WO2023026562A1

WO2023026562A1 - Liquid accommodation member for writing instrument, refill for writing instrument, writing instrument, and liquid accommodation member for application tool

Info

Publication number: WO2023026562A1
Application number: PCT/JP2022/014349
Authority: WO
Inventors: 沙希田中; 淳中島; 翔渡邉; 秀寿市川; 容治竹内
Original assignee: 三菱鉛筆株式会社
Priority date: 2021-08-23
Filing date: 2022-03-25
Publication date: 2023-03-02

Abstract

Provided is a liquid accommodation member for a writing instrument, the member being free of plastic and which exhibits excellent durability and reliability.　A liquid accommodation member 11 is constituted by: an innermost layer; an intermediate layer formed by a plurality of layers; and an outermost layer. At least one of the layers other than the outermost layer is formed as a paper base material laminate layer. Other layers are formed as paper base material layers, and the outermost layer is formed as a paper base material layer. Moreover, the paper base material laminate layer has a structure in which a paper base material laminate molded into a strip-shaped sheet is wound in a spiral shape. The paper base material layers have a structure in which a paper base material molded into a strip-shaped sheet is wound in a spiral shape. The innermost layer and the outermost layer are brought into contact so that the peripheral edge portions of the strip-shaped sheets overlap each other, and then are wound in a spiral shape.

Description

Liquid storage member for writing instrument, refill for writing instrument, liquid storage member for writing instrument and applicator

The present invention relates to a liquid storage member for writing instruments, a refill for writing instruments, and a writing instrument using a paper base material.

For example, a refill for a writing instrument such as a ballpoint pen is manufactured by press-fitting a ballpoint pen tip, which is a writing member, or a relay member (joint) that supports the ballpoint pen tip, into one end (tip) of an ink containing tube. It is used while housed in the barrel.

In addition, transparent or translucent plastic such as polypropylene has been conventionally used for the ink storage tube in order to ensure ease of molding and visibility of the amount of ink.

By the way, in recent years, the problem of microplastics flowing into the ocean has been attracting attention, and there is a growing momentum to tackle global environmental problems, such as refraining from using disposable plastics.

Proposals have also been made with a focus on eliminating plastics for each part that constitutes a writing instrument. Patent Document 1 discloses a composite material in which a synthetic resin having a barrier property and a metal such as aluminum are laminated on a paper base material. A writing instrument having a barrel formed by spirally forming the same is disclosed.

In order to improve the water resistance and gas barrier properties of the barrel used in this writing instrument, from the outer surface of the barrel, aluminum foil label paper and liner paper, the back of which is made of kraft paper, are laminated in two layers. It has a structure in which a layer and then a polyester film having an aluminum deposition film on the outside are laminated.

According to this shaft tube, by using a composite material containing a paper base material, it is possible to provide a writing instrument that can achieve low pollution while maintaining content resistance.

In addition, in Patent Document 2 below, an ink storage tube molded using a plastic such as polypropylene is replaced with an ink storage tube containing a paper base material to reduce the amount of plastic used and reduce the impact on the environment. A ballpoint pen refill is disclosed. Specifically, the ink storage tube is a paper base laminate having two layers: an inner layer of a paper base and an intermediate layer that is a metal layer or a silica deposition layer formed on the outer peripheral surface of the inner layer. , and an outer layer of a paper base formed on the outer peripheral surface of the intermediate layer, and the density of the paper base of the inner layer is 0.8 g/cm ³ or more.

Further, in JP-A No. 2002-200011, there is disclosed a water-based 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. A member is disclosed. 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.

JP-A-62-70097 Japanese Patent Application Laid-Open No. 2021-16976 JP-A-2001-146091

As mentioned above, products using paper substrates are suitable for reducing pollution.In particular, if a material containing pulp or paper is used as a substrate, we can provide environmentally friendly products that can replace plastics. be able to.

On the other hand, a refill for a writing instrument such as a ballpoint pen is produced by press-fitting a ballpoint pen tip, which is a writing member, or a joint that supports the ballpoint pen tip, into the tip of an ink containing tube. In the step of press-fitting the joint or the like into the tip of the ink containing tube, for example, as shown in FIG. there is However, if a paper-based ink storage tube is used in consideration of environmental problems instead of the plastic ink storage tube, the pressure from the inside to the outside due to the press-fitting of the joint may cause the ink storage tube to break or break. Peeling of the adhesive surface may occur. In addition, ink storage tubes such as ballpoint pens, which are often written at a fixed angle of inclination, are prone to problems such as dimensional change (deformation) and breakage due to bending and twisting forces, and this problem provides a stable writing sensation. may not be In other words, there is still room for improvement in terms of durability and reliability compared to plastic ink storage tubes, which are excellent in rigidity.

The present invention has been made to solve the above-mentioned problems, and replaces a liquid storage tube (ink storage tube) for writing instruments such as ink molded using plastic with a liquid storage tube for writing instruments containing a paper base material. To provide a liquid storage member for a writing instrument, a refill for the writing instrument, and a writing instrument which are excellent in durability and reliability while eliminating plastic by replacing with

A liquid storage member for a writing instrument according to the present invention is composed of an innermost layer that contacts a liquid, an intermediate layer formed of at least two layers, and an outermost layer. At least one layer is formed as a layer of a paper base laminate in which a metal layer or a silica deposition layer is laminated on the outer surface side of an inner layer formed of a paper base, and the other layers are formed as layers of the paper base. Furthermore, we decided to form the outermost layer as a layer of a paper substrate. The layer of the paper base laminate has a structure in which the paper base laminate formed into a belt-like sheet is spirally wound so that the inner layer faces inside, and the paper base layer has a structure of paper formed into a belt-like sheet. Each has a structure in which a base material is wound in a spiral shape, and the innermost layer and the outermost layer are characterized by being spirally wound with the peripheral edge portions of the belt-like sheets in contact with each other so as to overlap.

In particular, the intermediate layer has a two-layer structure, and the innermost layer and the intermediate layer, which are layers other than the outermost layer, include at least one of the three layers obtained by adding the two layers of the intermediate layer to the innermost layer. , is preferably formed as a layer of a paper base laminate.

According to the present invention, for example, even when pressure (load) is applied from the inside to the outside of the tip portion of the liquid storage member due to press fitting, the repulsive force due to the overlap of the contact points can easily tear or peel off the adhesive surface. It is possible to obtain a highly reliable and durable liquid containing member that does not generate .

Further, in the liquid storage member for a writing instrument according to the present invention, an adhesive layer, which is an adhesive layer containing polyolefin resin, is provided between at least one of the layers from the innermost layer to the outermost layer. As a result, the strength of the liquid containing member is increased, so that a certain effect can be obtained with respect to the problems of breakage of the liquid containing member and peeling of the adhesive surface.

Further, in the liquid containing member for a writing instrument according to the present invention, each layer forming the intermediate layer is spirally wound with the peripheral edge portions of the belt-shaped sheet in contact with each other so as not to overlap each other, or at least one layer is The peripheral portions are brought into contact with each other so as to be overlapped and wound in a spiral shape. As a result, for example, when the pipes are contacted in a non-overlapping manner and wound in a spiral, the thickness of the pipe can be reduced. Thus, a liquid storage member for a writing instrument is obtained.

Furthermore, in the liquid storage member for a writing instrument according to the present invention, the paper base laminate is such that the inner layer and the metal layer are bonded together with an adhesive containing polyolefin resin. This makes it possible to obtain a liquid containing member with even better strength.

In addition, in the liquid storage member for a writing instrument according to the present invention, it is desirable that the paper substrate laminate and the paper substrate are belt-shaped sheets with a width of 4 to 20 mm. Moreover, it is desirable that the liquid containing member for a writing instrument according to the present invention has a total length change rate of less than 0.7% after 300 m of writing. Further, it is desirable that the liquid storage member for a writing instrument according to the present invention has a bending strength of 0.5 N or more under a load in a state inclined at 60°.

Further, a refill for a writing instrument according to the present invention is characterized by comprising the liquid storage member for the writing instrument according to the present invention, ink for the writing instrument stored inside the liquid storage member for the writing instrument, and a writing member. do.

Further, in the writing instrument refill according to the present invention, the outer surface of the liquid storage member for writing instrument is removed until the metal layer or silica deposition layer forming the layer of the paper base laminate is exposed, and the metal layer or silica vapor deposition layer is removed. It is desirable to be able to display information on the deposited layer.

Further, the writing instrument according to the present invention is configured such that the refill for the writing instrument according to the present invention is housed in a barrel, and the barrel contains biomass-derived polyolefin.

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, by improving the ink scraping performance (reducing the amount of ink remaining on the inner wall of the refill), even when the follower moves to the surface where the ink remains after starting to use the writing instrument, the ink that flows between the inner wall and the follower will remain. It becomes difficult to remain, and the degree of adhesion between the inner wall and the follower can be maintained. Ink leakage from the rear end of the refill can be prevented even when the tip of the writing part is placed upward.

According to the present invention, it is possible to provide a liquid storage member for a writing instrument, a refill for a writing instrument, and a writing instrument that are excellent in durability and reliability while eliminating plastic.

