulcanized fiber can be used.
The density of these paper substrates is preferably 0.8 g/cm ³ or more. By using a paper substrate having a density of 0.8 g/cm ³ or more, sufficient water resistance and oil resistance can be imparted.
More preferably, the paper substrate constituting the inner layer 1 is made of glassine paper, parchment paper or vulcanized fiber and has a density of 0.8 g/cm ³ or more.

Glassine paper is a paper with high density and high transparency. It strengthens the coupling of In the present invention, glassine paper with a basis weight of 20-50 g/m ² is used. By using glassine paper as the paper base material constituting the inner layer 1, it becomes easy to impart water resistance and oil resistance. Alternatively, glassine paper having a basis weight of 20 to 50 g/m ² may be used as a base paper, and a coating liquid such as polyvinyl alcohol aqueous solution may be applied to one or both sides of the base paper. The thickness of the glassine paper is usually 20-50 μm, preferably 20-30 μm.

Parchment paper and vulcanized fiber are treated with concentrated sulfuric acid and zinc chloride solution during the manufacturing process to strengthen the direct bonding between cellulose fibers, that is, to increase the density of cellulose hydrogen bonds between cellulose fibers. is. Therefore, if parchment paper and vulcanized fiber are used as the paper substrate constituting the inner layer 1, the generation of paper dust can be effectively suppressed.

For parchment paper, for example, one with a basis weight of 20 to 100 g/m ² is used, and preferably mineral oil is used instead of water in accordance with the water absorption test method for paper and paperboard (Cobb method). The oil resistance is improved so that the oil absorption is 13 g/m ² or less. The thickness of the parchment paper is usually 20-100 μm, preferably 20-60 μm.

Vulcanized fiber is easier to thicken than parchment paper due to the difference in reactivity during the manufacturing process. Therefore, it is suitable when thick paper is required as the paper substrate. The thickness of the vulcanized fiber is usually 0.08 to 1 mm, preferably 0.1 to 0.5 mm, considering the compressive strength of the paper tube portion after forming the liquid containing member 10 and the ease of handling during manufacture. . In addition, the density of vulcanized fiber is higher than that of general paper tube base paper, usually 0.8 to 1.4 g/cm ³ . , 0.8 to 1.3 g/cm ³ .

Also, parchment paper and vulcanized fiber may be subjected to resin impregnation treatment or glass coating treatment. By performing the above treatment, the bonding between cellulose fibers is further strengthened, and even when these papers are used as the paper substrate constituting the inner layer 1, the generation of paper dust can be suppressed.

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

In the present invention, in order to prevent liquid such as ink from being absorbed by the inner layer 1, the side of the inner wall 1 that comes into contact with the liquid is coated with a treatment agent selected from silicone oil, fluorosurfactant, and olefinic polymer. process. The treatment agent serves to prevent liquid such as ink from adhering to the wall surface of the liquid storage tube.

Silicone oils include, for example, dimethylpolysiloxane, methylphenylpolysiloxane, and hydrogenpolysiloxane (eg, methylhydrogenpolysiloxane). These may be alkyl-modified, polyether-modified, higher fatty acid amide-modified, higher fatty acid ester-modified, or modified polysiloxanes such as fluorine-modified (fluorosilicones). Specifically, TSF451 series, TSF456 series and TSF458 series (all manufactured by Toshiba Silicone Co., Ltd.) and the like can be mentioned.
You may use the said silicone oil 1 type or in combination of 2 or more types.

The fluorosurfactant has a role of imparting water-resistant adhesion to the paper material while maintaining the wettability of the liquid such as ink to the paper material. Examples of fluorosurfactants include perfluoroalkyl group adducts, perfluoroalkenyl ethylene oxide adducts, perfluorobutanesulfonic acid group adducts, and the like, and high molecular weight polymers. Specifically, a perfluoroalkenyl structure having a double bond and branches in the molecule, for example, a polymer of (CF ₃ ) ₂ CF ₂ C═C(F)CF ₃ [Ftergent 100 manufactured by Neos Co., Ltd., the same 100C, 110, 140A, 150, 150CH, AK, 501, 250, 251, 222F, 300, 310, 400SW] and a perfluorobutanesulfonic acid group (FC-4430, FC-4432 manufactured by 3M Japan Co., Ltd.).
The fluorine-based surfactants may be used singly or in combination of two or more.

