Liquid storage member for applicator

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]

[0001] The present invention relates to a liquid containing member for an applicator, which is made of paper. [Background technology]

[0002] Transparent or translucent plastics such as polypropylene have traditionally been used for ink storage components in 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 the use of plastic for the various parts that make up writing instruments.

[0003] For example, Patent Document 1 discloses a writing instrument equipped with a barrel formed by spiral molding using a composite material in which a paper base is laminated with a synthetic resin having barrier properties and a metal such as aluminum. In order to improve water resistance and gas barrier properties, the barrel used in this writing instrument has a structure in which, from the outer surface of the barrel, an aluminum foil label paper with a kraft paper backing and two layers of liner paper are laminated, and then a polyethylene layer is laminated on the inner surface, followed by a polyester film with an aluminum vapor deposition film on the outside.

[0004] 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. In this aqueous ink storage member, because the storage tube base is molded from a biodegradable resin, it does not swell with aqueous ink and undergo dimensional changes, and it is biodegradable over time, which contributes to reducing the amount of waste disposal.

[0005] However, when ink is filled into a barrel or a housing tube made of such paper material and an ink follower is then filled in, the ink tends to stain the inner wall of the barrel or the housing tube. The ink scraping ability of this stained surface is easily reduced, and when the follower moves to the stained surface after use, ink remains between the inner wall and the follower, and when the writing instrument is placed face up, the ink remaining between the inner wall and the follower can cause ink to leak or flow back.

[0006] To solve these problems, efforts have been 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 film on its surface, a barrier layer, and an innermost layer. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 62-70097 [Patent Document 2] Japanese Patent Application Laid-Open No. 2001-146091 [Patent Document 3] Japanese Patent Application Laid-Open No. 2007-152357 [Patent Document 4] Japanese Patent Application Laid-Open No. 2004-17991 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention aims to provide a liquid container for an applicator, which has an inner surface made of paper and is treated with a specific treatment agent to form a liquid-repellent film on the inner surface of the liquid container, thereby improving the liquid scraping performance and preventing leakage or backflow of liquid when the applicator is placed facing up. [Means for solving the problem]

[0009] The liquid containing member for an applicator of the present invention has at least three layers: an inner layer made of a paper base material; a paper base material laminate having an intermediate layer which is a metal layer or a silica vapor-deposited layer formed on the outer surface side of the inner layer; and an outer layer made of a paper base material formed on the outer surface side of the intermediate layer; the liquid containing member has a structure in which the paper base material 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; and is characterized in that it 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 surfactant, and olefin-based polymer. [Effects of the Invention]

[0010] According to the present invention, by treating the inner surface of a paper-made liquid container with a specific treatment agent, an ink-repellent film is formed on the inner surface of the liquid container, improving ink scraping performance. Furthermore, improved ink scraping performance (reduced ink remaining on the refill's inner wall) reduces the amount of ink remaining between the inner wall and the follower even when the follower moves to the ink-stained surface after starting use of the writing instrument, thereby maintaining close contact between the inner wall and the follower. This also prevents ink from leaking from the rear end of the refill, even when the tip of the writing part is placed facing upward. [Brief explanation of the drawings]

[0011] [Figure 1]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 line A-A'. [Figure 2] Fig. 2 shows the three-layer structure of an inner layer, an intermediate layer, and an outer layer that constitute 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 an adhesive layer is provided between the inner layer, the intermediate layer, and the outer layer. DETAILED DESCRIPTION OF THE INVENTION

[0012] 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, the 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 joint 11 as a writing member.

[0013] Specifically, the joint 11 has a cylindrical rear end portion that joins with the liquid containing member 10, and a cylindrical front end portion that has a larger outer diameter than the rear end portion, and the ballpoint pen tip 12 is attached to this front end portion. An adhesive is applied in advance to the rear end portion of the joint 11 to ensure a certain level of joining strength at the joint with the liquid containing member 10, and in this state, the rear end portion of the joint 11 is press-fitted into the front end of the liquid containing member 10 to join the joint 11 and the liquid containing member 10. This connects the liquid containing member 10 and the ballpoint pen tip 12 via the joint 11 so that ink can flow through them.

