Liquid storage member for applicator

Abstract

To provide a liquid storage member for an applicator capable of restricting a liquid spill of an ink follower or a scattering into the ink due to a reversal phenomenon by enhancing performance of the ink follower and improving a degree of adhesion or friction resistance with an interior wall of a liquid storage tube using a paper base material.SOLUTION: A liquid storage member for an applicator comprises: a liquid storage tube using a paper base material; and an ink follower filled in the liquid storage tube, having a phase angle at shearing strain amplitude of 0-30% at 25°C, 1 Hz equal to or less than 50°, and having an oil separation degree when left for 24 hours at 60°C equal to or less than 5%.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Transparent or translucent plastics such as polypropylene have traditionally been used for ink storage components in writing instruments such as ballpoint pens. However, in recent years, there has been growing momentum to address global environmental issues, such as by reducing the use of plastic, and proposals have been made to eliminate the use of plastic for the various parts that make up writing instruments.

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

[0004] Patent Document 2 discloses an aqueous ink storage member that uses an ink storage tube with a multilayer structure, in which one or more layers of another resin are formed inside a storage tube base molded from a biodegradable resin. In this aqueous ink storage member, because the storage tube base is molded from a biodegradable resin, it does not swell with aqueous ink and undergo dimensional changes, and it is biodegradable over time, which contributes to reducing the amount of waste disposal.

[0005] When ink is filled into a barrel or storage tube using these paper base materials and then an ink follower is filled, the adhesion between the inner wall of the barrel or storage tube and the ink follower may be insufficient. For example, when an impact is applied, the ink and follower may scatter inside the writing instrument, or when stored upright at high temperatures, the follower may leak from the storage tube.

[0006] To solve these problems, improvements to the performance of ink followers are being considered. For example, a water-based ballpoint pen that has excellent stability over time and line drying properties, as well as excellent resistance to drying of the pen tip, and does not cause problems such as blobbing, line cracking, or ink dripping, requires water-based ink to be applied at a temperature of 25°C and a shear rate of 1 sec. -1 The viscosity is 20,000 mPa·sec or more at a temperature of 25°C and a shear rate of 100 sec -1 An ink follower having a viscosity of 5000 mPa·sec or more at 2000 kJ / s is used (Patent Document 3).

[0007] Furthermore, Patent Document 4 describes an ink follower for aqueous ballpoint pens that has stable tracking regardless of pen body specifications, ink outflow during writing, or writing speed, and that does not cause ink backflow due to lack of ink follower during writing, or that does not scatter the ink follower even when subjected to a drop impact.The ink follower has viscoelasticity with a predominantly elastic response, and has a value of 0.5 to 12% in an oil separation test (60°C, 24h) in accordance with JISK2220-5.7-1993, and an ink follower whose tan δ value is 0.1 to 1.5 over the entire frequency range at a temperature of 25°C and an angular frequency of 0.1 to 630 rad / sec, and whose value in an oil separation test (60°C, 24h) in accordance with JISK2220-5.7-1993 is 0.5 to 12%. It has also been reported that an ink follower containing a non-volatile or hardly volatile organic solvent and a non-styrene thermoplastic elastomer that is soluble or swells in the organic solvent exhibits viscoelasticity with predominantly elastic response (Patent Document 5).

[0008] However, when previous ink followers were used in storage tubes using a paper base material, the adhesion and frictional resistance between the inner wall and the ink follower was insufficient, which could cause the ink follower to leak or cause a reversal phenomenon, causing it to splash into the ink, which would have a negative impact not only on the performance of the writing instrument but also on its appearance, so it was necessary to develop an ink follower suitable for storage tubes using a paper base material. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 62-70097 [Patent Document 2] Japanese Patent Application Laid-Open No. 2001-146091 [Patent Document 3] Japanese Patent Application Laid-Open No. 2006-193688 [Patent Document 4] International Publication No. 2003-057507 [Patent Document 5] Japanese Patent Application Laid-Open No. 2004-142323 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention aims to provide a liquid storage member for an applicator that can improve the performance of the ink follower and increase the degree of adhesion and frictional resistance with the inner wall of a liquid storage member made of a paper base material, thereby suppressing liquid leakage from the ink follower and splashing into the ink due to the inversion phenomenon. [Means for solving the problem]

[0011] The liquid containing member for an applicator of the present invention is characterized by comprising: a liquid containing tube using a paper base material; and an ink follower filled into the liquid containing tube, the ink follower having a phase angle of 50° or less at a shear strain amplitude of 0 to 30% at 25°C and 1 Hz, and an oil separation rate of 5% or less when left at 60°C for 24 hours. The phase angle of the liquid filled in the liquid containing tube at 25° C. and 1 Hz with a shear strain amplitude of 0 to 30% is preferably 45° or less.

[0012] The ink follower preferably contains at least one base oil selected from the group consisting of liquid paraffin, poly-α-olefin, synthetic aromatic hydrocarbon, mineral oil, polybutene, and silicone oil. The liquid containing member for an applicator is preferably used in a paper refill for a writing implement. [Effects of the Invention]

[0013] According to the present invention, by improving the adhesion and frictional resistance between the inner wall of a liquid containing tube made of a paper base material and the ink follower filled in the liquid containing tube, it is possible to provide a liquid containing member for an applicator that improves ink scraping performance and can suppress liquid leakage when the applicator is placed upright and the occurrence of inversion of the ink follower. [Brief explanation of the drawings]

[0014] [Figure 1] Fig. 1 shows an example of the configuration of a refill including a liquid containing member for an applicator of the present invention, in which Fig. 1(a) is a front view of the appearance of the refill, and Fig. 1(b) is a cross-sectional view of the refill taken along the line A-A'. [Figure 2] Fig. 2 shows the three-layer structure of an inner layer, an intermediate layer, and an outer layer that constitute a liquid containing member for an applicator of the present invention. Fig. 2(a) shows a configuration in which an adhesive layer is provided between the inner layer and the intermediate layer, Fig. 2(b) shows a configuration in which an adhesive layer is provided between the intermediate layer and the outer layer, and Fig. 2(c) shows a configuration in which an adhesive layer is provided between the inner layer, the intermediate layer, and the outer layer. DETAILED DESCRIPTION OF THE INVENTION

[0015] The liquid containing member for an applicator of the present invention will be described in detail below with reference to the drawings. FIG. 1 shows an example of the configuration of a refill including a liquid containing member 10 for an applicator of the present invention, where FIG. 1(a) shows a front view of the appearance of the refill, and FIG. 1(b) shows a cross-sectional view of the refill taken along the line A-A'. In Figure 1, for example, the refill housed in the barrel of a ballpoint pen comprises a liquid container 10 for an applicator (hereinafter simply referred to as "liquid container 10"), which is a long, thin, cylindrical ink container tube made of paper and containing ink (not shown), a joint 11 attached to the tip of this liquid container 10, and a ballpoint pen tip 12 attached to the tip of joint 11 as a writing member.