Olefinic polymers are polymers composed of one or more olefinic 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. It may be a copolymer with saturated carboxylic acid (eg, (meth)acrylic acid), α,β-unsaturated carboxylic acid ester (eg, (meth)acrylic acid ester), vinyl alcohol, styrene, or the like.

As the olefin-based polymer, a propylene-based polymer is preferable 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 olefinic polymer may be used singly or in combination of two or more.

The coating method in the present invention is not particularly limited and may be selected according to need. are mentioned. After applying the inner wall treating agent to the paper substrate by the above method, the inner wall treating agent is fixed to the paper substrate through a drying process.

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

Next, 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 will be described. The adhesive used in the present invention may be an adhesive composed of one or more polyolefin resins, or an adhesive obtained by mixing the polyolefin resin and other resins.

Polyolefin resins specifically include polyethylene-based 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. Among these, polypropylene ionomer and maleic anhydride-modified polypropylene are preferred.

Other resins specifically include acrylic acid copolymer, ethylene/vinyl alcohol copolymer (EVOH), ethylene/acrylic acid copolymer (EAA), ethylene/methacrylic acid copolymer (EMAA), Epoxy resins, carbodiimide cross-linking agents, ethylene/vinyl acetate copolymers, polyvinyl alcohol, and the like.

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

Adhesives containing polyolefin resins are used in the form of dispersion-type or emulsion-type resin liquids in which polyolefin resins or mixtures of polyolefin resins and other resins are used as base polymers. Additives such as a silane coupling agent may be added to the resin liquid, if necessary. Among these, dispersion-type adhesives such as polypropylene ionomers and maleic anhydride-modified polypropylene are preferable from the viewpoint of excellent adhesiveness and handleability.

An adhesive containing polyolefin resin is applied to at least one of between the inner layer 1 and the intermediate layer 2 and 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), or an adhesive layer 5 may be provided between the intermediate layer 2 and the outer layer 3. (FIG. 2b), or an adhesive layer 5 may be provided both between 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 a polyolefin resin having excellent adhesive strength and ink resistance to paper materials, the layers of the liquid containing member 10 are brought into close contact between the inner layer 1, the intermediate layer 2 and the outer layer 3, and the liquid is contained. Ink can be prevented from leaking out of the member 10 . The ink resistance represents the extent to which elution of the adhesive resin component into the ink can be suppressed. When an adhesive containing a polyolefin resin is used, the compatibility with the ink is low, so the polyolefin resin does not dissolve into the ink, and an effect on ink resistance can be expected.

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

The adhesive containing polyolefin resin is applied to the vicinity of the center of the inner layer 1 or the intermediate layer 2 in a raised manner. Then, while pressing the inner layer 1 and the intermediate layer 2, the adhesive is spread over the entire surface to be bonded, and the two layers are bonded so that no air bubbles remain in the bonding portion and there is no defective bonding portion. After bonding the inner layer 1 and the intermediate layer 2 together, they are pressed and fixed until the adhesive is cured.

The adhesive containing polyolefin resin is applied to the inner layer 1 or the 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 all be formed of a paper base material laminate using a paper base material and a metal layer or a silica deposition layer of the same thickness, or may be formed of a paper base material having a different thickness. A paper base laminate using a metal layer or a silica deposition layer may be appropriately combined to form the paper base laminate.
In the paper base laminate, the ratio of the thickness of the paper base to the thickness of the metal layer or silica deposition layer is about 2/1 to 1200/1.