[0014] The liquid containing member 10 of the present invention has at least three layers: an inner layer 1 made of a paper base material; a paper base laminate including an intermediate layer 2 that is a metal layer or a silica-deposited layer and formed on the outer surface side of the inner layer 1; and an outer layer 3 made of a paper base material and formed on the outer surface side of the intermediate layer 2, with the paper base laminate structure spirally wound and the outer layer 3 made of the paper base material spirally wound around the outer surface side 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.

[0015] The paper substrate that constitutes the inner layer 1 can be any of a variety of well-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 0.8 g / cm 3 The density is preferably 0.8 g / cm or more. 3 By using the above paper substrate, sufficient water resistance and oil resistance can be imparted. The paper substrate constituting the inner layer 1 is glassine paper, parchment paper or vulcanized fiber and has a density of 0.8 g / cm 3 More preferably, it is above that.

[0016] Glassine paper is a high-density, highly transparent paper that is made by extensively beating virgin pulp to increase the 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, the basis weight is 20 to 50 g / m 2By using glassine paper as the paper base material constituting the inner layer 1, it becomes easy to impart water resistance and oil resistance. 2 Alternatively, the glassine paper may be used as a base paper, and one or both sides of the base paper may be coated with a coating solution such as an aqueous polyvinyl alcohol solution. The thickness of the glassine paper is usually 20 to 50 μm, and preferably 20 to 30 μm.

[0017] 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 the cellulose hydrogen bonds between the cellulose fibers. For this reason, 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.

[0018] Parchment paper has a basis weight of 20 to 100 g / m 2 Preferably, the oil absorption is 13 g / m when mineral oil is used instead of water according to the water absorption test method for paper and paperboard (Cobb method). 2 Parchment paper with improved oil resistance is used so that it satisfies the following criteria: The thickness of the parchment paper is usually 20 to 100 μm, and preferably 20 to 60 μm.

[0019] Vulcanized fiber can be made thicker than parchment paper due to differences in reactivity during the manufacturing process. Therefore, it is suitable when thick paper is required as the paper substrate. The thickness of vulcanized fiber is usually 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 storage member 10 is formed and ease of handling during manufacturing. In addition, the density of vulcanized fiber is higher than that of general paper tube base paper, and is usually 0.8 to 1.4 g / cm. 3 In the present invention, taking into consideration the strength and availability of the paper tube, the 3 is preferred.

[0020] Parchment paper and vulcanized fiber may also be subjected to a resin impregnation or glass coating process, which strengthens the bonds between the cellulose fibers and reduces the generation of paper dust when used as the paper base material for the inner layer 1.

[0021] 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 under vacuum using an electron beam. 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.

[0022] In the present invention, in order to prevent liquid such as ink 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, fluorine-based surfactants, and olefin-based polymers. The treatment agent serves to prevent liquid such as ink from adhering to the wall surface of the liquid containing tube.

[0023] 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 Silicones Co., Ltd.). The silicone oils may be used alone or in combination of two or more.

[0024] Fluorosurfactants contribute to the water-resistant adhesion of paper while maintaining the wettability of inks and other liquids. Examples of fluorosurfactants include high-molecular-weight polymers of perfluoroalkyl group adducts, perfluoroalkenyl ethylene oxide adducts, and perfluorobutanesulfonic acid group adducts. Specific examples include polymers of (CF)CFC=C(F)CF containing a double bond and a branched perfluoroalkenyl structure in the molecule (e.g., Ftergent 100, 100C, 110, 140A, 150, 150CH, AK, 501, 250, 251, 222F, 300, 310, and 400SW, manufactured by Neos Co., Ltd.), and those containing perfluorobutanesulfonic acid groups (e.g., FC-4430 and FC-4432, manufactured by 3M Japan Ltd.). The fluorosurfactants may be used alone or in combination of two or more.