[0016] Specifically, the joint 11 has a cylindrical rear end portion that joins with the liquid containing member 10, and a cylindrical front end portion that has a larger outer diameter than the rear end portion, and the ballpoint pen tip 12 is attached to this front end portion. An adhesive is applied in advance to the rear end portion of the joint 11 to ensure a certain level of joining strength at the joint with the liquid containing member 10, and in this state, the rear end portion of the joint 11 is press-fitted into the front end of the liquid containing member 10 to join the joint 11 and the liquid containing member 10. This connects the liquid containing member 10 and the ballpoint pen tip 12 via the joint 11 so that ink can flow through them.

[0017] The liquid containing member 10 is a liquid containing tube made of a paper base material filled with an ink follower that has a phase angle of 50° or less at a shear strain amplitude of 0 to 30% at 25°C and 1 Hz, and an oil separation rate of 3% or less when left standing at 60°C for 24 hours.

[0018] The ink follower is not limited as long as it is a non-water-soluble organic solvent with a phase angle of 50° or less at a shear strain amplitude of 0 to 30% at 25°C and 1 Hz and an oil separation rate (60°C, 24 hours) of 5% or less, but from the perspective of maintaining the performance of the applicator over a long period of time due to its non-volatile properties, it preferably contains at least one base oil selected from the group consisting of poly-alphaolefins, synthetic aromatic hydrocarbons, mineral oils, polybutenes, and silicone oils.

[0019] Mineral oil is a mixture of hydrocarbons obtained from petroleum. For example, commercially available products such as Diana Process Oil PW-380 (manufactured by Idemitsu Kosan Co., Ltd.) are used. Poly-α-olefins are synthetic oils obtained by polymerizing α-olefins and are the starting material for the reaction. Typical examples of α-olefins include 1-octene, 1-decene, and 1-dodecene. Commercially available products include barrel process oil P-380 (manufactured by Matsumura Oil Co., Ltd.) and barrel process oil P-1500 (manufactured by Matsumura Oil Co., Ltd.). As the synthetic aromatic hydrocarbon, for example, Diana Process Oil NR-26 (manufactured by Idemitsu Kosan Co., Ltd.) is used.

[0020] From the viewpoint of maintaining the performance of the applicator over a long period of time, the polybutene used is a non-volatile polybutene with a number average molecular weight of 600 or more. Commercially available polybutenes include Nissan Polybutene 200N (manufactured by NOF Corporation), Polybutene 30N (manufactured by NOF Corporation), Polybutene HV-15 (manufactured by Shin-Nippon Chemical Co., Ltd.), and 35R (manufactured by Idemitsu Kosan Co., Ltd.).

[0021] Any silicone oil may be used as long as it is non-volatile, and commercially available products such as the TSF451 series, TSF456 series, and TSF458 series (all manufactured by GE Toshiba Silicones Co., Ltd.) may be used.

[0022] These base oils can be used alone or in combination of two or more, and the amount used is 70 to 99.8% by weight, preferably 85 to 99.5% by weight, based on the total weight of the ink follower.

[0023] The ink follower is preferably prepared by further blending a viscoelasticity imparting agent in addition to the base oil. Examples of viscoelasticity imparting agents include non-styrene thermoplastic elastomers such as non-styrene thermoplastic elastomers, vinyl chloride thermoplastic elastomers, olefin thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers, and polyurethane thermoplastic elastomers, as well as metal soaps, etc. Among these, olefin thermoplastic elastomers are preferred.

[0024] Olefin-based thermoplastic elastomers are thermoplastic elastomers that use polyolefins such as polypropylene or polyethylene for the hard segments and ethylene-propylene-diene rubber for the soft segments. Examples include Milastomer-6030N, Milastomer-803N, Milastomer-9070N, Milastomer-M4800N, Milastomer-S500, Milastomer-H0500 (Mitsui Chemicals, Inc.), Engage-8842, Milastomer-8130, Milastomer-8180, Milastomer-8150, Milastomer-8100, Milastomer-8200, Milastomer-8407, Milastomer-8452, Milastomer-8411, Milastomer-8003, Milastomer-8585, Milastomer-8401, Milastomer-8440, Milastomer-8480, Milastomer-8450, Milastomer-8402, Milastomer-8540, Milastomer-8445, and Milastomer-8403 (DuPont Dow Elastomers). Examples of suitable ethylene glycol ethers include ethylene glycol ethers (manufactured by AES Japan K.K.), SANTOPRENE-101-55, SANTOPRENE-101-64, SANTOPRENE-101-73, SANTOPRENE-101-80, SANTOPRENE-101-87, SANTOPRENE-103-40, SANTOPRENE-103-50, SANTOPRENE-111-45, SANTOPRENE-111-55, SANTOPRENE-111-64, SANTOPRENE-111-73, SANTOPRENE-111-80, and SANTOPRENE-111-87 (manufactured by AES Japan K.K.), and THERMORUN-2920, THERMORUN-2940, THERMORUN-3550, THERMORUN-3650, THERMORUN-3601, THERMORUN-3801, THERMORUN-3980, and THERMORUN-5850 (manufactured by Mitsubishi Chemical Corporation).