1 is a diagram showing an example of a configuration of a refill for a writing instrument including a liquid containing member for a writing instrument according to the present invention; FIG. FIG. 2 is a diagram showing an example of the layer structure of the liquid containing member according to the present invention. FIG. 3 is a diagram schematically showing an example of the amount of change in total length change. FIG. 4 is a diagram showing how a load is applied to a refill that is tilted at 60°. FIG. 5 is a diagram showing an example of a state in which character information is printed on the exposed metal layer or silica deposited layer. FIG. 6 is a diagram showing an example of the configuration of a writing instrument in which a refill for writing instrument is housed in a barrel. FIG. 7 is a diagram showing the layer structure of the liquid containing member in Comparative Examples 1 to 3. FIG. FIG. 8 is a diagram showing a conventional refill. 9A and 9B are views showing an example of a configuration of a refill including the liquid container for applicator of the present invention, FIG. 9A is a front view of the appearance of the refill, and FIG. It is a cross-sectional view taken along line -A'. 10A and 10B are views showing a three-layer structure of an inner layer, an intermediate layer and an outer layer constituting the liquid containing member for an applicator of the present invention. FIG. 10A shows an adhesive layer between the inner layer and the intermediate layer. FIG. 10(b) shows a form having an adhesive layer between the intermediate layer and the outer layer, and FIG. 10(c) shows a form having an adhesive layer between the inner layer, the intermediate layer and the outer layer It is a figure which shows.

<First embodiment>
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of a liquid storage member for a writing instrument, a refill for a writing instrument, and a writing instrument according to the present invention will be described in detail with reference to the drawings. It should be noted that the present invention is not limited by this embodiment.

<Refill for writing instruments>
1A and 1B are diagrams showing an example of the configuration of a writing instrument refill including a writing instrument liquid storage member according to the present invention, FIG. shows a cross-sectional view of a refill for a writing instrument taken along the line AA'.

In FIG. 1, for example, a writing instrument refill 10 (hereinafter also simply referred to as "refill 10") accommodated in the barrel of a ball-point pen has a long and thin cylindrical shape that uses paper as a base material and stores ink (not shown). A liquid containing member 11 for a writing instrument (hereinafter also simply referred to as "liquid containing member 11") which is an ink containing tube, a joint 12 attached to the tip of the liquid containing member 11, and a tip of the joint 12 as a writing member. A ball-point pen tip 13 is attached.

Specifically, the joint 12 is formed with a cylindrical rear end portion that is joined to the liquid containing member 11 and a cylindrical front end portion with a smaller outer diameter than the rear end portion. A ballpoint pen tip 13 is attached. Adhesive is applied in advance to the rear end portion of the joint 12 in order to give a certain joint strength to the joint portion with the liquid containing member 11. The joint 12 and the liquid containing member 11 are joined by press-fitting into the rear end portion of the joint 12 . As a result, the liquid containing member 11 and the ball-point pen tip 13 are connected via the joint 12 so that the ink can flow.

In addition, the ball-point pen tip 13 accommodates a spring 13a inside, and this spring 13a pushes the writing ball 13b at the tip of the ball-point pen tip 13 forward. This structure prevents ink from leaking when not in use.

Note that the configuration of the refill 10 of the present embodiment is an example, and is not limited to the above. For example, as long as the liquid containing member 11 and the ballpoint pen tip 13 are connected so that ink can flow, the structure and shape of the joint 12 may be different from those shown in FIG. A configuration in which the liquid containing member 11 and the ball-point pen tip 13 are directly connected may be employed.

<Details of the ballpoint pen tip>
The ball-point pen tip 13 having the above-described structure comprises, in detail, the writing ball 13b, the holder 13c holding the writing ball 13b at its tip, and the inside of the holder 13c to urge the writing ball 13b forward. and a spring 13a that is an elastic member. The holder 13c is made of bismuth-containing ferritic stainless steel having a Vickers hardness of 200 or more and 450 or _less . The side portion is a tapered portion _13c2 having a truncated cone shape. Further, on the inner periphery of the holder 13c, there are a ball house _13c3 which is an internal space of the tapered portion _13c2 , a back hole _13c4 which is a hole extending from the rear end of the holder 13c to the vicinity of the ball house _13c3 , and a ball house. An ink hole _13c5 , which is a hole having a circular cross section and penetrates between the back hole _13c3 and the back hole _13c4 , is provided.

As the writing ball 13b that can be used in the ballpoint pen tip 13, cemented carbide containing tungsten carbide as a main component and cobalt, nickel, chromium, or the like as a binder phase, or ceramics containing silicon carbide, zirconia, alumina, or the like as a main component. Body etc. are used. As for the diameter of the ball, a conventionally known one having a diameter of 0.1 mm or more and less than 2.1 mm may be used.

A ferritic stainless steel material containing bismuth (Bi) is used as the material of the holder 13c that holds the writing ball 13b that can be used with the ballpoint pen tip 13. Bismuth has properties similar to those of lead (Pb), which is an additive generally used for the purpose of obtaining machinability, but has a lower ionization tendency than lead. Therefore, it is less likely to be eluted into ink than lead. In addition, unlike lead, which is harmful, it is harmless and has no impact on the environment. Moreover, the Vickers hardness of the holder material is desirably 200 or more and 450 or less. If the Vickers hardness is less than 200, the ball seat, which is the contact portion, is significantly scraped as the writing ball rotates during writing, making it difficult to continue writing for a long time. Moreover, when the Vickers hardness exceeds 450, it becomes difficult to form a tip portion having a diameter reduced inwardly. The Vickers hardness is measured at an internal position 0.2 mm from the outer surface of the holder toward the center, and other measurement methods conform to JIS Z2244.

<Structure of Liquid Storage Member>
The liquid containing member 11 according to the present embodiment is composed of a first layer that is the innermost layer that contacts liquid, second and third layers that are intermediate layers, and a fourth layer that is the outermost layer. An adhesive layer 21 containing a polyolefin resin (hereinafter simply (referred to as "adhesive layer 21") is provided. Note that FIG. 1B shows, as an example, the case where the adhesive layer 21 is provided between all the layers.

FIG. 2 is a diagram showing an example of the layer structure of the liquid containing member according to the present invention. As described above, the liquid containing member 11 of this embodiment is composed of four layers, ie, the first to fourth layers. For example, the fourth layer, which is the outermost layer, is formed as a paper base layer. In addition, for the first to third layers, which are the innermost layer and the intermediate layer, at least one of these layers is a metal layer on the outer surface side of the inner layer formed as a layer of the paper base material. Alternatively, it is a paper substrate laminate configured as a composite material in which silica deposition layers are laminated. That is, when any one of the first to third layers is a paper base laminate, the remaining two layers are formed as paper base layers. Further, when any two of the first to third layers are paper base laminates, the remaining one layer is formed as a paper base layer. Also, all of the first to third layers may be paper base laminates. Although not shown, an adhesive layer 21 may be interposed between the layers of the paper base laminate (between the inner layer and the metal layer).

In the present embodiment, the first to third layers (the innermost layer and the intermediate layer) are obtained by spirally winding the paper base laminate formed into a belt-like sheet so that the inner layer faces inside. It has a structure or a structure in which the paper base material formed into a strip-shaped sheet is spirally wound, and the fourth layer has a structure in which the paper base material formed into a strip-shaped sheet is spirally wound. . At this time, the first innermost layer and the fourth outermost layer are spirally wound with the peripheral edge portions of the belt-like sheets in contact with each other so as to overlap each other. The overlapping width of the contact points is preferably 1 mm at maximum, more preferably 0.1 mm to 1 mm, and most preferably 0.2 mm to 0.8 mm. By setting the maximum overlap width to 1 mm, it is possible to suppress leakage of liquid from the contact point (joint). Furthermore, even when pressure (load) is applied from the inside to the outside on the tip of the liquid containing member 11 due to press-fitting, the repulsive force caused by overlapping contact points does not easily cause breakage or peeling of the adhesive surface. Thus, it is possible to obtain the liquid containing member 11 having excellent strength and durability. In addition, if the width of the overlap exceeds 1 mm, a step occurs at the overlapped portion, which may lead to leakage of the liquid.

On the other hand, for the second and third layers, which are intermediate layers, for example, the peripheral edge portions of the belt-shaped sheet are brought into contact with each other so that they do not overlap and are spirally wound (see FIG. 2(a)). Thereby, the pipe thickness can be suppressed. The winding method of the intermediate layer is not particularly limited. For example, at least one of the second layer and the third layer may be spirally wound with the peripheral portions of the belt-like sheet in contact with each other so as to overlap each other. Moreover, the overlapping width of the contact portion at this time is the same as that of the first layer and the fourth layer. In the example of FIG. 2(b), both the second layer and the third layer are spirally wound with the peripheral edge portions of the belt-like sheets in contact with each other so as to overlap each other. By increasing the number of spirally wound layers by bringing the peripheral edge portions of the belt-like sheets into overlapping contact with each other, the repulsive force is further strengthened, and the liquid storage member 11 having more excellent reliability and durability can be obtained.

Also, in the present embodiment, the interval between joints (contact points) between adjacent layers is defined. For example, the distance between the joints between adjacent layers (the joint between the first layer and the second layer, the joint between the second layer and the third layer, etc.) is 1 mm along the longitudinal direction of the liquid containing member 11. It is preferably 3 mm or more and 1/2 or less of the sheet width, and more preferably 3 mm or more and 1/2 or less of the sheet width.

In the present embodiment, as an example, the intermediate layer has a two-layer structure (second layer and third layer), but it is not limited to this. The number of intermediate layers may be, for example, three or more depending on the usage conditions and product specifications (materials, dimensions, etc.) of the writing instrument. When the number of intermediate layers is three or more, that is, when the intermediate layers have a three-layer structure, a four-layer structure, . In this case, as for the layers other than the outermost layer (the innermost layer and the intermediate layer), at least one of these layers forms a layer of the paper base laminate as described above.

<Paper substrate and paper substrate laminate>
The paper base material (paper base material used in the first to fourth layers (including the inner layer of the paper base laminate)) includes fine paper, medium quality paper, one-sided glossy paper, kraft paper, and one-sided paper. Various known papers such as 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 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 is 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 this embodiment, glassine paper with a basis weight of 20 to 50 g/m ² is used. By using glassine paper as a paper substrate, 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, 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, in consideration of the compressive strength of the paper tube portion after manufacturing the liquid containing member 11 and ease of handling during manufacturing. is. 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 . Then, 0.8 to 1.3 g/cm ³ is preferable.