After adhering the intermediate layer 2 to the inner layer 1, the laminate is cut with a bobbin slitter or the like to obtain a paper base laminate in the form of a belt-like sheet. Next, the paper base laminate is spirally wound around a mandrel (paper tube manufacturing machine) for processing the liquid containing member 10 so that the inner layer 1 faces inside. Incidentally, the surface of the mandrel may be coated with an appropriate amount of the above-mentioned treatment agent, and the inner wall treatment may be applied to the inner layer 1 at the time of winding. After that, in order to bond the outer layer 3, the outer intermediate layer 2 is coated with an adhesive containing polyolefin resin or the like.

The paper base laminate is generally a belt-like sheet cut to a width of 4 to 20 mm, preferably 5 to 15 mm. By spirally winding such a wide paper base laminate, the required length of the liquid containing member 10 can be reached without winding many times, and as a result, contact between the paper bases can be achieved. The number of surfaces, that is, the number of seams 4 is small, and leakage of the liquid contained in the liquid containing member 10 can be suppressed.

An outer layer 3 is formed by spirally winding a paper base material around the outer side of the intermediate layer 2 . The outer layer 3 is also preferably formed using a paper substrate having a width of 4 to 20 mm, specifically 6 to 15 mm. This is because, similarly to the paper base laminate, if the number of seams 4' is reduced, leakage of the liquid in the liquid containing member 10 can be prevented.
The paper base material constituting the inner layer 1 can be used as the paper base material constituting the outer layer 3 . Alternatively, the outer layer 3 may be attached to the intermediate layer 2 using an adhesive containing the polyolefin resin. The application method and application amount of the adhesive containing the polyolefin resin at this time are also the same as the application method and application amount for the inner layer 1 or the intermediate layer 2 .

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

As described above, the liquid containing member 10 has a structure in which the paper base material laminate is spirally wound along the longitudinal direction of the liquid containing member 10 so that the adjacent surfaces thereof are not overlapped with each other. The overlapping width of the adjacent surfaces is 1 mm at maximum, even if the adjacent surfaces overlap at the contact points between the paper base laminates, that is, at the seams 4 . Leakage of liquid from the seam 4 can be suppressed by contacting the seam 4 without overlapping or by setting the width of the overlap to a maximum of 1 mm. If the overlapping width at the seam 4 exceeds 1 mm, a step occurs at the overlapping portion, which may lead to liquid leakage.

As with the paper base laminate, the outer layer 3 is preferably wound with the adjacent surfaces in contact with each other. The joint 4′ between the outer layers 3 and the joint 4 between the paper base laminates are 1 mm or more along the longitudinal direction of the liquid containing member for an applicator and have a width of the paper base laminate or the outer layer 3. The distance is preferably 1/2 or less, and more preferably 3 mm or more and 1/2 or less of the width of the paper base laminate or the outer layer 3 . Even if the seams 4' between the outer layers 3 are slightly overlapped, there is no problem of liquid leakage.

After the inner layer 1, the intermediate layer 2 and the outer layer 3 are formed, the liquid containing member 10 produced as described above is pulled out from the mandrel, and a cylindrical molded body is formed into a predetermined shape necessary for the liquid containing member 10 for an applicator. It is finished by cutting it to length and drying it for several hours under moderate temperature and humidity.

The obtained liquid containing member 10 has a smaller diameter than a normal paper tube or the like, and its outer diameter is usually 20 mm or less, preferably 15 mm or less, more preferably 10 mm or less, and the lower limit of the outer diameter is , usually 1 mm or more, preferably 2 mm or more. Strict dimensional accuracy is required for such a small-diameter liquid containing member. Therefore, the smaller the outer diameter of the liquid containing member 10 is, the more the paper-based laminate and the outer layer made of the paper-based material are spirally wound, and the adjacent surfaces of the paper-based laminate are brought into contact with each other so as not to overlap each other. In addition, it is preferable that adjacent surfaces of the outer layers made of the paper substrate are brought into contact with each other.

The tube thickness of the liquid containing member 10 is usually 0.07 to 0.6 mm, specifically 0.2 to 0.4 mm. By setting the pipe thickness of the liquid containing member 10 within the above range, a sufficient amount of liquid can be contained, and the barrier properties are improved, making it easy to suppress leakage and deterioration of the liquid.