[0025] These viscoelasticity imparting agents can be used alone or in combination of two or more, and the amount used may be an amount that allows the ink follower to exhibit excellent viscoelasticity in elastic response, and is 0.2 to 30%, preferably 0.5 to 15%, and more preferably 0.5 to 10% of the total amount of the ink follower.

[0026] The properties of the ink follower (shear strain, oil separation, etc.) can be optimized by selecting the type and amount of base oil and viscoelasticity imparting agent used, as well as by selecting the manufacturing conditions.

[0027] The ink follower in the present invention has a phase angle of 50° or less, preferably 45° or less, more preferably 25 to 42° at 25° C. and 1 Hz with a shear strain amplitude of 0 to 30%. Shear strain is a dynamic viscoelastic property and is measured by measuring the shear (shear deformation) of the ink follower. Shear measurement is the ratio of the strain to the deformation in the gap between the flat sample and the measurement stage. Specifically, the ink follower sample is placed flat on the measurement stage and held in place by applying a load to prevent it from loosening. In this state, a vibrator connected to the sample via an axis is activated to apply dynamic stress to the sample. When the vibrator is activated, dynamic stress is applied to the sample as a stimulus, and dynamic strain is generated in the sample in response. When the dynamic stress and dynamic strain are converted into electrical signals and output from the respective detectors, two waveforms (phases) are aligned on the time axis. The ratio of the stress peak value to the strain peak value of the waveform is defined as shear strain, and the phase angle (°) is calculated for shear strain amplitudes of 0 to 50%. The phase angle indicates the delay in the sample's response to the applied strain.

[0028] In addition to shear strain, the ink follower of the present invention has an oil separation rate of 5% or less when left standing at 60°C for 24 hours. The oil separation rate is determined by conducting an oil separation test in accordance with JISK 2220-5.7-1993 at 60°C for 24 hours. When using a conventional plastic liquid reservoir tube made of polypropylene or other plastic, moderate oil separation is necessary to reduce frictional resistance between the liquid reservoir tube and the ink follower and improve tracking performance. However, in the present invention, if oil separation occurs between the follower and the inner wall of the liquid reservoir tube, adhesion between the follower and the inner wall of the liquid reservoir tube decreases, leading to ink leakage through the oil separation. Therefore, even if the ink follower has sufficient elasticity, an oil separation rate of more than 5% is likely to cause oil separation, which can lead to poor appearance due to backflow of the ink follower or poor writing performance due to reverse writing.

[0029] The oil separation test according to JIS K 2220-5.7-1993 involves filling a metal wire cone filter, as specified in the JIS standard, with a test sample, leaving it in an environment at 100°C for 24 hours, and measuring the amount of oil that separates out from the wire cone filter. In the present invention, the evaluation is carried out at 60°C in order to evaluate the performance of the writing instrument over time.

[0030] In the present invention, the ink follower contains a base oil and a viscoelasticity imparting agent, and exhibits viscoelasticity with a superior elastic response, thereby enabling the effects of the present invention to be exerted. Furthermore, by imparting appropriate viscoelasticity, the occurrence of oil separation phenomenon can be suppressed, and backflow and reverse flow of the ink follower can be suppressed.

[0031] The ink follower is prepared by mixing the base oil and the viscoelasticity imparting agent by heating and stirring or heating and kneading. If necessary, a thickening aid (such as fine particle silica), a surfactant, or an antioxidant may be added. The viscoelasticity of the resulting ink follower can be adjusted by further kneading it again in a dispersing machine such as a roll mill or kneader, or by heating.

[0032] The liquid containing tube using a paper substrate according to the present invention has at least three layers: an inner layer 1 that comes into contact with the liquid, an intermediate layer 2, and an outer layer 3; and has a polyolefin resin-containing adhesive layer 5 (hereinafter simply referred to as "adhesive layer 5") between the inner layer 1 and the intermediate layer 2 and / or between the intermediate layer 2 and the outer layer 3. Figure 2c shows an embodiment in which adhesive layers 5 are provided both between the inner layer 1 and the intermediate layer 2 and between the intermediate layer 2 and the outer layer 3. Of this three-layer structure, the inner layer 1 and the intermediate layer 2 are paper substrate laminates, which are composite materials in which a metal layer or a silica vapor-deposited layer is laminated on the surface of a paper substrate. As described above, the paper substrate laminate may have an adhesive layer 5 interposed therebetween.

[0033] The paper substrate that constitutes the inner layer 1 can be any of a variety of well-known materials, such as fine paper, medium-quality paper, one-side glossy paper, kraft paper, one-side glossy kraft paper, bleached kraft paper, paperboard, white paperboard, liner, lightly coated paper, coated paper, art paper, cast-coated paper, glassine paper, parchment paper, and vulcanized fiber. The density of these paper substrates is 0.8 g / cm 3 The density is preferably 0.8 g / cm or more. 3 By using the above paper substrate, sufficient water resistance and oil resistance can be imparted. The paper substrate constituting the inner layer 1 is glassine paper, parchment paper or vulcanized fiber and has a density of 0.8 g / cm 3 More preferably, it is the above.

[0034] Glassine paper is a high-density, highly transparent paper that is made by extensively beating virgin pulp to increase the specific surface area, and then treating the paper with a supercalender to densify it and strengthen the bonds between the cellulose fibers. In the present invention, the basis weight is 20 to 50 g / m 2 By using glassine paper as the paper base material constituting the inner layer 1, it becomes easy to impart water resistance and oil resistance. 2 Alternatively, the glassine paper may be used as a base paper, and one or both sides of the base paper may be coated with a coating solution such as an aqueous polyvinyl alcohol solution. The thickness of the glassine paper is usually 20 to 50 μm, and preferably 20 to 30 μm.

[0035] Parchment paper and vulcanized fiber are made by treating them with concentrated sulfuric acid or zinc chloride solution during the manufacturing process to strengthen the direct bonds between the cellulose fibers, i.e., increase the density of the cellulose hydrogen bonds between the cellulose fibers. Therefore, if parchment paper or vulcanized fiber is used as the paper base material that makes up the inner layer 1, the generation of paper dust can be effectively suppressed.