In addition, parchment paper and vulcanized fiber may be subjected to resin impregnation treatment or glass coating treatment. By applying this treatment, the bonding between the cellulose fibers is further strengthened, and the generation of paper dust can be suppressed even when these papers are used as the paper substrate.

The paper base laminate is a composite material in which a metal layer or a silica deposition layer is laminated on the outer surface side of the inner layer formed as a layer of the paper base. The metal layer constituting the paper base laminate may be formed by bonding a metal foil such as an aluminum foil to one side of the paper base using an adhesive containing a polyolefin resin, or may be made of aluminum or aluminum and zinc. An alloy or the like may be provided by electron beam vapor deposition under vacuum.

<Adhesive>
Here, the adhesive containing polyolefin resin used in the adhesive layer 21 will be described. The adhesive containing polyolefin resin may be an adhesive made of one or more kinds of polyolefin resins, or an adhesive obtained by mixing this polyolefin resin with other resins.

Polyolefin resins specifically 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. Among these, polypropylene ionomer 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 cross-linking agents, ethylene/vinyl acetate copolymers, polyvinyl alcohol, and the like.

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

The adhesive containing the polyolefin resin of the present embodiment is used in the form of a dispersion-type or emulsion-type resin liquid that uses a polyolefin resin or a mixture of a polyolefin resin and other resins as a base polymer. Additives such as a silane coupling agent may be added to this 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.

The adhesive containing the above-described polyolefin resin is applied between the first and second layers, between the second and third layers, and between the third and fourth layers of the liquid containing member 11. or one. That is, the adhesive layer 21 may be provided between the first layer and the second layer, between the second layer and the third layer, or between the third layer and the fourth layer. The adhesive layer 21 may be provided on any two of them, or the adhesive layer 21 may be provided between all these layers. Also, an adhesive layer 21 may be provided between each layer (between the inner layer and the metal layer) that constitutes the paper base laminate. By applying an adhesive containing a polyolefin resin having excellent adhesion and ink resistance to a paper material, the interlayers are adhered to each other, effectively preventing the ink from leaking out of the liquid containing member 11. can be done. Here, the ink resistance represents the extent to which elution of the adhesive resin component into the ink can be suppressed. If the ink resistance is insufficient, the strength of the refill decreases and the amount of volatility increases. 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 addition, by applying an adhesive containing a polyolefin resin having the above effect between each layer of the first to fourth layers and between each layer constituting the paper base laminate (between the inner layer and the metal layer) Since the strength of the liquid containing member 11 is increased, a certain effect can be obtained with respect to the problems of tearing of the liquid containing member 11 and peeling of the adhesive surface.

In this embodiment, at least one of between the first and second layers, between the second and third layers, and between the third and fourth layers in the liquid containing member 11 is It is sufficient to bond with an adhesive containing polyolefin resin, and for interlayers not coated with an adhesive containing polyolefin resin, other adhesives such as vinyl acetate resin, acrylic resin, or polyvinyl alcohol are used together. It is also possible to

<Production method>
Next, a method for manufacturing the liquid containing member 11 will be described. In this embodiment, as an example, a case will be described in which the first layer (innermost layer) is formed of a paper base laminate, and the second to fourth layers are formed as paper base layers. As for the paper base laminate, as an example, a metal layer is laminated on the outer surface side of the inner layer formed as a layer of the paper base. Further, in the present embodiment, the first and fourth layers are brought into contact so that the peripheral edge portions of the belt-shaped sheets overlap each other, and the second and third layers are brought into contact so that the peripheral edge portions do not overlap each other. and wound in a spiral shape.

According to the above premise, for example, when forming the innermost layer, first, an adhesive containing a polyolefin resin is applied so as to pile up near the center of the inner layer or metal layer that constitutes the paper base laminate. Next, while pressing the inner layer and the metal layer, 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. Then, after bonding the inner layer and the metal layer together, they are pressed and fixed until the adhesive is hardened. Thus, a paper base laminate configured as a composite material is obtained. The amount of the adhesive containing polyolefin resin applied to the inner layer or metal layer is 5-50 g/m ² , preferably 5-25 g/m ² .

In addition, the paper base laminate may be formed using a paper base material and a metal layer (or silica deposition layer) of the same thickness, or a paper base material and a metal layer (or silica deposition layer) of different thickness. may be formed by combining them as appropriate. In the paper base laminate, the ratio of the thickness of the paper base to the thickness of the metal layer (or silica deposited layer) is preferably about 2/1 to 1200/1.

Next, the paper base laminate formed as the composite material is cut into a width of 4 to 20 mm with a bobbin slitter or the like to obtain a paper base laminate formed into a belt-like sheet.

Next, the obtained paper base laminate is spirally wound around a mandrel (paper tube manufacturing machine) for processing the liquid containing member 11 so that the inner layer faces inside. At this time, for the paper base laminate forming the first layer, the strip-shaped sheet is spirally wound with the peripheral edge portions of the strip-shaped sheet contacting each other so as to overlap each other.

Through the above steps, the first layer (innermost layer) is formed. In order to make it easier to pull out the mandrel after forming the first to fourth layers (outermost layer), the mandrel must be pretreated with an appropriate lubricant or the inner layer It is preferable to apply an appropriate amount of lubricant to the surface on which the mandrel is to be wound.

The paper base laminate is preferably a belt-shaped sheet cut into a width of 4 to 20 mm, more preferably a belt-shaped sheet cut into a width of 5 to 15 mm. By spirally winding such a wide paper base laminate, the required length of the liquid containing member 11 can be reached without winding many times, and as a result, the paper base laminate can be obtained. The number of contact points, that is, the number of joints can be reduced, and leakage of the liquid contained in the liquid containing member 11 can be suppressed.

Next, on the outer surface side of the first layer, a strip-shaped sheet of paper is spirally wound to form the second layer. At this time, the paper substrate forming the second layer is spirally wound with the peripheral edge portions of the belt-like sheet in contact with each other so as not to overlap each other. The second layer is preferably formed using a paper substrate having a width of 4 to 20 mm, more preferably using a paper substrate having a width of 6 to 15 mm. This is because, similarly to the above-described paper base laminate, by reducing the number of seams, leakage of the liquid in the liquid containing member 11 can be prevented. Also, the paper substrate forming the inner layer of the paper substrate laminate can be used as the paper substrate forming the second layer. Alternatively, an adhesive containing polyolefin resin may be applied to the metal layer on the outer surface side of the first layer, and the second layer may be adhered to this metal layer. The amount of the adhesive containing the polyolefin resin used here is about the same as the amount applied to the inner layer or metal layer of the paper base laminate.

Next, on the outer surface side of the second layer, a strip-shaped paper base material is spirally wound to form the third layer. At this time, the paper base material forming the third layer is spirally wound with the peripheral edge portions of the belt-like sheet in contact with each other so as not to overlap each other, similarly to the second layer. Similarly to the second layer, the third layer is preferably formed using a paper base material having a width of 4 to 20 mm, more preferably using a paper base material having a width of 6 to 15 mm. This is because, similarly to the above, by reducing the number of joints, leakage of the liquid in the liquid containing member 11 can be prevented. As the paper base material forming the third layer, the paper base material forming the inner layer and the second layer of the paper base laminate can be used. Alternatively, an adhesive containing a polyolefin resin may be applied to the outer surface of the second layer, and the paper substrate of the third layer may be adhered to the adhesive-applied surface. The amount of the adhesive containing the polyolefin resin used here is about the same as the amount applied to the inner layer or metal layer of the paper base laminate.

Finally, on the outer surface side of the third layer, a strip-shaped paper base material is spirally wound to form the fourth layer (outermost layer). At this time, the paper base material forming the outermost layer is spirally wound with the peripheral edge portions of the belt-like sheet being brought into contact with each other so as to overlap each other. As with the third layer, the outermost layer is preferably formed using a paper base material with a width of 4 to 20 mm, and more preferably formed using a paper base material with a width of 6 to 15 mm. This is because, similarly to the above, by reducing the number of joints, leakage of the liquid in the liquid containing member 11 can be prevented. As the paper base material forming the outermost layer, the paper base material forming the inner layer, the second layer and the third layer of the paper base laminate can be used. Alternatively, an adhesive containing a polyolefin resin may be applied to the outer surface of the third layer, and the paper base material of the outermost layer may be adhered to the adhesive-applied surface. The amount of the adhesive containing the polyolefin resin used here is about the same as the amount applied to the inner layer or metal layer of the paper base laminate.

Then, after forming the first, second, third and fourth layers, the mandrel is pulled out, the cylindrical molded body is cut into a predetermined length required for the liquid containing member 11, and heated to an appropriate temperature and temperature. The desired liquid containing member 11 is obtained by drying for several hours under humidity. In the present embodiment, for convenience of explanation, the second layer and the third layer are spirally wound with the peripheral edge portions thereof in contact with each other so as not to overlap each other. As with the first and fourth layers, the layers and the third layer can also be spirally wound with their peripheral edge portions in contact so as to overlap each other. In addition, in the present embodiment, the second layer and the third layer are formed as layers of the paper base material. It is also possible to

The outer diameter of the liquid containing member 11 produced as described above 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. .

The thickness of the liquid containing member 11 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 11 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.

In addition, it is preferable that the liquid containing member 11 has a total length change rate of less than 0.7% after writing 300 m after being filled with ink (so-called initial stage). The change in the total length means that the creep stress constantly applied to the ink containing tube 11 due to writing causes the liquid containing member 11 to deform due to bending and the like, thereby shortening the total length in the axial direction. FIG. 3 is a diagram schematically showing an example of the amount of change in the total length with respect to the initial length, showing the state before writing and the state after writing of the refill for writing instrument. The total length change rate (%) can be expressed by the following formula (1).