The applicator of the present invention is not limited as long as it is provided with the liquid storage member 10, and may be a padding type or direct liquid type writing instrument, or a cosmetic tool such as an eyeliner, mascara or concealer, but is preferably used. is a writing utensil.

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

Liquid storage members used in Examples and Comparative Examples were manufactured and evaluated as follows.
[Production Example 1]
A 25 μm thick glassine paper (25 g/m ² in basis weight, 1.0 g/cm ³ in density) and a 6.5 μm thick aluminum foil were bonded together with an adhesive containing a polyolefin resin (Chemipearl S500, manufactured by Mitsui Chemicals, Inc.). The laminated paper having an adhesive layer thickness of 6.5 μm and a total thickness of 38 μm was cut into a width of 13 mm with a bobbin slitter.
500 mg/m ² of silicone oil (KF-415, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to the surface of the glassine paper side.
Using a roll applicator, 12 g/m ² of the adhesive containing the polyolefin resin was applied to the aluminum foil side, which is the outer layer of the strip-shaped laminated paper, and the outer circumference of the mandrel of a paper tube manufacturing machine (Langston). It was spiral-wound in a single layer so that the glassine paper was on the inside.
Next, coated paper (basis weight: 85 g/m ² ) having a thickness of 66 µm and cut to a width of 13 mm by a bobbin slitter was spirally wound in a single layer on the outer layer of the laminated paper, ie, the aluminum foil.
At this time, the lamination paper and the coated paper were each wound so that the adjacent faces were not overlapped but abutted against each other. In addition, it was wound so that the contact points between the laminated paper sheets and the contact points between the coated paper sheets were separated by 3 mm along the longitudinal direction.
The resulting spiral tube was cut to a length of 89.3 mm to obtain a liquid storage tube (paper tube 1) with an inner diameter of 3.8 mm.

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

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

[Production Example 4]
In Production Example 1, liquid storage is performed in the same manner as in Production Example 1, except that the strip-shaped laminated paper is spirally wound not in a single layer but in a double spiral on the outer peripheral surface of the mandrel of the paper tube manufacturing machine (Langston). A tube (paper tube 4) was obtained.

[Production Example 5]
In Production Example 4, instead of glassine paper, 25 μm-thick parchment paper (basis weight: 25 g/m ² , density: 1.0 g/cm ³ ) and 6.5 μm-thick aluminum foil were used as the bonding paper. A liquid storage tube (paper tube 5) was obtained in the same manner as in Production Example 4, except for using an adhesive containing a polyolefin resin.

[Production Example 6]
In Production Example 4, as the bonding paper, a 0.4-μm-thick silica deposition layer was placed on a 25-μm-thick glassine paper (basis weight: 25 g/m ² , density: 1.0 g/cm ³ ) instead of aluminum foil. A liquid storage tube (cardboard tube 6) was obtained in the same manner as in Production Example 4, except for using one formed with

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

[Production Example 8]
In Production Example 4, the liquid storage tube (paper tube 8) was prepared in the same manner as in Production Example 4, except that the distance between the contact point between the laminated paper sheets and the contact point between the coated paper sheets was 5 mm instead of 3 mm. got

[Production Example 9]
A liquid storage 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 each example and comparative example were prepared according to the following formulation.
<Coating liquid 1> (total amount 100% by mass)
Spiron Violet C-RH [manufactured by Hodogaya Chemical Industry Co., Ltd.] 8%
Spiron Yellow C-GNH [manufactured by Hodogaya Chemical Industry Co., Ltd.] 5%
Printex #35 [manufactured by Degussa Japan Co., Ltd.] 8%
Polyvinyl butyral BL-1 [manufactured by Sekisui Chemical Co., Ltd.] 4%
Polyvinyl butyral BH-3 [manufactured by Sekisui Chemical Co., Ltd.] 0.7%
Hi-Rack 110H [manufactured by Hitachi Chemical Co., Ltd.] 10%
SOLSPERSE 28000 [manufactured by Nippon Lubrizol Co., Ltd.] 1%
(Acid value: 29, weight average molecular weight: about 3400)
Benzotriazole 0.5%
3-methoxy-3-methyl-1-butanol 62.8%