[0025] 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.

[0026] 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.

[0027] The application method in the present invention is not particularly limited and may be selected as necessary, and examples thereof include spraying, dipping, brush coating, roller coating, roll coating, gravure coating, flexography, inkjet coating, etc. After the inner wall treatment agent is applied to the paper substrate by any of the above methods, the inner wall treatment agent is fixed to the paper substrate through a drying step.

[0028] The amount of coating agent applied to the inner wall is 100 to 1000 mg / m 2 The range is preferably 200 to 800 mg / m 2 The range is.

[0029] Next, we will explain the adhesive used between the inner layer 1 and the intermediate layer 2, or between the intermediate layer 2 and the outer layer 3. The adhesive used in the present invention may be an adhesive made of one or more polyolefin resins, or may be an adhesive made by mixing the polyolefin resin with other resins.

[0030] Specific examples of polyolefin resins include polyethylene ionomers, polypropylene ionomers, polypropylene elastomers, polyethylene elastomers, high-density polyethylene, low-density polyethylene, and modified polyolefin resins such as maleic anhydride-modified polypropylene. Of these, polypropylene ionomers and maleic anhydride-modified polypropylene are preferred.

[0031] Other resins include, for example, 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, or polyvinyl alcohol.

[0032] When polyolefin resin is mixed with other resins, the proportion of polyolefin resin in the total amount of adhesive is about 60 to 97% by weight, preferably 90 to 97% by weight, and the proportion of polyolefin resin in the total amount of polyolefin resin and other resins is about 68 to 98% by weight, preferably 93 to 98% by weight.

[0033] 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. Among these, dispersion adhesives such as polypropylene ionomers and maleic anhydride-modified polypropylenes are preferred due to their excellent adhesive properties and ease of handling.

[0034] 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. Specifically, 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 with 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 adhesive resin component can be prevented from leaching into ink. When an adhesive containing polyolefin resin is used, its low compatibility with ink prevents the polyolefin resin from dissolving into the ink, which is expected to improve ink resistance.

[0035] 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, and other adhesives, such as general-purpose adhesives based on vinyl acetate resin, acrylic resin and polyvinyl alcohol, may also be used in combination.

[0036] 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 while the adhesive is spread 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.

[0037] The adhesive containing polyolefin resin for the inner layer 1 or the intermediate layer 2 is 5 to 50 g / m 2 Approximately, preferably 5 to 25 g / m 2 Apply in the amount of

[0038] 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.

[0039] After adhering the intermediate layer 2 to the inner layer 1, the paper substrate laminate is cut using a bobbin slitter or the like to obtain a strip-shaped sheet. Next, the paper substrate laminate is spirally wound around a mandrel (paper tube manufacturing machine) for processing the liquid containing member 10, with the inner layer 1 facing inward. Note that an appropriate amount of the treatment agent may be applied to the surface of the mandrel in advance, and the inner layer 1 may be subjected to an inner wall treatment during winding. Thereafter, an adhesive containing a polyolefin resin or the like is applied to the outer intermediate layer 2 to adhere the outer layer 3.

[0040] The paper substrate laminate is a strip-shaped sheet cut into a width of usually 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 winding it many times. 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 in the liquid containing member 10 can be suppressed.

[0041] 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, reducing the number of seams 4' can prevent leakage of the liquid inside the liquid containing member 10. The paper substrate constituting the outer layer 3 can be the same as the paper substrate constituting the inner layer 1. Alternatively, the outer layer 3 may be attached to the intermediate layer 2 using an adhesive containing the polyolefin resin. 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.

[0042] The ratio of the thicknesses (μm) of the inner layer 1, the intermediate layer 2 and the outer layer 3 is usually 20-60:0.025-12:50-200, and preferably 20-30:0.025-12:50-200.