Total length change rate = (change amount/initial length) x 100 (%) (1)

If the total length change rate is 0.7% or more, it may affect the feeling of writing, especially before the ink runs out. Since the liquid containing member 11 manufactured with the configuration of the present embodiment has excellent reliability and durability as described above, it is possible to achieve a total length change rate of less than 0.7%.

When the refill 10 is used with the refill 10 tilted at 60°, that is, when a load is applied to the refill 10 when the refill 10 is tilted at 60°, the bending strength of the liquid containing member 11 should be 0.5 N or more. is preferred. FIG. 4 is a diagram showing how a load is applied to the refill 10 tilted at 60°. If the bending strength of the liquid containing member 11 is less than 0.5 N, it may easily buckle during writing. Since the liquid containing member 11 manufactured with the configuration of this embodiment has excellent reliability and durability as described above, it is possible to achieve a bending strength of 0.5 N or more.

Further, it is preferable that the difference between the outer diameter and the inner diameter of the liquid containing member 11 is 0.3 mm or more.

Also, in this embodiment, a laser or the like is used to remove the outer surface of the liquid containing member 11 of the refill 10 until the metal layer or silica deposition layer is exposed. This makes it possible to add (print) character information such as product names and lot numbers, for example, due to the visual difference between the outer surface of the liquid containing member 11 and the metal layer or silica deposition layer. FIG. 5 is a diagram showing an example of a state in which character information is printed on the exposed metal layer or silica deposition layer. In FIG. 5, as an example, character information "20210822" is printed on the surface of the metal layer or silica deposition layer of the paper base laminate forming the third layer.

<effect>
As described above, in the liquid containing member 11 of the present embodiment, the first layer that is the innermost layer in contact with the liquid, the second and third layers that are intermediate layers, and the fourth layer that is the outermost layer At least one of the first, second, and third layers is laminated with a metal layer or silica deposition layer on the outer surface side of the inner layer formed of a paper base material. The fourth layer was formed as a layer of the paper base laminate, the other layers were formed as layers of the paper base, and the fourth layer was formed as a layer of the paper base. In addition, the layer of the paper base laminate has a structure in which the paper base laminate formed into a belt-like sheet is spirally wound so that the inner layer faces inside, and the paper base layer is a paper formed into a belt-like sheet. Each has a structure in which the base material is wound in a spiral shape, and the first layer and the fourth layer are wound in a spiral shape with the peripheral edge portions of the belt-like sheets in contact with each other so as to overlap each other. As a result, even when pressure (load) is applied from the inside to the outside on the tip of the liquid containing member 11 due to press-fitting, the repulsive force due to overlapping contact points will not easily cause breakage or peeling of the adhesive surface. A liquid containing member 11 having excellent reliability and durability can be obtained.

Although there are no particular restrictions on the refill 10 including the liquid containing member 11 of the present embodiment, it is preferable to use the following inks.

<Ink>
Suitable inks to be contained in the liquid containing member 11 of the present embodiment include a black coloring component and at least C.I. I. Acid Yellow 36, C.I. I. Acid Yellow 23, C.I. I. Acid Yellow 36 or C.I. I. A first gist is an ink composition containing at least one or a mixture of two or more selected from salt-forming dyes containing Acid Yellow 23 as a component, an amphoteric surfactant, and zinc ions, and a black coloring component. and at least C.I. I. Acid Yellow 36, C.I. I. Acid Yellow 23, C.I. I. Acid Yellow 36 or C.I. I. It incorporates a black ink composition containing at least one or a mixture of two or more selected from salt-forming dyes containing Acid Yellow 23 as a component, and an amphoteric surfactant.

The acid dye binds to the positively charged portion of the amphoteric surfactant, and the zinc ion binds to the negatively charged portion of the amphoteric surfactant, causing a binding reaction and dissolving in the ink as a coloring agent that exhibits a black color, forming highly black handwriting. can do.

The amphoteric surfactant is used to bind with the acid dye in the ink composition in the positively charged portion and to cause a binding reaction with zinc ions in the negatively charged portion.

Examples of amphoteric surfactants include betaine-type amphoteric surfactants and imidazoline-type amphoteric surfactants. Specifically, NIKKOL AM 301 (lauryldimethylaminoacetate betaine, manufactured by Nikko Chemicals Co., Ltd.), NIKKOL 3130N (coconut fatty acid amidopropyl betaine, manufactured by Nikko Chemicals Co., Ltd.), NIKKOL 101 (2-alkyl-N- Carboxymethyl-N-hydroxyethylimidazolinium betaine, manufactured by Nikko Chemicals Co., Ltd.), Amogen SH (lauryl betaine, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Amphot PB-30L (laurylamidopropyl acetate betaine, manufactured by Co., Ltd.) Adeka), betaine-type amphoteric surfactants such as AB-35L (laurylaminoacetic acid betaine, manufactured by Adeka Co., Ltd.), Amogen K (alkylamine carboxylic acid derivative, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the like. An imidazoline type amphoteric surfactant such as AOL (lauryl dimethyl amino oxide, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) can be used. In particular, the betaine-type amphoteric surfactant NIKKOL AM 3130N (coconut oil fatty acid amidopropyl betaine, manufactured by Nikko Chemicals Co., Ltd.) has an acid dye that binds to this amphoteric surfactant and further binds and reacts with zinc ions. As a result, a black color can be obtained, and handwriting with a high degree of blackness can be obtained, which is preferable. These amphoteric surfactants may be used alone or in combination of two or more. The amphoteric surfactant content is preferably 0.005% by weight or more and 10.0% by weight or less with respect to the total amount of the ink composition.

The acid dye is C.I. I. Acid Yellow 36 and/or C.I. I. It is not particularly limited as long as it contains at least Acid Yellow 23. Further, as a black coloring component, C.I. I. Acid Yellow 36 and/or C.I. I. When using a salt-forming dye of Acid Yellow 23 and a basic dye, it may be an unreacted substance of the salt-forming reaction.

The zinc ions may be zinc ions ionized by blending a zinc-containing compound in the ink composition, or zinc ions eluted from the metal member in contact with the ink composition being zinc or a zinc-containing alloy. It's okay.

Compounds containing zinc include zinc chloride, zinc oxide, zinc oxalate, zinc acetate, zinc borate, zinc formate, zinc lactate, zinc phosphate, zinc pyrophosphate, zinc salicylate, zinc stearate, zinc sulfate, zinc sulfide. Zinc etc. are mentioned. The compounding amount of the zinc-containing compound is preferably 0.005% by weight or more and 10.0% by weight with respect to the total amount of the ink composition.

The metal member that comes into contact with the ink composition includes a ball holder used in a ballpoint pen tip. The material of the metal member is not particularly limited as long as it contains zinc. Specifically, copper-zinc alloys such as red brass, brass, and detonator copper, copper-zinc-lead alloys such as free-cutting brass and nipple brass, copper-zinc-tin such as naval brass and condenser brass. Copper-zinc-nickel alloys such as alloys, nickel silver, cupronickel, nickel silver for springs, nickel silver for forging, copper-zinc-nickel-lead alloys such as free-cutting nickel silver, copper-zinc-for brass for musical instrument valves, etc. Examples include lead-manganese-tin alloys, copper-tin-phosphorus-zinc alloys such as phosphor bronze for springs, copper-zinc-aluminum-iron-manganese-nickel alloys such as high-strength brass, and aluminum-zinc alloys. In particular, nickel silver is preferable because it is excellent in workability and has a beautiful appearance color.

Black coloring components include conventionally known acid dyes, basic dyes, salt-forming dyes, and the like. Salt-forming dyes of acid dyes and basic dyes are particularly preferred.

Specifically, C.I. I. Acid Yellow 36 and C.I. I. Salt forming dye with Basic Violet 3, C.I. I. Acid Yellow 23 and C.I. I. Salt forming dye with Basic Violet 3, C.I. I. Acid Yellow 23 and C.I. I. A salt forming dye with Basic Violet 1 can be used.

The blending amount of the black coloring component in the ink composition is preferably 10% by weight or more and 50% by weight or less with respect to the total amount of the ink composition.

In addition, pigments, organic solvents, resins, and the like may be appropriately added to the ink composition of the present embodiment.

Examples of pigments include carbon black, insoluble azo pigments, azo lake pigments, condensed azo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, anthraquinone pigments, Organic pigments such as dioxazine-based pigments, indigo-based pigments, thioindigo-based pigments, quinophthalone-based pigments, perinone, and perylene-based pigments are included. These pigments may be used alone or in combination of two or more.

Organic solvents include ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether, ethylene glycol. monoisopropyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, Diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, propylene glycol monomethyl Ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol tertiary butyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene Glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, 3-methyl-3-methoxy-1-butyl acetate, etc. glycol ethers, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, octylene glycol, glycerol Glycols such as phosphorus, polyethylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, 1,3-butanediol, 1,5-pentanediol, benzyl alcohol, β-phenylethyl alcohol, α -methylbenzyl alcohol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, 3-methyl-3-methoxy Alcohols such as pentanol, lauryl alcohol, tridecyl alcohol, isodecyl alcohol, isotridecyl alcohol, methyl isopropyl ether, ethyl ether, ethyl propyl ether, ethyl butyl ether, isopropyl ether, butyl ether, hexyl ether, 2-ethylhexyl ether, etc. and esters such as 2-ethylhexyl acetate, isobutyl isobutyrate, ethyl lactate and butyl lactate. These may be used alone or in combination of two or more. The blending amount of these organic solvents is preferably 10% by weight or more and 90% by weight or less with respect to the total amount of the ink.