[0036] Parchment paper has a basis weight of 20 to 100 g / m 2 Preferably, the oil absorption is 13 g / m when mineral oil is used instead of water according to the water absorption test method for paper and paperboard (Cobb method). 2 Parchment paper with improved oil resistance is used so that it satisfies the following criteria: The thickness of the parchment paper is usually 20 to 100 μm, and preferably 20 to 60 μm.

[0037] Vulcanized fiber can be made thicker than parchment paper due to differences in reactivity during the manufacturing process. Therefore, it is suitable when thick paper is required as the paper substrate. The thickness of vulcanized fiber is usually 0.08 to 1 mm, preferably 0.1 to 0.5 mm, taking into consideration the compressive strength of the paper tube portion after forming the liquid storage member 10 and ease of handling during manufacturing. In addition, the density of vulcanized fiber is higher than that of general paper tube base paper, and is usually 0.8 to 1.4 g / cm. 3 However, in the present invention, taking into consideration the strength and availability of the paper tube, the 3 It is preferable to do so.

[0038] Parchment paper and vulcanized fiber may also be subjected to a resin impregnation or glass coating process, which strengthens the bonds between the cellulose fibers and reduces the generation of paper dust when used as the paper base material for the inner layer 1.

[0039] The intermediate layer 2 is a metal layer or a silica vapor deposition layer. The metal layer may be formed by adhering a metal foil such as aluminum foil to one side of the paper substrate with an adhesive containing a polyolefin resin, or by depositing aluminum or an alloy of aluminum and zinc under vacuum using an electron beam.

[0040] The polyolefin resin-containing adhesive used in the present invention will now be described. The polyolefin resin-containing adhesive may be an adhesive made of one or more polyolefin resins, or may be an adhesive made by mixing the polyolefin resin with other resins.

[0041] Specific examples of polyolefin resins include polyethylene ionomers, polypropylene ionomers, polypropylene elastomers, polyethylene elastomers, high-density polyethylene, low-density polyethylene, and modified polyolefin resins such as maleic anhydride-modified polypropylene. Of these, polypropylene ionomers and maleic anhydride-modified polypropylene are preferred.

[0042] Other resins include, for example, acrylic acid copolymers, ethylene-vinyl alcohol copolymers (EVOH), ethylene-acrylic acid copolymers (EAA), ethylene-methacrylic acid copolymers (EMAA), epoxy resins, carbodiimide crosslinkers, ethylene-vinyl acetate copolymers, or polyvinyl alcohol.

[0043] When polyolefin resin is mixed with other resins, the proportion of polyolefin resin in the total amount of adhesive is about 60 to 97% by weight, preferably 90 to 97% by weight, and the proportion of polyolefin resin in the total amount of polyolefin resin and other resins is about 68 to 98% by weight, preferably 93 to 98% by weight.

[0044] The polyolefin resin-containing adhesive of the present invention is used in the form of a dispersion or emulsion type resin liquid, with a polyolefin resin or a mixture of a polyolefin resin and other resins as the base polymer. Additives such as a silane coupling agent may be added to the resin liquid as needed. Among these, dispersion type adhesives such as polypropylene ionomer and maleic anhydride-modified polypropylene are preferred because of their excellent adhesive properties and ease of handling.

[0045] The adhesive containing polyolefin resin is applied between the inner layer 1 and the intermediate layer 2, or between the intermediate layer 2 and the outer layer 3. Specifically, as shown in Figure 2, an adhesive layer 5 may be applied between the inner layer 1 and the intermediate layer 2 (Figure 2a), between the intermediate layer 2 and the outer layer 3 (Figure 2b), or between both the inner layer 1 and the intermediate layer 2 and between the intermediate layer 2 and the outer layer 3 (Figure 2c). By applying an adhesive containing polyolefin resin, which has excellent adhesion to paper and ink resistance, the inner layer 1, the intermediate layer 2, and the outer layer 3 of the liquid containing tube are tightly adhered to each other, preventing ink leakage to the outside of the liquid containing tube. Ink resistance refers to the degree to which the adhesive resin components can be prevented from leaching into the ink. When an adhesive containing polyolefin resin is used, its low compatibility with ink prevents the polyolefin resin from dissolving in the ink, which is expected to improve ink resistance.

[0046] In the present invention, any one of the inner layer 1, the intermediate layer 2 and the outer layer 3 may be bonded together with an adhesive containing a polyolefin resin, and other adhesives, such as general-purpose adhesives based on vinyl acetate resin, acrylic resin and polyvinyl alcohol, may also be used in combination.

[0047] The adhesive containing polyolefin resin is applied in a mound near the center of the inner layer 1 or intermediate layer 2. Next, the inner layer 1 and intermediate layer 2 are pressed together while the adhesive is spread over the entire bonding surface, bonding the two layers together without leaving any air bubbles or adhesive defects. After bonding the inner layer 1 and intermediate layer 2 together, they are pressed together and fixed in place until the adhesive hardens.

[0048] The adhesive containing polyolefin resin for the inner layer 1 or the intermediate layer 2 is 5 to 50 g / m 2 Approximately, preferably 5 to 25 g / m 2 Apply in the amount of

[0049] The inner layer 1 and middle layer 2 of the liquid storage tube may be formed from a paper substrate laminate using a paper substrate and a metal layer or a silica vapor deposition layer of the same thickness, or may be formed by appropriately combining paper substrate laminates using paper substrates and metal layers or silica vapor deposition layers of different thicknesses. In the paper substrate laminate, the ratio of the thickness of the paper substrate to the thickness of the metal layer or silica vapor deposition layer is about 2 / 1 to 1200 / 1.

[0050] After adhering the intermediate layer 2 to the inner layer 1, the laminate is cut into a width of 4 to 20 mm using a bobbin slitter or similar to obtain a strip-shaped sheet of a paper substrate laminate. The paper substrate laminate is then spirally wound around a mandrel (a paper tube manufacturing machine) with the inner layer 1 facing inward. To facilitate removal of the mandrel after the inner layer 1, intermediate layer 2, and outer layer 3 have been formed, it is preferable to pre-treat the surface of the mandrel with a suitable lubricant or to apply an appropriate amount of lubricant to the surface of the inner layer 1 (paper substrate) that will be wound around the mandrel. Then, to adhere the outer layer 3, an adhesive such as an adhesive containing a polyolefin resin is applied to the outer intermediate layer 2.