<Coating liquid 2> (total amount 100% by mass)
FUJI RED 2510 [manufactured by 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 exchange water 68.28%

<Coating liquid 3> (total amount 100% by mass)
Vinyblan GV5651 [manufactured by Nissin Chemical Industry Co., Ltd.] 80%
(Polyvinyl acetate emulsion; solid content 40%)
Acid dye Red 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 the ink and the ink follower is placed in a temperature cycle environment of -10°C to 35°C (continuous operation with a temperature rise time and a temperature drop time of 6 hours each, and a hold time of 6 hours) with the pen tip facing upward. After standing for two weeks at an angle of 45 degrees, writing was performed until the ink ran out. The paper tube after writing was cut along the longitudinal direction, 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 face up]
The liquid containing member filled with the ink and the ink follower is placed in a temperature cycle environment of -10°C to 35°C (continuous operation with a temperature rise time and a temperature drop time of 6 hours each, and a hold time of 6 hours) with the pen tip facing upward. After writing for 400 m, the pen tip was turned upward with ink remaining, and the pen was left for 1 week in an environment of 25° C. and 65% humidity. The presence or absence of ink leakage was visually observed according to the following evaluation criteria.
A: No leakage of ink was observed B: Slight leakage of ink C: Leakage of ink

[Example 1]
A paper tube 1 was filled with 0.7 g of the coating liquid 1, and polybutene as an ink follower was filled to a length of about 10 mm.
The refill is placed in a temperature cycle environment of -10°C to 35°C (continuous operation with a temperature rise time and a temperature drop time of 6 hours each, and a hold time of 6 hours) with the pen tip tilted upward at 45 degrees and allowed to stand for 2 weeks. bottom.
After writing until the ink ran out, the ink scraping performance was evaluated.
On the other hand, after writing for 400 m, the tip of the pen was turned upward, and the pen was allowed to stand for one week in an environment of 25° C. and 65% humidity to evaluate ink leakage.
The glassine paper was slightly soaked with ink, so the ink scraping performance evaluation was B, but the ink did not leak even when left standing upright, so it was A.
Table 1 shows the types of processing agents used and the evaluation results.

[Example 2]
A paper tube 2 was filled with 0.7 g of the coating liquid 1, and polybutene as an ink follower was filled to a length of about 10 mm.
In the same manner as in Example 1, ink scraping performance and ink leakage when left facing upward were evaluated. The evaluation was A for both ink scraping performance and ink leakage.
Table 1 shows the types of processing agents used and the evaluation results.

[Example 3]
A paper tube 3 was filled with 0.7 g of the coating liquid 1, filled with polybutene as an ink follower to a length of about 10 mm, 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.
In the same manner as in Example 1, ink scraping performance and ink leakage when left facing upward were evaluated. The evaluation was A for both ink scraping performance and ink leakage.
Table 1 shows the types of processing agents used and the evaluation results.

[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.
In the same manner as in Example 1, ink scraping performance and ink leakage when left facing upward were evaluated. A large amount of ink remained on the inner wall, and the ink scraping performance was C. In addition, the ink leaked when the ink containing member was left standing upward, and the evaluation was C.
Table 1 shows the types of processing agents used and the evaluation results.

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 base laminate comprising an inner layer made of a paper base, an intermediate layer formed on the outer surface side of the inner layer and being a metal layer or a silica deposition layer, and formed on the outer surface side of the intermediate layer, having at least three layers consisting of an outer layer made of a paper substrate,
A structure in which the paper base laminate is spirally wound, and a structure in which an outer layer made of the paper base is spirally wound on the outer surface side of the intermediate layer, and
An adhesive layer containing a polyolefin resin is provided between at least one of the inner layer and the intermediate layer and 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, fluorosurfactant, and olefinic polymer.

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