Resins are added to disperse pigments, impart stringiness, prevent show-through of handwriting, adjust viscosity, and promote dissolution of dyes. melamine-based resins, cellulose-based resins, condensation resins of ketones such as cyclohexanone, acetophenone, and urea and formaldehyde, condensation resins of cyclohexanone and hydrogenated resins thereof, maleic acid resins, co-polymers of styrene and maleic acid esters Polymers, copolymers of styrene and acrylic acid or their esters, polyamides that are condensates of polymerized fatty acids and polyamines, epoxy resins, polyvinyl alkyl ethers, coumarone-indene resins, polyterpenes, rosin resins and their hydrogenation rosin-modified maleic acid resin, rosin-modified phenolic resin, vinylpyrrolidone-vinyl acetate copolymer, polymethacrylate, polyoxyethylene, polyvinyl butyral resin, polyvinyl alcohol resin, polyvinyl acetal resin, vinyl acetate and Copolymers of polyvinylpyrrolidone, acrylic resin salts, copolymers of acrylic acid and alkyl methacrylate or their salts, cellulose derivatives such as hydroxypropylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, ethylcellulose, hydroxypropylated guar gum, methylcellulose, ethylcellulose , polyvinylacetamide, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, polyacrylic acid, polysaccharides such as carboxyvinyl polymer, and benzylidene sorbitol. In particular, polyvinyl butyral resin is preferable because it has a small change in viscosity over time and is excellent in pigment dispersion stability and fixability. These may be used alone or in combination of two or more. The blending amount of these resins is preferably 0.05% by weight or more and 30.0% by weight or less with respect to the total amount of the ink composition.

The viscosity of the ink at 25° C. and a shear rate of 100 s ⁻¹ is preferably 10 mPa·s or more and 5000 mPa·s or less. In particular, 200 mPa·s or more and 1000 mPa·s or less is more preferable.

The pH is preferably 3.0 or more and 10.0 or less. In particular, 6.0 or more and 8.0 or less is more preferable.

The black oil-based ink composition of this embodiment can be produced by the following method.

A black coloring component and/or an acid dye and an amphoteric surfactant are sufficiently mixed with a stirrer such as a homomixer to bind the acid dye to the positively charged portion of the amphoteric surfactant, and then a pigment if necessary. , an organic solvent, a resin, etc. are added and mixed with a stirrer. Next, a zinc-containing compound is added and thoroughly mixed with a stirrer to bond zinc ions to the negatively charged portion of the amphoteric surfactant.

When zinc or a zinc-containing alloy is used for the metal member that comes into contact with the ink composition, the black coloring component and/or the acid dye and the amphoteric surfactant are sufficiently mixed with a stirrer such as a homomixer to obtain an amphoteric surfactant. After binding the acid dye to the positively charged part of the surfactant, pigments, organic solvents, resins, etc. are added as necessary and mixed with a stirrer.

It is also possible to replace the stirrer with a dispersing machine such as a homogenizer for mixing and dispersion, or remove coarse particles and insoluble components from the obtained black oily ink by filtering or using a centrifugal separator. It can also be heated using an electric heater, band heater, or the like, or cooled using a cooler. It is preferable that the ink temperature at the time of manufacture is 5° C. or more and 95° C. or less.

In the refill 10 of the present embodiment, the black oil-based ink composition is filled through the joint 12 into the liquid containing member 11 having the ballpoint pen tip 13 attached to the tip. By housing the refill 10 in the barrel, a ball-point pen, which is the writing implement of the present embodiment, was obtained.

<Structure of Writing Instruments>
6A and 6B are views showing an example of the configuration of a ballpoint pen, which is a writing instrument in which a refill for a writing instrument is housed in a barrel. FIG. 6A shows a front view of the appearance of the writing instrument in a writing state, and FIG. shows a cross-sectional view of the writing instrument in the writing state, FIG. 6(c) shows a front view of the appearance of the writing instrument in the stored state, and FIG. 6(d) shows a cross-sectional view of the writing instrument in the stored state.

6, the writing instrument 30 includes a barrel 31 which is a tubular member formed in a tubular shape, an operating member 32 provided in the front portion of the barrel 31 and formed in a tubular shape, and the refill 10 described above. , and the operation member 32 moves in the front-rear direction with respect to the shaft cylinder 31 . At this time, the state in which the tip of the ballpoint pen tip 13 protrudes from the operation member 32 is called the writing state, and the state in which the tip of the ballpoint pen tip 13 is retracted into the operation member 32 is called the retracted state.

The barrel 31 includes a cylindrical barrel main body 31a with a closed rear end and a columnar refill extending forward from the inner surface of the closed rear end of the barrel main body 31a beyond the barrel main body. and a holding portion 31b. On the inner peripheral surface of the rear portion of the barrel main body 31a, a ridge-like convex portion protruding radially inward is formed in a spiral shape, and the convex portion as a whole forms a female screw portion 31c.

An insertion hole for inserting the refill 10 is formed in the refill holding portion 31b, and a fitting portion 31d for fitting the rear end of the refill 10 is formed at the back of the insertion hole. The inner diameter of the fitting portion 31 d is formed to be substantially the same as or slightly smaller than the outer diameter of the rear end of the refill 10 . Therefore, the refill 10 inserted into the insertion hole of the refill holding portion 31b is fixed and held by fitting the rear end of the refill 10 to the fitting portion 31d of the refill holding portion 31b so as not to come off easily. .

Note that the configuration of the writing instrument 30 of the present embodiment is an example, and is not limited to the above. For example, as long as writing is possible with the refill 10 housed, any structure and shape may be used.

<Materials of barrel and operation member>
The barrel and the operating member contain biomass-derived polyolefin as a material of environmental load. Biomass-derived polyolefin uses biomass-derived ethylene as a raw material. Biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use biomass-derived fermented ethanol obtained from plant raw materials. Plant raw materials are not particularly limited, and conventionally known plants can be used. For example, corn, sugar cane, beet and manioc may be mentioned.

　Biomass-derived polyolefins are obtained by polymerizing biomass-derived ethylene-containing monomers. When biomass-derived ethylene is used as a raw material monomer, the polymerized polyolefin is biomass-derived. Note that the polyolefin raw material monomer does not have to contain 100% by mass of biomass-derived ethylene.

The monomer that is the raw material for the biomass-derived polyolefin may further contain at least one selected from fossil fuel-derived ethylene and fossil fuel-derived α-olefin, and may further contain a biomass-derived α-olefin.

The number of carbon atoms in the α-olefin is not particularly limited. The number of carbon atoms in the α-olefin is usually an integer of 3-20. Preferred α-olefins are butylene, hexene and octene.

Biomass-derived polyolefins and fossil fuel-derived polyolefins do not differ in physical properties such as molecular weight, mechanical properties, and thermal properties, so in order to distinguish between them, the degree of biomass plastic specified in ASTM D6866 is generally used. Used. Radiocarbon 14C exists in the atmosphere at a rate of 1 in 1012, and this rate does not change even with carbon dioxide in the atmosphere. Therefore, the carbon of biomass-derived polyolefin contains radioactive carbon 14C. In contrast, the carbon of petroleum-derived resins contains almost no radioactive carbon-14C. Therefore, by measuring the concentration of radioactive carbon 14C in the resin with an accelerator mass spectrometer, the content ratio of the plant-derived resin in the resin, that is, the degree of biomass plasticity can be obtained.

The degree of biomass plasticity of biomass-derived polyolefin is not particularly limited. The biomass plastic degree of the biomass-derived polyolefin is preferably 80% or more as the lower limit from the viewpoint of consideration for the environment in the concept of carbon neutrality. The upper limit is not particularly limited, but is usually less than 99% because other agents may be mixed during molding. Therefore, the degree of biomass plasticity of the biomass-derived polyolefin is preferably 80% or more and less than 99%.

Suitable examples of biomass-derived polyolefins include polyethylene-based resins and polypropylene-based resins. It is preferable to use a polyethylene-based resin because the restoration rate can be improved by silanol cross-linking. Polyethylene-based resins include high-density polyethylene (HDPE) with a density of 0.941 g/cm ³ or more, and linear low-density polyethylene resin (LLDPE) with a density of 0.910 g/cm ³ or more and less than 0.94 g/cm ³ . , a low-density polyethylene resin (LDPE) having a density of 0.910 g/cm ³ or more and less than 0.940 g/cm ³ . The melt flow rate (MFR) of polyolefin is not particularly limited. MFR (JIS K6922-1: 1997 Annex (190° C., 21.18N load)) is preferably 1 g to 30 g/10 min, preferably 1 g to 25 g/10 min, from the viewpoint of moldability. More preferably, it is from 1 g to 20 g/10 minutes.

As biomass-derived polyolefins, Braskem's product names "SHA7260" (HDPE), "SBC818" (LDPE), "SLL118/21" (LLDPE), etc. can be used.

<Second embodiment>
Next, an embodiment of a liquid container for applicator according to the present invention will be described in detail with reference to the drawings. It should be noted that the present invention is not limited by this embodiment.

As described above,

Patent Literatures

1 and 2 disclose writing instruments using paper as a base material. In the writing instruments using paper as a base material, ink is filled in a barrel or a storage tube using paper material. Furthermore, when the ink follower is filled, a phenomenon is observed in which ink or the like remains on the inner wall of the barrel or the containing tube. This residual surface tends to reduce the ink scraping performance. Leakage and backflow of ink sometimes occurred through the remaining ink between the followers.

In order to solve these problems, it is being considered to improve the performance of the barrel or storage tube by imparting water and oil repellency to the paper substrate. For example, Japanese Patent Application Laid-Open No. 2007-152357 discloses that a tubular casting manufacturing part used as a runner pipe or the like when manufacturing a casting has a water-repellent paper tube layer made of kraft paper as the outermost layer. , a heat-resistant paper tube layer containing inorganic fibers, organic fibers and a thermosetting resin is provided inside the water-repellent paper tube layer. In addition, in Japanese Patent Laid-Open No. 2004-17991, the outermost layer, a paper base material provided with a silicone-based water-repellent coating film on its surface, a barrier layer, and the innermost layer are sequentially laminated. A paper container is described.