[0051] The paper substrate laminate is preferably a strip-shaped sheet cut to a width of 4 to 20 mm, more preferably 5 to 15 mm. By spirally winding such a wide paper substrate laminate, the required length of the liquid containing member 10 can be achieved without winding it multiple times, and as a result, the number of contact surfaces between the paper substrates, i.e., the number of seams 4, can be reduced, and leakage of the liquid contained in the liquid containing tube can be suppressed.

[0052] A paper base material is further spirally wound around the outside of the intermediate layer 2 to form the outer layer 3. The outer layer 3 is also preferably formed using a paper base material having a width of 4 to 20 mm, specifically 6 to 15 mm. As with the paper base material laminate, reducing the number of seams 4' can prevent leakage of the liquid inside the liquid containing member 10. The paper substrate constituting the outer layer 3 can be the same as the paper substrate constituting the inner layer 1. Alternatively, the outer layer 3 may be attached to the intermediate layer 2 using an adhesive containing the polyolefin resin. The application method and amount of the adhesive containing the polyolefin resin in this case are similar to those for the inner layer 1 or the intermediate layer 2.

[0053] The ratio of the thicknesses (μm) of the inner layer 1, the intermediate layer 2 and the outer layer 3 is usually 20-60:0.025-12:50-200, and preferably 20-30:0.025-12:50-200.

[0054] As described above, the liquid containing tube of the present invention has a structure in which a paper base laminate is spirally wound along the longitudinal direction of the liquid containing tube, with adjacent surfaces of the paper base laminate in contact with each other so as not to overlap. Even if adjacent surfaces overlap at the contact point between the paper base laminates, i.e., at seam 4, the overlap width is limited to a maximum of 1 mm. By making seam 4 contact so as not to overlap, or by limiting the overlap width to a maximum of 1 mm, leakage of liquid from seam 4 can be suppressed. If the overlap width at seam 4 exceeds 1 mm, a step will occur at the overlapping portion, which may lead to liquid leakage.

[0055] As with the paper base laminate, the outer layers 3 are preferably wound with their adjacent surfaces in contact. The seams 4' between the outer layers 3 and the seams 4 between the paper base laminates are preferably spaced apart along the longitudinal direction of the liquid containing member 10 by a distance of 1 mm or more and half or less of the width of the paper base laminate or the outer layer 3, more preferably 3 mm or more and half or less of the width of the paper base laminate or the outer layer 3. Note that even if the seams 4' between the outer layers 3 overlap slightly, there is no risk of liquid leakage.

[0056] The liquid storage member 10 manufactured as described above is completed by forming the inner layer 1, the intermediate layer 2, and the outer layer 3, removing the mandrel, cutting the cylindrical molded body to the specified length required for the liquid storage member 10, and drying it for several hours under appropriate temperature and humidity.

[0057] The resulting liquid containing member 10 has a smaller diameter than a typical paper tube, and its outer diameter is usually 20 mm or less, preferably 15 mm or less, and more preferably 10 mm or less, with the lower limit of the outer diameter usually being 1 mm or more, preferably 2 mm or more. Such a small-diameter liquid containing member requires strict dimensional accuracy. Therefore, the smaller the outer diameter of the liquid containing member 10, the more preferable it is that, when spirally winding the paper substrate laminate and the outer layer made of a paper substrate, the paper substrate laminate be brought into contact with adjacent surfaces so as not to overlap, and the outer layer made of a paper substrate be brought into contact with adjacent surfaces.

[0058] The tube thickness of the liquid containing member 10 is usually 0.07 to 0.6 mm, specifically 0.2 to 0.4 mm. By setting the tube thickness of the liquid containing member 10 within this range, a sufficient amount of liquid can be contained, the barrier properties are improved, and leakage and deterioration of the liquid can be easily suppressed.

[0059] The applicator of the present invention is not limited as long as it is equipped with the liquid containing member 10, and may be a padded or direct-fill type writing instrument, or a cosmetic tool such as eyeliner, mascara, or concealer, but is preferably a writing instrument.

[0060] In the case of a writing instrument, the pen tip may be any of brush bristles, soft pens, hard pens, etc. Specific examples of writing instruments include fountain pens, ballpoint pens, marking pens, felt-tip pens, correction tools, and brush pens. In this case, the ink contained in the liquid containing member 10 may be either water-based (gel) ink or oil-based ink, and depending on the type of pen, ink for ballpoint pens, pressurized ballpoint pens, marking pens, etc. is used. [Example]

[0061] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The liquid containing tubes used in the examples and comparative examples were manufactured as follows. [Manufacturing Example 1] 25 μm thick glassine paper (basis weight 25 g / m 2 , density 1.0g / cm 3 The laminated paper, which was made by laminating a 6.5 μm thick sheet of paper and a 6.5 μm thick aluminum foil with an adhesive containing polyolefin resin (Chemipearl S500, manufactured by Mitsui Chemicals, Inc.), had a total thickness of 38 μm and an adhesive layer thickness of 6.5 μm.The laminated paper was cut into 13 mm widths using a bobbin slitter. The adhesive containing the polyolefin resin was applied to the aluminum foil side, which was the outer layer of the strip-shaped adhesive paper, at a rate of 12 g / m using a roll-type applicator. 2 The paste was applied to the mandrel of a paper tube manufacturing machine (Langston), and the mandrel was spirally wound in a single layer with the glassine paper facing inward. Next, a 66 μm thick coated paper (basis weight 85 g / m) was cut into 13 mm widths using a bobbin slitter. 2 ) was spirally wrapped in a single layer on the aluminum foil, which was the outer layer of the laminate. At this time, the adhesive paper and the coated paper were wound so that their adjacent surfaces were butted against each other without overlapping, and the adhesive paper and the coated paper were wound so that the contact points between the adhesive paper and the coated paper were 3 mm apart in the longitudinal direction. The obtained spiral tube was cut to a length of 89.3 mm to obtain a paper liquid storage tube (paper tube 1) with an inner diameter of 3.8 mm.