[0043] 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 of the paper base laminate in contact so as not to overlap. 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 bringing the seam 4 into contact so as not to overlap, or by limiting the overlap width to a maximum of 1 mm, it is possible to prevent liquid leakage from the seam 4. If the overlap width at seam 4 exceeds 1 mm, a step will occur at the overlapping portion, which may lead to liquid leakage.

[0044] As with the paper base laminate, the outer layers 3 are preferably wound with their 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 or less of the width of the paper base laminate or the outer layer 3, more preferably 3 mm or more and half 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 overlap slightly, this does not pose a problem of liquid leakage.

[0045] The liquid containing member 10 produced as described above is completed by forming the inner layer 1, the intermediate layer 2, and the outer layer 3, removing the mandrel, cutting the cylindrical molded body to the specified length required for the liquid containing member 10 for the applicator, and drying it for several hours under appropriate temperature and humidity.

[0046] The resulting liquid containing member 10 has a smaller diameter than a typical paper tube, and its outer diameter is usually 20 mm or less, preferably 15 mm or less, and more preferably 10 mm or less, with the lower limit of the outer diameter usually being 1 mm or more, preferably 2 mm or more. Such a small-diameter liquid containing member requires strict dimensional accuracy. Therefore, the smaller the outer diameter of the liquid containing member 10, the more preferable it is that, when spirally winding the paper substrate laminate and the outer layer made of a paper substrate, the paper substrate laminate be brought into contact with adjacent surfaces so as not to overlap, and the outer layer made of a paper substrate be brought into contact with adjacent surfaces.

[0047] 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 tube thickness of the liquid containing member 10 within this range, a sufficient amount of liquid can be contained, the barrier properties are improved, and leakage and deterioration of the liquid can be easily suppressed.

[0048] The applicator of the present invention is not limited 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.

[0049] In the case of a writing instrument, the pen tip may be any of brush bristles, soft pens, hard pens, etc. Specific examples of writing instruments 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, marking pens, etc. is used. [Example]

[0050] The liquid containing members used in the examples and comparative examples were manufactured and evaluated as follows. [Manufacturing Example 1] 25 μm thick glassine paper (basis weight 25 g / m 2 , density 1.0g / cm 3 The laminated paper, which was made by laminating a 6.5 μm thick sheet of paper and a 6.5 μm thick aluminum foil with a polyolefin resin-containing adhesive (Chemipearl S500, manufactured by Mitsui Chemicals, Inc.), had a total thickness of 38 μm and an adhesive layer thickness of 6.5 μm.The laminated paper was cut into 13 mm widths using a bobbin slitter. Silicone oil (KF-415, Shin-Etsu Chemical Co., Ltd.) was applied to the surface of the glassine paper at a rate of 500 mg / m 2 It was applied with. 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 a rate of 12 g / m using a roll-type applicator. 2 The paste was applied to the mandrel of a paper tube manufacturing machine (Langston), and the mandrel was spirally wound in a single layer with the glassine paper facing inward. Next, a 66 μm thick coated paper (basis weight 85 g / m) was cut into 13 mm widths using a bobbin slitter. 2 ) was spirally wrapped in a single layer on the aluminum foil, which was the outer layer of the laminate. At this time, the adhesive paper and the coated paper were wound so that their adjacent surfaces were butted 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.

[0051] [Manufacturing Example 2] A liquid storage 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 silicone oil (KF-415, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0052] [Manufacturing Example 3] A liquid storage 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 silicone oil (KF-415, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0053] [Manufacturing Example 4] A liquid storage tube (paper tube 4) was obtained in the same manner as in Production Example 1, except that in Production Example 1, a strip-shaped adhesive paper was spirally wound twice, instead of once, around the outer surface of the mandrel of the paper tube manufacturing machine (Langston).