In the second embodiment, the inner surface of the liquid containing member made of paper is replaced with a liquid containing tube containing a paper base material to eliminate plastics. By treating the inner surface of the liquid storage member with a specific treatment agent, a liquid-repellent film is formed on the inner surface of the liquid storage member, improving the ability to scrape off the liquid. An object of the present invention is to provide a liquid storage member that can prevent

<Liquid storage member>
Hereinafter, the liquid container member for applicator of the present invention will be described in detail with reference to the drawings.
9A and 9B are diagrams showing an example of a configuration of a refill including the liquid container member 40 for an applicator of the present invention. FIG. 9A shows a front view of the appearance of the refill, and FIG. 9B shows the refill. AA' arrow cross-sectional view is shown.
In FIG. 9, for example, the refill accommodated in the barrel of a ballpoint pen is an applicator liquid accommodating member 40 (hereinafter simply referred to as , a joint 41 (corresponding to the joint 12 shown in FIG. 1) attached to the tip of the liquid accommodation member 40, and a ballpoint pen tip attached to the tip of the joint 41 as a writing member. 42 (corresponding to the ball-point pen tip 13 shown in FIG. 1).

Specifically, the joint 41 is formed with a cylindrical rear end portion that is joined to the liquid containing member 40 and a cylindrical tip portion with a larger outer diameter than the rear end portion. A chip 42 is attached. Adhesive is applied in advance to the rear end portion of the joint 41 in order to give a certain joint strength to the joint portion with the liquid containing member 40. The joint 41 and the liquid containing member 40 are joined by press-fitting into the tip of the member 40 . As a result, the liquid containing member 40 and the ball-point pen tip 42 are connected via the joint 41 so that ink can flow.

The liquid containing member 40 of the present invention is a paper base laminate comprising an inner layer 51 made of a paper base and an intermediate layer 52 formed on the outer surface side of the inner layer 51 and being a metal layer or silica deposition layer, and A structure having at least three layers consisting of an outer layer 53 formed on the outer surface side of the intermediate layer 52 and made of a paper substrate, and a structure in which the paper substrate laminate is spirally wound, and the intermediate layer 52 It has a structure in which the outer layer 53 made of the paper base material is spirally wound on the outer surface side. In addition, the liquid containing member 40 has an adhesive layer 55 containing polyolefin resin (hereinafter simply referred to as “adhesive The inner surface of the inner layer 51 is treated with at least one treatment agent selected from the group consisting of silicone oil, fluorosurfactant, and olefinic polymer.

The paper base material constituting the inner layer 51 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 51 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 51, 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 51, the generation of paper dust can be effectively suppressed.

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 40 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 .

In addition, parchment paper and vulcanized fiber may be subjected to resin impregnation treatment or glass coating treatment. By performing the above treatment, the bonding between the cellulose fibers is further strengthened, and even when these papers are used as the paper substrate constituting the inner layer 51, the generation of paper dust can be suppressed.

The intermediate layer 52 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 51 and an intermediate layer 52 is usually used as a composite material in which a metal layer or silica deposition layer is laminated on the surface of a paper base.

<Inner wall treatment>
In the present invention, in order to prevent liquid such as ink from being absorbed by the inner layer 51, the liquid-contacting side of the inner layer 51 is at least coated with silicone oil, a fluorosurfactant, and an olefinic polymer. The inner wall is treated with a kind of treatment agent. The treatment agent serves to prevent liquid such as ink from adhering to the wall surface of the liquid containing member 40 .

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.

An olefinic polymer is a polymer 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. is 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 .

<Adhesive>
Next, the adhesive used between the inner layer 51 and the intermediate layer 52 and/or between the intermediate layer 52 and the outer layer 53 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.

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 a polyolefin resin is mixed with other resins, the proportion of the polyolefin resin in the total amount of the adhesive is about 60-97% by weight, preferably 90-97% by weight. Further, when the polyolefin resin and other resins are totaled, the ratio of the polyolefin resin is about 68 to 98% by weight, preferably 93 to 98% by weight.

Adhesives containing polyolefin resins are used in the form of dispersion-type or emulsion-type resin liquids that use polyolefin resins or mixtures of polyolefin resins and other resins 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 51 and the intermediate layer 52 and between the intermediate layer 52 and the outer layer 53 . That is, as shown in FIG. 10, an adhesive layer 55 may be provided between the inner layer 51 and the intermediate layer 52 (FIG. 10(a)), or an adhesive layer 55 may be provided between the intermediate layer 52 and the outer layer 53. 55 may be provided (FIG. 10B), or an adhesive layer 55 may be provided both between the inner layer 51 and the intermediate layer 52 and between the intermediate layer 52 and the outer layer 53 (FIG. 10B). 10(c)). By applying an adhesive containing a polyolefin resin having excellent adhesive strength and ink resistance to paper materials, the inner layer 51, the intermediate layer 52 and the outer layer 53, that is, the layers of the liquid containing member 40 are closely attached, Ink can be prevented from leaking to the outside of the liquid containing member 40 . 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 51, the intermediate layer 52 and the outer layer 53 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 so as to rise near the center of the inner layer 51 or the intermediate layer 52 . Next, while pressing the inner layer 51 and the intermediate layer 52, 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 bonding defect. After bonding the inner layer 51 and the intermediate layer 52 together, they are pressed and fixed until the adhesive is cured.

The adhesive containing polyolefin resin is applied to the inner layer 51 or the intermediate layer 52 in an amount of about 5 to 50 g/m ² , preferably 5 to 25 g/m ² .

<Production method>
The inner layer 51 and the intermediate layer 52 of the liquid containing member 40 may all be formed of a paper substrate laminate using a paper substrate and a metal layer or a silica deposition layer of the same thickness, or may be formed of paper substrates and layers of different thicknesses. 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 52 to the inner layer 51, the sheet is cut with a bobbin slitter or the like to obtain a paper base laminate in the form of a belt-shaped sheet. Next, the paper base laminate is spirally wound around a mandrel (paper tube manufacturing machine) for processing the liquid containing member 40 so that the inner layer 51 faces inside. Incidentally, the surface of the mandrel may be coated with an appropriate amount of the treating agent, and the inner wall treatment may be applied to the inner layer 51 at the time of winding. After that, in order to adhere the outer layer 53 , an adhesive containing polyolefin resin is applied to the outer intermediate layer 52 .

The paper base laminate is a belt-shaped sheet that is usually cut to a width of 4 to 20 mm, preferably 5 to 15 mm. If such a wide paper base laminate is spirally wound, the required length of the liquid containing member 40 can be reached without winding many times, and as a result, contact between the paper bases can be achieved. The number of surfaces, ie seams 54, is small, and leakage of the liquid contained in the liquid containing member 40 can be suppressed.

An outer layer 53 is formed by spirally winding a paper substrate around the intermediate layer 52 . The outer layer 53 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 54' is reduced, leakage of the liquid in the liquid containing member 40 can be prevented.
As the paper base material constituting the outer layer 53, the paper base material constituting the above-described inner layer 51 can be used. Alternatively, the outer layer 53 may be attached to the intermediate layer 52 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 51 or the intermediate layer 52 .

The thickness ratio (μm) of the inner layer 51, the intermediate layer 52 and the outer layer 53 is usually 20-60:0.025-12:50-200, preferably 20-30:0.025-12: 50-200.

As described above, the liquid containing member 40 has a structure in which the paper base material laminate is spirally wound along the longitudinal direction of the liquid containing member 40 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 54 . Leakage of liquid from the seams 54 can be reduced by contacting the seams 54 without overlapping or by using a maximum overlap width of 1 mm. If the overlapping width at the seam 54 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 53 is preferably wound with the adjacent surfaces in contact with each other. The joint 54′ between the outer layers 53 and the joint 54 between the paper base laminates are 1 mm or more along the longitudinal direction of the applicator liquid containing member 40, and the width of the paper base laminate or the outer layer 53 is 1 mm or more. 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 53. Even if the seams 54' between the outer layers 53 are slightly overlapped, there is no problem of liquid leakage.

After the inner layer 51, the intermediate layer 52 and the outer layer 53 are formed, the liquid containing member 40 manufactured 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 40 for the 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 40 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 40 . Therefore, the smaller the outer diameter of the liquid containing member 40 is, the more the paper-based laminate and the outer layer 53 made of the paper-based laminate are brought into contact with each other so that the adjacent surfaces do not overlap each other when spirally winding the paper-based laminate. Moreover, it is preferable that adjacent surfaces of the outer layer 53 made of a paper base material are brought into contact with each other.

The thickness of the liquid containing member 40 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 40 within the above range, a sufficient amount of liquid can be contained, and the barrier property is 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 40, and may be a padding type or direct liquid type writing instrument, or a cosmetic tool such as eyeliner, mascara and concealer, but is preferably. is a writing utensil.

In the case of writing utensils, the pen tip can be either brush, soft brush, or 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 40 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. be.

<Example 1>
<Manufacture of liquid storage member>
In Example 1, the first layer (the innermost layer) was formed of the paper base laminate, and the second to fourth layers were formed as layers of the paper base. In addition, in Example 1, as shown in FIG. 2(a), the first and fourth layers were brought into contact with the peripheral edge portions of the belt-shaped sheets so as to overlap each other, and the second and third layers were subjected to the above-described contact. The peripheral portions are brought into contact with each other so as not to overlap each other, and are wound in a spiral shape.