[0062] [Manufacturing Example 2] A liquid storage tube (paper tube 2) was obtained in the same manner as in Production Example 1, except that in Production Example 1, the strip-shaped adhesive paper was spirally wound twice, instead of once, around the outer surface of the mandrel of the paper tube manufacturing machine (Langston).

[0063] [Manufacturing Example 3] In Production Example 2, instead of glassine paper, parchment paper having a thickness of 25 μm (basis weight 25 g / m) was used as the adhesive paper. 2 , density 1.0g / cm 3 A liquid storage tube (paper tube 3) was obtained in the same manner as in Production Example 2, except that a paper tube 3 was used in which the paper tube 3 was laminated with an aluminum foil having a thickness of 6.5 μm using an adhesive containing polyolefin resin.

[0064] [Manufacturing Example 4] In Production Example 2, a glassine paper having a thickness of 25 μm (basis weight 25 g / m) was used as the adhesive paper. 2 , density 1.0g / cm 3 A liquid storage tube (paper tube 4) was obtained in the same manner as in Production Example 2, except that a 0.4 μm thick silica vapor deposition layer was formed on the paper tube 1 instead of aluminum foil.

[0065] [Manufacturing Example 5] A liquid storage tube (paper tube 5) was obtained in the same manner as in Production Example 2, except that the adjacent surfaces of the coated paper were not butted together but were wound with an overlap of 1 mm.

[0066] [Manufacturing Example 6] A liquid storage tube (paper tube 6) was obtained in the same manner as in Production Example 2, except that the distance between the contact points of the laminated papers and the contact points of the coated papers was 5 mm instead of 3 mm.

[0067] The inks used in the examples and comparative examples were prepared according to the following formulations. <Coating solution 1> (total amount 100% by mass) Spiron Violet C-RH [Hodogaya Chemical Co., Ltd.] 8% Spiron Yellow C-GNH [Hodogaya Chemical Co., Ltd.] 5% Printex #35 [Degussa Japan Co., Ltd.] 8% Polyvinyl butyral BL-1 [Sekisui Chemical Co., Ltd.] 4% Polyvinyl butyral BH-3 [Sekisui Chemical Co., Ltd.] 0.7% Hi-Lac 110H [Hitachi Chemical Co., Ltd.] 10% SOLSPERSE 28000 [Lubrizol Japan Co., Ltd.] 1% (Acid value: 29, weight average molecular weight: approx. 3400) Benzotriazole 0.5% 3-Methoxy-3-methyl-1-butanol 62.8%

[0068] <Coating liquid 2> (total amount 100% by mass) FUJI RED 2510 [Fuji Pigment Co., Ltd.] 8% Joncryl 61J [BASF Japan Ltd.] 6% Xanthan gum KELSAN S [manufactured by Sansho Co., Ltd.] 0.32% Isopropyl phosphate 0.5% Bioden 421 [Nippon Soda Co., Ltd.] 0.2% Benzotriazole 0.3% Triethanolamine 1.4% Propylene glycol 15% Ion-exchanged water 68.28%

[0069] <Coating solution 3> (total amount 100% by mass) Vinyblan GV5651 [Nissin Chemical Industry Co., Ltd.] 80% (Polyvinyl acetate emulsion; solids content 40%) Acidic dye Red No. 227 0.22% Yellow No. 4 0.34% Blue No. 1 0.08% Purified water 19.36%

[0070] The ink follower used in each of the examples and comparative examples was prepared according to the following formulation: The total of the base oil and the viscoelasticity imparting agent was taken as 100% by mass. [Ink Follower 1] Ink follower 1 was prepared by mixing 94.5% polybutene 30N (polybutene; manufactured by NOF Corporation) as the base oil with 3.5% Tuftec H1053 (hydrogenated thermoplastic elastomer; manufactured by Asahi Kasei Corporation) and 2.0% aluminum stearate #30 (aluminum soap; manufactured by Kawamura Chemical Industries, Ltd.) as the viscoelasticity imparting agent, heating the mixture to a temperature at which the elastomer dissolves, and kneading using a planetary mixer and a roll mill.

[0071] [Ink Follower 2] Ink follower 2 was prepared by mixing 95.3% Diana Process Oil PW-90 (mineral oil; manufactured by Idemitsu Kosan Co., Ltd.) as the base oil and 4.7% DYNARON 6200P (hydrogenated styrene-butadiene elastomer; manufactured by JSR Corporation) as the viscoelasticity imparting agent, heating it to a temperature at which the elastomer melts, and kneading it in a planetary mixer.

[0072] [Ink Follower 3] As the base oil, 56.0% of Diana Process Oil PW-90 (mineral oil; manufactured by Idemitsu Kosan Co., Ltd.) and 40.0% of Barrel Process Oil P-1500 (poly-alphaolefin; manufactured by Matsumura Oil Co., Ltd.) were mixed with 4.0% of aluminum stearate #30 (aluminum soap; manufactured by Kawamura Chemical Industries Co., Ltd.) as a viscoelasticity imparting agent. The mixture was heated to a temperature at which the elastomer would dissolve, and then kneaded using a planetary mixer and a roll mill to prepare ink follower 3.

[0073] [Ink Follower 4] 96.0% of barrel process oil B-05 (synthetic aromatic hydrocarbon; manufactured by Matsumura Oil Co., Ltd.) was mixed as the base oil and 4.0% of DYNARON 6200P (hydrogenated styrene-butadiene elastomer; manufactured by JSR Corporation) was mixed as the viscoelasticity imparting agent. The mixture was heated to a temperature at which the elastomer dissolved, and then kneaded in a planetary mixer to prepare ink follower 4.