[0054] [Manufacturing Example 5] In Production Example 4, instead of glassine paper, parchment paper having a thickness of 25 μm (basis weight 25 g / m) was used as the adhesive paper. 2 , density 1.0g / cm 3 A liquid storage tube (paper tube 5) was obtained in the same manner as in Production Example 4, except that a liquid storage tube (paper tube 5) was used, which was made by laminating a 6.5 μm thick aluminum foil with an adhesive containing polyolefin resin.

[0055] [Manufacturing Example 6] In Production Example 4, a glassine paper having a thickness of 25 μm (basis weight 25 g / m) was used as the adhesive paper. 2 , density 1.0g / cm 3 A liquid storage tube (paper tube 6) was obtained in the same manner as in Production Example 4, except that a 0.4 μm thick silica vapor deposition layer was formed on the paper tube 1 instead of aluminum foil.

[0056] [Manufacturing 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 abutted against each other but were overlapped by 1 mm when wound.

[0057] [Manufacturing Example 8] A liquid storage tube (paper tube 8) was obtained in the same manner as in Production 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.

[0058] [Manufacturing 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.

[0059] 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 [Hodogaya Chemical Co., Ltd.] 8% Spiron Yellow C-GNH [Hodogaya Chemical Co., Ltd.] 5% Printex #35 [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 [Lubrizol Japan Co., Ltd.] 1% (Acid value: 29, weight average molecular weight: approx. 3400) Benzotriazole 0.5% 3-Methoxy-3-methyl-1-butanol 62.8%

[0060] <Coating liquid 2> (total amount 100% by mass) FUJI RED 2510 [Fuji Pigment Co., Ltd.] 8% Joncryl 61J [BASF Japan Ltd.] 6% Xanthan gum KELSAN S [manufactured by Sansho Co., Ltd.] 0.32% Isopropyl phosphate 0.5% Bioden 421 [Nippon Soda Co., Ltd.] 0.2% Benzotriazole 0.3% Triethanolamine 1.4% Propylene glycol 15% Ion-exchanged water 68.28%

[0061] <Coating solution 3> (total amount 100% by mass) Vinyblan GV5651 [Nissin Chemical Industry Co., Ltd.] 80% (Polyvinyl acetate emulsion; solids 40%) Acid dye Red No. 227 0.22% Yellow No. 4 0.34% Blue No. 1 0.08% Purified water 19.36%

[0062] [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° 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 longitudinally, 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 remains C: A large amount of ink remains on the inner wall of the paper tube.

[0063] [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 after writing 400m, 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: A small amount of ink was leaking C: Ink was leaking

[0064] [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 a 45° angle with the pen tip facing upward. After writing until the ink was gone, the ink scraping performance was evaluated. After writing 400m, the pen was turned with the nib facing upwards and left to stand for one week in an environment of 25°C and 65% humidity, and ink leakage was evaluated. Since a small amount of ink had soaked into the glassine paper, the ink scraping performance was rated a B, but the ink did not leak even when placed face up, so it was rated an A. The types of treatment agents used and the evaluation results are shown in Table 1.

[0065] [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 approximately 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 treatment agents used and the evaluation results are shown in Table 1.

[0066] [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 treatment agents used and the evaluation results are shown in Table 1.

[0067] [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 treatment agents used and the evaluation results are shown in Table 1.

[0068] [Table 1] [Explanation of symbols]

[0069] 10 Liquid storage member for applicator 11 Joints 12 Ballpoint pen tips 1 Inner layer 2. Middle class 3 Outer layer 4, 4' seam 5 Adhesive layer

Claims

[Claim 1] A paper substrate laminate having at least three layers, comprising 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 / cm 3 or more, an intermediate layer which is a metal layer or a silica vapor deposition layer formed on the outer surface side of the inner layer, and an outer layer made of a paper substrate which is 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, characterized in that 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 in an amount of 100 to 1000 mg / m 2 .

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