Specifically, for the first layer (innermost layer), 25 μm-thick glassine paper (basis weight: 25 g/m ² , density: 1.0 g/cm ³ ) and 6.5 μm-thick aluminum foil are combined with polyolefin resin. An adhesive containing Chemipearl S500 manufactured by Mitsui Chemicals, Inc. was used for bonding. Then, the laminated paper having a total thickness of 38 μm including the thickness of the adhesive layer of 6.5 μm was cut to a width of 13 mm with a bobbin slitter.

Then, using a roll-type 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 mandrel of a paper tube manufacturing machine (Langston) was applied. was spirally wound around the outer peripheral surface of the glassine paper so that the glassine paper was on the inside. At this time, the lamination paper was wound in a spiral shape with the peripheral edge portions brought into contact with each other so as to overlap each other. The overlapping width of the contact points was set to 0.5 mm.

Next, for the second layer, 66 μm-thick coated paper (basis weight: 85 g/m ² ) cut to a width of 13 mm by a bobbin slitter was spirally wound on the outer layer of the laminated paper, aluminum foil. . At this time, the coated paper was wound in a spiral shape so that the peripheral edge portions thereof were brought into contact with each other so as not to overlap each other and butted against each other. In addition, the first layer and the second layer were wound so that the seam was 3 mm apart in the longitudinal direction.

Next, for the third layer, 66 μm-thick coated paper (basis weight: 85 g/m ² ) cut to a width of 13 mm by a bobbin slitter was spirally wound on the paper substrate of the second layer. At this time, the coated paper was wound in a spiral shape so that the peripheral edge portions thereof were brought into contact with each other so as not to overlap each other and butted against each other. Also, the second layer and the third layer were wound so that the seam was separated by 3 mm along the longitudinal direction.

Next, for the fourth layer (outermost layer), coated paper with a thickness of 66 μm (basis weight: 85 g/m ² ) cut to a width of 13 mm by a bobbin slitter was spirally wound on the paper substrate of the third layer. rice field. At this time, the coated paper was spirally wound with the peripheral edge portions thereof in contact with each other so as to overlap each other. The overlapping width of the contact points was set to 0.5 mm. Moreover, it was wound so that the joint of the third layer and the joint of the fourth layer were separated by 3 mm along the longitudinal direction.

After the first, second, third and fourth layers are formed, the mandrel is pulled out, the tubular spiral tube is cut to a length of 89.3 mm, and is heated for several hours under moderate temperature and humidity. By drying, a liquid containing member (ink containing tube) of Example 1 having an inner diameter of 3.8 mm was obtained.

<Evaluation of Liquid Storage Member>
The tip of the obtained liquid containing member of Example 1 was press-fitted into the joint, and breakage of the liquid containing member and peeling of the adhesive surface were confirmed. As a result, the liquid containing member of Example 1 was evaluated as good (A), with neither tearing of the liquid containing member nor peeling of the adhesive surface occurring (see Table 1).

In addition, for Example 1, the amount of decrease in total length in 300 m writing was evaluated. Evaluation of the total length reduction amount in 300m writing,
・Writing load: 200g
・Speed: 4.5m/min
・Writing angle: 60°
and other conditions conforming to JIS S6039 (oil-based ballpoint pen and refill). The amount of decrease in total length indicates the rate of change in total length according to the above formula (1) for the total length of the liquid containing member excluding the joint and ballpoint pen tip. As a result, the liquid storage member of Example 1 had a total length change rate of 0.3% (less than 0.7%), and was evaluated as good (see Table 1).

Further, in the refill state with the liquid containing member of Example 1 attached, a position 10 mm forward from the rear end of the liquid containing member is grasped,
・Descent speed 10mm/min
・Tilted at 60° (see Fig. 4)
The load until the liquid containing member buckles (bends) was measured under the conditions of . As a result, the bending strength of the liquid containing member of Example 1 was 1.3 N (0.5 N or more), and the evaluation was good (see Table 1).

<Example 2>
<Manufacture of liquid storage member>
In Example 2, similarly to Example 1, the first layer (innermost layer) was formed of a paper base laminate, and the second to fourth layers were formed as paper base layers. Further, in Example 2, as shown in FIG. 2(b), for all layers (first to fourth layers), the peripheral edge portions of the belt-shaped sheets are brought into contact so as to overlap each other, and are spirally wound. and

Specifically, first, for the first layer (innermost layer), a layer of the paper base laminate was formed in the same procedure as in Example 1 described above. Next, for the second layer, 66 μm-thick coated paper (basis weight: 85 g/m ² ) cut to a width of 13 mm by a bobbin slitter was spirally wound on the outer layer of the laminated paper, aluminum foil. . At this time, the coated paper was spirally wound with the peripheral edge portions thereof in contact with each other so as to overlap each other. The overlapping width of the contact points was set to 0.5 mm. In addition, the first layer and the second layer were wound so that the seam was 3 mm apart in the longitudinal direction.

Next, for the third layer, 66 μm-thick coated paper (basis weight: 85 g/m ² ) cut to a width of 13 mm by a bobbin slitter was spirally wound on the paper substrate of the second layer. At this time, the coated paper was spirally wound with the peripheral edge portions thereof in contact with each other so as to overlap each other. The overlapping width of the contact points was set to 0.5 mm. Also, the second layer and the third layer were wound so that the seam was separated by 3 mm along the longitudinal direction.

Next, for the fourth layer (outermost layer), a paper base layer was formed in the same procedure as in Example 1 described above.

After the first, second, third and fourth layers are formed, the mandrel is pulled out, the tubular spiral tube is cut to a length of 89.3 mm, and is heated for several hours under moderate temperature and humidity. By drying, a liquid containing member (ink containing tube) of Example 2 having an inner diameter of 3.8 mm was obtained.

<Evaluation of Liquid Storage Member>
The tip of the obtained liquid containing member of Example 2 was press-fitted into the joint, and breakage of the liquid containing member and peeling of the adhesive surface were confirmed. As a result, the liquid containing member of Example 2 was evaluated as good (A), with neither tearing of the liquid containing member nor peeling of the adhesive surface occurring (see Table 1).

In addition, regarding Example 2, an evaluation was made of the amount of decrease in the total length in 300m writing. The evaluation of the amount of decrease in total length in 300 m writing was performed under the same conditions as in Example 1. As a result, the liquid storage member of Example 2 had a total length change rate of 0.3% (less than 0.7%), and was evaluated as good (see Table 1).

In addition, in the refill state with the liquid containing member of Example 2 attached, under the same conditions as in Example 1, the load until the liquid containing member buckles (bends) was measured. As a result, the bending strength of the liquid containing member of Example 2 was 1.5 N (0.5 N or more), and the evaluation was good (see Table 1).

<Comparative Example 1>
<Manufacture of liquid storage member>
FIG. 7 is a diagram showing the layer structure of the liquid containing member in Comparative Examples 1 to 3. FIG. In Comparative Example 1, similarly to Example 1, the first layer (innermost layer) was formed of a paper base laminate, and the second to fourth layers were formed as paper base layers. Further, in Comparative Example 1, as shown in FIG. 7A, for all layers (first layer to fourth layer), the peripheral portions of the belt-shaped sheets are brought into contact with each other so as not to overlap, and are spirally wound. I decided to

Then, using a roll-type 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 mandrel of a paper tube manufacturing machine (Langston) was applied. was spirally wound around the outer peripheral surface of the glassine paper so that the glassine paper was on the inside. At this time, the lamination paper was wound in a spiral shape so that the peripheral edge portions were brought into contact with each other so as not to overlap each other and butted against each other.

Next, for the fourth layer (outermost layer), coated paper with a thickness of 66 μm (basis weight: 85 g/m ² ) cut to a width of 13 mm by a bobbin slitter was spirally wound on the paper substrate of the third layer. rice field. At this time, the coated paper was wound in a spiral shape so that the peripheral edge portions thereof were brought into contact with each other so as not to overlap each other and butted against each other. Moreover, it was wound so that the joint of the third layer and the joint of the fourth layer were separated by 3 mm along the longitudinal direction.

After the first, second, third and fourth layers are formed, the mandrel is pulled out, the tubular spiral tube is cut to a length of 89.3 mm, and is heated for several hours under moderate temperature and humidity. By drying, a liquid containing member (ink containing tube) of Comparative Example 1 having an inner diameter of 3.8 mm was obtained.

<Evaluation of Liquid Storage Member>
The tip of the obtained liquid containing member of Comparative Example 1 was press-fitted into the joint to check for breakage of the liquid containing member and peeling of the adhesive surface. As a result, for the liquid containing member of Comparative Example 1, both tearing of the liquid containing member and peeling of the adhesive surface occurred, and the evaluation was unsatisfactory (B) (see Table 1).

In addition, for Comparative Example 1, an evaluation was made of the amount of decrease in total length in 300m writing. The evaluation of the amount of decrease in total length in 300 m writing was performed under the same conditions as in Example 1. As a result, the liquid storage member of Comparative Example 1 had a total length change rate of 2.8% (0.7% or more), and was evaluated as unsatisfactory (see Table 1).

In addition, in the refill state with the liquid containing member of Comparative Example 1 attached, under the same conditions as in Example 1, the load until the liquid containing member buckles (bends) was measured. As a result, the bending strength of the liquid containing member of Comparative Example 1 was 0.49 N (less than 0.5 N), and the evaluation was poor (see Table 1).

<Comparative Example 2>
<Manufacture of liquid storage member>
In Comparative Example 2, similarly to Example 1, the first layer (innermost layer) was formed of a paper base laminate, and the second to fourth layers were formed as paper base layers. Further, in Comparative Example 2, as shown in FIG. 7B, for the first to third layers, the peripheral edge portions of the belt-shaped sheets were brought into contact so as not to overlap each other, and for the fourth layer, the peripheral edge portions were brought into contact with each other. were brought into contact with each other so as to overlap each other, and each was wound in a spiral shape.