[0074] [Ink Follower 5] 93.0% of Diana Process Oil NR-26 (mineral oil; manufactured by Idemitsu Kosan Co., Ltd.) was used as the base oil, and 4.0% of Tuftec H1053 (hydrogenated thermoplastic elastomer; manufactured by Asahi Kasei Corporation) and 3.0% of aluminum stearate #30 (aluminum soap; manufactured by Kawamura Chemical Industries, Ltd.) were used as viscoelasticity imparting agents. The mixture was heated to a temperature at which the elastomer dissolved, and then kneaded using a kneader, planetary mixer, and roll mill to prepare ink follower 5.

[0075] [Ink Follower 6] Ink follower 6 was prepared by mixing 95.0% Diana Process Oil PW-90 (mineral oil; Idemitsu Kosan Co., Ltd.) as the base oil with 2.0% DYNARON 6200P (hydrogenated styrene-butadiene elastomer; JSR Corporation) and 3.0% Tuftec H1053 (hydrogenated thermoplastic elastomer; Asahi Kasei Corporation) as the viscoelasticity imparting agents. The mixture was heated to a temperature at which the elastomers dissolved, and then kneaded using a planetary mixer and a roll mill.

[0076] [Ink Follower 7] 98.0% barrel process oil P-1500 (poly-alphaolefin; manufactured by Matsumura Oil Co., Ltd.) was used as the base oil, and 2.0% aluminum stearate #30 (aluminum soap; manufactured by Kawamura Chemical Industries Co., Ltd.) was used as the viscoelasticity imparting agent. The mixture was heated to a temperature at which the elastomer would dissolve, and then kneaded using a planetary mixer to prepare ink follower 7.

[0077] [Ink Follower 8] 96.5% of KF-96 (silicone oil; manufactured by Shin-Etsu Chemical Co., Ltd.) as the base oil and 3.5% of AEROSILR974 (manufactured by EVONIK) as the viscoelasticity imparting agent were mixed, heated to a temperature at which the elastomer dissolved, and kneaded using a planetary mixer to prepare ink follower 8.

[0078] [Ink Follower 9] Ink follower 9 was prepared by mixing 98.0% barrel process oil P-1500 (poly-alphaolefin; manufactured by Matsumura Oil Co., Ltd.) as the base oil and 2.0% DYNARON 6200P (hydrogenated styrene-butadiene elastomer; manufactured by JSR Corporation) as the viscoelasticity imparting agent, heating the mixture to a temperature at which the elastomer melts, and kneading it in a planetary mixer.

[0079] Shear Strain The ink follower sample was placed on the measurement stage, and a load was applied to hold the sample in place. A vibrator (Anton Paar MCR-302) connected to the sample via an axis was then driven to apply dynamic stress to the sample. The ratio of the peak stress value to the peak strain value in the two waveforms (phases) converted from the dynamic stress and dynamic strain was taken as the shear strain, and the phase angle (°) at a shear strain amplitude of 5% (25°C) was calculated. Table 1 shows the phase angle (°) results for ink followers 1 to 9 at a shear strain amplitude of 5% (25° C.).

[0080] [Oil separation degree] An oil separation test was conducted in accordance with JIS K 2220-5.7-1993. Specifically, a metal wire mesh cone filter specified in the JIS standard was filled with ink follower, left in an environment of 60°C for 24 hours, and the amount of oil that separated out from the wire mesh cone filter was measured. Table 1 shows the oil separation results (60°C, 24 hours) of ink followers 1 to 9.

[0081] [Ink follower reversal or backflow] (i) Evaluation of reflux The liquid reservoir was filled with ink and ink follower, and a refill was made by combining a fitting and a pen tip with a ball diameter of 0.7 mm. The refill was left standing at 50°C for one week with the pen tip facing up. Backflow was judged by visually evaluating the degree of ink leakage from the rear end of the refill according to the following criteria. A: There is no ink leakage from the rear end of the refill, and no ink seepage is observed between the ink follower and the inner wall. B: There is no ink leakage from the rear end of the refill, but no ink seepage is observed between the ink follower and the inner wall. C: Ink is leaking from the rear end of the refill, and the rear end of the refill is stained with ink.

[0082] (ii) Evaluation of reversals The refill was left standing for two weeks with the pen tip facing upward and tilted at a 45° angle in a temperature cycle environment where temperatures were cycled from -10°C to 35°C every 12 hours, and then the presence or absence of reversal of the ink follower was evaluated by the quality of the drawn line drawn in a spiral on writing paper according to the following evaluation criteria. The drawn line was visually checked for rubbing and color unevenness and judged according to the following criteria. A: No rubbing or color unevenness was observed, and writing performance was good. B: Slight rubbing and color unevenness were observed, but there was no problem with writing. C: There was noticeable rubbing and uneven color of the drawn lines, resulting in poor writing.

[0083] [Example 1] 0.7 g of coating liquid 1 was filled into paper tube 1, and ink follower 1 was further filled to a length of about 10 mm to seal the rear end of the coating liquid. Next, a stainless steel fitting was attached to the side opposite the sealed portion of the paper tube 1, and a pen tip consisting of a tip with a ball diameter of 0.7 mm was attached to the tip of the fitting. The obtained liquid containing member 10 was left to stand for two weeks in a temperature cycle environment of -10°C to 35°C (continuous operation with a temperature rise time and a temperature fall time of 6 hours each, and a hold time of 6 hours) in an environment tilted at an angle of 45° with the pen tip facing upward. The backflow and reverse evaluations for ink follower 1 were both A. The results are shown in Table 1.

[0084] [Example 2] 0.7 g of coating liquid 1 was filled into paper tube 1, and ink follower 2 was further filled to a length of about 10 mm to seal the rear end of the coating liquid. Next, a stainless steel fitting was attached to the side opposite the sealed portion of the paper tube 1, and a pen tip consisting of a tip with a ball diameter of 0.7 mm was attached to the tip of the fitting. The obtained liquid containing member 10 was left to stand for two weeks in a temperature cycle environment of -10°C to 35°C (continuous operation with a temperature rise time and a temperature fall time of 6 hours each, and a hold time of 6 hours) in an environment tilted at an angle of 45° with the pen tip facing upward. The backflow and reversal evaluations for ink follower 2 were both A. The results are shown in Table 1.