Specifically, first, for the first layer (innermost layer), a layer of the paper base laminate was formed in the same procedure as in Comparative Example 1 described above. Next, for the second layer and the third layer, a paper base layer was formed in the same procedure as in Comparative Example 1 described above. Then, for the fourth layer (outermost layer), a paper base layer was formed in the same procedure as in Example 1 described above.

After the first, second, third and fourth layers are formed, the mandrel is pulled out, the tubular spiral tube is cut to a length of 89.3 mm, and is heated for several hours under moderate temperature and humidity. By drying, a liquid containing member (ink containing tube) of Comparative Example 2 having an inner diameter of 3.8 mm was obtained.

<Evaluation of Liquid Storage Member>
The tip of the obtained liquid containing member of Comparative Example 2 was press-fitted into the joint to check for breakage of the liquid containing member and peeling of the adhesive surface. As a result, for the liquid containing member of Comparative Example 2, both tearing of the liquid containing member and peeling of the adhesive surface occurred, and the evaluation was unsatisfactory (B) (see Table 1).

In addition, for Comparative Example 2, an evaluation was made of the amount of decrease in total length in 300m writing. The evaluation of the amount of decrease in total length in 300 m writing was performed under the same conditions as in Example 1. As a result, the liquid containing member of Comparative Example 2 had a total length change rate of 0.6% (less than 0.7%), and was evaluated as good (see Table 1).

In addition, in the refill state with the liquid containing member of Comparative Example 2 attached, under the same conditions as in Example 1, the load until the liquid containing member buckles (bends) was measured. As a result, the bending strength of the liquid containing member of Comparative Example 2 was 0.85 N (0.5 N or more), and the evaluation was good (see Table 1).

<Comparative Example 3>
<Manufacture of liquid storage member>
In Comparative Example 3, as in Example 1, the first layer (innermost layer) was formed of a paper base laminate, and the second to fourth layers were formed as paper base layers. In Comparative Example 3, as shown in FIG. 7(c), the first layer was brought into contact with the peripheral edge portions of the belt-shaped sheet, and the second to fourth layers were brought into contact with each other. They were brought into contact with each other so as not to overlap each other, and were wound in a spiral shape.

Specifically, first, for the first layer (innermost layer), a layer of the paper base laminate was formed in the same procedure as in Example 1 described above. Next, for the second to fourth layers, layers of the paper substrate were formed in the same procedure as in Comparative Example 1 described above.

After the first, second, third and fourth layers are formed, the mandrel is pulled out, the tubular spiral tube is cut to a length of 89.3 mm, and is heated for several hours under moderate temperature and humidity. By drying, a liquid containing member (ink containing tube) of Comparative Example 3 having an inner diameter of 3.8 mm was obtained.

<Evaluation of Liquid Storage Member>
The tip of the obtained liquid containing member of Comparative Example 3 was press-fitted into the joint to check for breakage of the liquid containing member and peeling of the adhesive surface. As a result, the liquid containing member of Comparative Example 3 did not break and was evaluated as good (A). ) (see Table 1).

In addition, for Comparative Example 3, an evaluation was made of the amount of decrease in total length in 300m writing. The evaluation of the amount of decrease in total length in 300 m writing was performed under the same conditions as in Example 1. As a result, the liquid storage member of Comparative Example 3 had a total length change rate of 0.5% (less than 0.7%), and was evaluated as good (see Table 1).

In addition, in the refill state with the liquid containing member of Comparative Example 3 attached, under the same conditions as in Example 1, the load until the liquid containing member buckles (bends) was measured. As a result, the bending strength of the liquid containing member of Comparative Example 3 was 1.1 N (0.5 N or more), and the evaluation was good (see Table 1).

<Summary>
Table 1 summarizes the evaluation results of Example 1, Example 2, Comparative Example 1, Comparative Example 2 and Comparative Example 3. In Table 1, "OW" means overlap (contact so that the peripheral parts of the strip sheet overlap each other), "butt" means no overlap, and "A" means that the evaluation is good. and "B" indicates that the evaluation is poor.

Subsequently, liquid containing members used in Examples 3 to 5 and Comparative Example 4 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 Examples 3 to 5 and Comparative Example 4 were prepared according to the following recipes.
<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 3]
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). 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 2 shows the types of processing agents used and the evaluation results.

[Example 4]
A paper tube 2 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 3, 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 2 shows the types of processing agents used and the evaluation results.

[Example 5]
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 3, 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 2 shows the types of processing agents used and the evaluation results.

[Comparative Example 4]
An ink containing member was produced in the same manner as in Example 3, except that the inner wall of the ink containing member was not treated.
In the same manner as in Example 3, 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 2 shows the types of processing agents used and the evaluation results.

As described above, the liquid containing member according to the present invention using a paper base material is useful for writing instruments that consider environmental issues such as elimination of plastics, and is particularly suitable as a substitute part for plastic liquid containing members.

10 Refill 11 Liquid storage member for writing instrument (liquid storage member)
12 Joint 13 Ballpoint pen tip 13a Spring 13b Writing ball 13c Holder 13c ₁ Cylindrical portion 13c ₂ Tapered portion 13c ₃ Ball house 13c ₄ Back hole 13c ₅ Ink hole 21 Adhesive layer 30 Writing instrument 31 Axle tube 31a Axle tube body 31b Refill holder 31c Female screw portion 31d Fitting portion 32 Operating member 40 Liquid containing member for applicator (liquid containing member)
41 Joint 42 Ballpoint Pen Tip 51 Inner Layer 52 Intermediate Layer 53 Outer Layers 54, 54' Seam 55 Adhesive Layer (Adhesive Layer)

Claims

Consists of an innermost layer in contact with a liquid, an intermediate layer formed of two or more layers, and an outermost layer,
For the layers other than the outermost layer, at least one of these layers is a paper base laminate layer in which a metal layer or silica deposition layer is laminated on the outer surface side of the inner layer formed by the paper base material. and forming the other layer as a layer of the paper base,
Furthermore, the outermost layer is formed as a layer of a paper substrate,
The layer of the paper base laminate has a structure in which the paper base laminate formed into a belt-like sheet is spirally wound so that the inner layer faces inside, and the layer of the paper base is paper formed into a belt-like sheet. Each has a structure in which the base material is wound in a spiral,
For the innermost layer and the outermost layer, the peripheral edge portions of the belt-shaped sheet are in contact with each other so as to overlap and are wound in a spiral.
A liquid storage member for a writing instrument, characterized by:
The intermediate layer has a two-layer structure,
Regarding the innermost layer and the intermediate layer, which are layers other than the outermost layer, at least one of the three layers obtained by adding the two layers of the intermediate layer to the innermost layer is used as a layer of the paper base laminate. Form,
The liquid containing member for a writing instrument according to claim 1, characterized in that:
An adhesive layer that is an adhesive layer containing a polyolefin resin is provided between at least one of the layers from the innermost layer to the outermost layer,
The liquid containing member for a writing instrument according to claim 1, characterized in that:
Each layer forming the intermediate layer is spirally wound with the peripheral edge portions of the belt-shaped sheet in contact with each other so that they do not overlap.
The liquid containing member for a writing instrument according to claim 1, characterized in that:
At least one of the layers forming the intermediate layer is spirally wound with the peripheral edge portions of the strip sheet in contact with each other so as to overlap.
The liquid containing member for a writing instrument according to claim 1, characterized in that:
The paper base laminate adheres the inner layer and the metal layer with an adhesive containing a polyolefin resin.
The liquid containing member for a writing instrument according to claim 1, characterized in that:
Using the paper base laminate and the paper base as a strip-shaped sheet with a width of 4 to 20 mm,
7. The liquid containing member for a writing instrument according to claim 1, characterized in that:
The total length change rate after 300 m writing is less than 0.7%,
7. The liquid containing member for a writing instrument according to claim 1, characterized in that:
A bending strength of 0.5 N or more under a load with an inclination of 60°,
7. The liquid containing member for a writing instrument according to claim 1, characterized in that:
a liquid storage member for a writing instrument according to any one of claims 1 to 6;
ink for a writing instrument stored inside the liquid storage member for a writing instrument;
a writing member;
comprising
A refill for a writing instrument characterized by:
The outer surface of the liquid storage member for a writing instrument is removed until the metal layer or silica deposition layer forming the layer of the paper base laminate is exposed, and information can be displayed on the metal layer or the silica deposition layer.
A refill for a writing instrument according to claim 10, characterized in that:
Using the paper base laminate and the paper base as a strip-shaped sheet with a width of 4 to 20 mm,
A refill for a writing instrument according to claim 10, characterized in that:
The total length change rate after 300 m writing is less than 0.7%,
A refill for a writing instrument according to claim 10, characterized in that:
A bending strength of 0.5 N or more under a load with an inclination of 60°,
A refill for a writing instrument according to claim 10, characterized in that:
The refill for the writing instrument according to claim 10 is configured to be accommodated in the barrel,
The barrel contains biomass-derived polyolefin,
A writing instrument characterized by:
The outer surface of the liquid storage member for a writing instrument is removed until the metal layer or silica deposition layer forming the layer of the paper base laminate is exposed, and information can be displayed on the metal layer or the silica deposition layer.
16. The writing instrument according to claim 15, characterized in that:
Using the paper base laminate and the paper base as a strip-shaped sheet with a width of 4 to 20 mm,
16. The writing instrument according to claim 15, characterized in that:
The total length change rate after 300 m writing is less than 0.7%,
16. The writing instrument according to claim 15, characterized in that:
A bending strength of 0.5 N or more under a load with an inclination of 60°,
16. The writing instrument according to claim 15, characterized in that:
A paper substrate laminate comprising an inner layer made of a paper substrate and an intermediate layer formed on the outer surface side of the inner layer and being a metal layer or a silica deposition layer, and a paper formed on the outer surface side of the intermediate layer an outer layer consisting of a base material, and at least three layers consisting of
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.