[0085] [Example 3] 0.7 g of the coating liquid 1 was filled into the paper tube 2, and further, an ink follower 3 was filled to a length of about 10 mm to seal the rear end of the coating liquid. Next, a stainless steel fitting was attached to the side opposite the sealed portion of the paper tube 2, and a pen tip consisting of a tip with a ball diameter of 0.7 mm was attached to the tip of the fitting. The obtained liquid containing member 10 was left to stand for two weeks in a temperature cycle environment of -10°C to 35°C (continuous operation with a temperature rise time and a temperature fall time of 6 hours each, and a hold time of 6 hours) in an environment tilted at an angle of 45° with the pen tip facing upward. The backflow and reversal evaluations for ink follower 3 were both A. The results are shown in Table 1.

[0086] [Example 4] The paper tube 3 was filled with 0.7 g of the coating liquid 2, and further filled with an ink follower 4 to a length of about 10 mm to seal the rear end of the coating liquid. Next, a stainless steel fitting was attached to the side opposite the sealed portion of the paper tube 3, and a pen tip consisting of a tip with a ball diameter of 0.7 mm was attached to the tip of the fitting. The obtained liquid containing member 10 was left to stand for two weeks in a temperature cycle environment of -10°C to 35°C (continuous operation with a temperature rise time and a temperature fall time of 6 hours each, and a hold time of 6 hours), tilted at an angle of 45° with the pen tip facing upward. The backflow and reversal evaluations for ink follower 4 were both A. The results are shown in Table 1.

[0087] [Example 5] The paper tube 4 was filled with 0.7 g of the coating liquid 2, and further filled with an ink follower 5 to a length of about 10 mm to seal the rear end of the coating liquid. Next, a stainless steel fitting was attached to the side opposite the sealed portion of the paper tube 4, and a pen tip consisting of a tip with a ball diameter of 0.7 mm was attached to the tip of the fitting. The obtained liquid containing member 10 was left to stand for two weeks in a temperature cycle environment of -10°C to 35°C (continuous operation with a temperature rise time and a temperature fall time of 6 hours each, and a hold time of 6 hours) in an environment tilted at an angle of 45° with the pen tip facing upward. The backflow and reversal evaluations for ink follower 5 were both A. The results are shown in Table 1.

[0088] [Example 6] The paper tube 6 was filled with 0.7 g of the coating liquid 3, and further filled with an ink follower 6 to a length of about 10 mm to seal the rear end of the coating liquid. Next, a stainless steel joint was attached to the opposite side of the sealed portion of the paper tube 6, and a pen tip consisting of a tip with a ball diameter of 0.7 mm was attached to the tip of the joint. The obtained liquid containing member 10 was left to stand for two weeks in a temperature cycle environment of -10°C to 35°C (continuous operation with a temperature rise time and a temperature fall time of 6 hours each, and a hold time of 6 hours), tilted at an angle of 45° with the pen tip facing upward. The backflow and reversal evaluations for ink follower 6 were both A. The results are shown in Table 1.

[0089] [Comparative Example 1] An ink containing member was produced in the same manner as in Example 1, except that the ink follower 1 in Example 1 was replaced with an ink follower 7. The ink follower leaked from the rear end of the refill, and color unevenness was observed in the writing test, so the rating was C. The results are shown in Table 1.

[0090] Comparative Example 2 An ink containing member was produced in the same manner as in Example 1, except that the ink follower 8 was used instead of the ink follower 1 in Example 1. The inverted evaluation of the ink follower 8 was A after it was placed face up, but after it was placed sideways, the ink follower 5 scattered from the pen tip into the ink, and leakage was observed between the inner wall of the ink reservoir tube and the ink follower, so it was rated C. The results are shown in Table 1.

[0091] Comparative Example 3 The paper tube 5 was filled with 0.7 g of the coating liquid 3, and further filled with an ink follower 9 to a length of about 10 mm to seal the rear end of the coating liquid. Next, a stainless steel joint was attached to the opposite side of the sealed portion of the paper tube 5, and a pen tip with a ball diameter of 0.7 mm was attached to the tip of the joint to prepare an ink containing member. The ink follower leaked from the rear end of the refill, resulting in a C in the backflow test, and slight rubbing and color unevenness were also observed in the writing test, resulting in a B. The results are shown in Table 1.

[0092] [Table 1]

[0093] In Table 1, *1 to *11 indicate the manufacturer. *1 NOF Corporation *2 Idemitsu Kosan Co., Ltd. *3 Idemitsu Kosan Co., Ltd. *4 Idemitsu Kosan Co., Ltd. *5 Matsumura Oil Co., Ltd. *6 Matsumura Oil Co., Ltd. *7 Shin-Etsu Chemical Co., Ltd. *8 JSR Corporation *9 Asahi Kasei Corporation *10 Kawamura Chemical Industries Co., Ltd. *11 EVONIK [Explanation of symbols]

[0094] 10 Liquid storage member for applicator 11 Joints 12 Ballpoint pen tips 1 Inner layer 2. Middle class 3 outer layer 4, 4' seam 5 Adhesive layer

Claims

1. a liquid containing tube using a paper substrate; The ink follower filled in the liquid reservoir tube has a phase angle of 50° or less at a shear strain amplitude of 0 to 30% at 25°C and 1 Hz, and an oil separation rate of 5% or less when left at 60°C for 24 hours. A liquid containing member for an applicator, comprising:

2. 2. The liquid containing member for an applicator according to claim 1, wherein the liquid filled in the liquid containing tube has a phase angle of 45° or less at 25° C. and 1 Hz with a shear strain amplitude of 0 to 30%.

3. 2. The liquid storage member for an applicator according to claim 1, wherein the ink follower contains at least one base oil selected from the group consisting of liquid paraffin, poly-alpha olefin, synthetic aromatic hydrocarbon, mineral oil, polybutene, and silicone oil.

4. The liquid containing member for an applicator according to claim 1 or 2, which is used in a paper refill for a writing implement.

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