JP4611715B2 - Applicator - Google Patents

Description

  The present invention relates to an applicator such as a correction pen containing oil-based ink, and also relates to an ink storage tube constituting the applicator.

  Conventionally, oil-based inks such as correction fluids do not adhere to the ink storage tube with use, exhibit self-cleaning properties, and all filled amounts can be used, and transparent or translucent containers have been used. Sometimes, a correction tool that can check the remaining amount is provided (for example, Patent Document 1).

  This Patent Document 1 has a coating part for applying a correction liquid as a content liquid at the tip, and a concealing agent and a hydrocarbon having a boiling point of 40 to 150 ° C. are provided on the side of the coating part in a tank for storing the correction liquid. A correction fluid comprising at least a system solvent and a film-forming agent soluble in the solvent, in contact with the rear interface of the correction fluid, and an organic solvent insoluble or hardly soluble in the hydrocarbon solvent of the correction fluid; It is disclosed that it is a correction tool that contains and arranges a backflow preventer comprising at least water, a viscosity modifier, and a surfactant, and contains a fluorosurfactant as the surfactant.

JP 2002-103884 A

  However, this correction tool is actually weak in the self-cleaning property, and the backflow prevention body (ink follower) tends to enter the correction liquid into the ink over time.

  Moreover, as patent document 2, it has a coating part which apply | coats the correction liquid which is a content liquid at the front-end | tip, and has a concealant and a boiling point 40-150 degreeC hydrocarbon in the said coating part side in the tank which accommodates the said correction liquid. A correction fluid comprising at least a system solvent and a film-forming agent soluble in the solvent, in contact with the rear interface of the correction fluid, and insoluble or poorly soluble in the viscosity modifier and the hydrocarbon solvent of the correction fluid. A backflow preventer composed of at least organic solvent and / or water is disposed, and at least an insoluble or hardly soluble organic solvent and / or water is applied to the inner wall of the correction liquid storage tank. A correction tool is provided which is characterized by being.

JP 2002-127680 A

  However, such a correction tool is also only an organic solvent and / or water which is insoluble or hardly soluble in the hydrocarbon solvent of the correction liquid on the inner wall of the storage tank. And / or water is lost and the self-cleaning property is lost.

  An object of the present invention is to provide an applicator such as a correction tool in which a backflow preventer is unlikely to enter the ink, and the sustainability of the self-cleaning effect is good.

  Nylon and polyethylene terephthalate resins are suitable as resins for containment pipes for correction inks. These resins have good wettability with oil-based inks such as correction inks, and are self-supporting by a backflow preventer (ink follower or ink follower). Since it was difficult to produce a cleaning effect, we considered that it was necessary to make the wetness of the oil-based ink and the ink containing tube worse, and improve the backflow prevention and the wetness of the pipe. By adding a polyvinyl alcohol resin as a polar resin that is poorly wetted with polar ink, and additionally adding a fluorosurfactant for the purpose of worsening the wettability, at the interface contacting at least the oil-based ink The present inventors have found that the above problems can be solved.

The present invention is an applicator in which at least oil-based ink is contained in an ink containing tube,
The ink containing tube has an interface at least in contact with the oil-based ink;
The interface includes at least polyvinyl alcohol and an ionic fluorosurfactant, and the polyvinyl alcohol includes a modified polyvinyl alcohol that is ionic opposite to the ionic fluorosurfactant. It is an applicator.

As a preferred embodiment of the present invention, the interface is composed of a coating layer formed on the inner wall surface of the ink containing tube, and the coating layer contains at least polyvinyl alcohol.

  In the present invention, it is preferable that polyvinyl alcohol and a fluorosurfactant are contained in the interface. Particularly, an applicator containing polyvinyl alcohol and a fluorosurfactant at the interface, the ionic fluorosurfactant as the fluorosurfactant, and the surfactant as the polyvinyl alcohol. An applicator containing a modified polyvinyl alcohol whose ionicity is reversed is preferable.

  As a result, it is possible to provide an applicator such as a correction tool in which the backflow preventer is unlikely to enter the ink and the self-cleaning effect has good durability. In particular, the interface contains polyvinyl alcohol and a fluorosurfactant, and the fluorosurfactant is an ionic fluorosurfactant, and the polyvinyl alcohol is ionic with respect to the ionicity of the surfactant. When ionic modified polyvinyl alcohol that is reversed is included, an ionic interaction can be provided between the polyvinyl alcohol and the surfactant, under a temperature environment exceeding normal temperature (20 ° C.), Specifically, even in a high temperature environment of 40 ° C. or higher, the self-cleaning effect can be maintained sufficiently, and the storage stability is excellent.

The ink storage tube used in the present invention is not affected by the aliphatic and alicyclic hydrocarbon solvents contained in the oil-based ink (does not absorb liquid), and may not be affected by the backflow prevention base material (polar substance). is important.
The ink containing tube that satisfies these requirements is preferably made of a resin selected from the group consisting of nylon resin, polyethylene terephthalate resin, and polybutylene terephthalate resin. Specifically, 4,6-nylon, 6-nylon, 6,6-nylon, 6,10-nylon, 6,12-nylon, 11-nylon, 12-nylon, PET (polyethylene terephthalate), PBT (poly) Butylene terephthalate). Nylon resin and PET (polyethylene terephthalate) are preferable in that the remaining amount can be confirmed from the outside, but in the applicator of the present invention containing polyvinyl alcohol and a fluorosurfactant at the interface of the ink containing tube at least in contact with the oil-based ink. By configuring the ink storage tube with nylon resin, PET (polyethylene terephthalate) or PBT (polybutylene terephthalate), it is possible to prevent ink streaks (passages) from forming in the ink storage tube over time. It is possible to prevent ink from leaking out from the streaks (paths) or losing the storage stability of the ink due to solvent flying.

  As PVA (polyvinyl alcohol) used in the present invention, those containing a lot of —OH groups (hydroxyl groups) and having a considerably high polarity (water-soluble) are desirable. In this sense, PVA is preferably a saponified or nearly saponified PVA, but partially saponified PVA can also be used. A more preferable PVA is a completely saponified type or a PVA close to a completely saponified type. For example, a saponification degree of 98.0 or more is preferable. Specifically, a completely saponified product is preferable, and PVA-102, PVA-103, PVA-104A, PVA-105, PVA-110, PVA-117, PVA- of the trade name “Kuraray Poval” series manufactured by Kuraray Co., Ltd. 117H, PVA-120, PVA-124, PVA-135, and PVA-HC can be used. Among these, a trade name “Kuraray Poval PVA105” (degree of saponification 98 to 99 mol%, degree of polymerization 500) manufactured by Kuraray Co., Ltd. is preferable. In addition, NH-26, NH-20, NH-18, N-300, NM-14, NM-11, and NL-05 of Nippon Gohsei's product name "GOHSENOL N-type POVAL" series are preferred. . Moreover, VC-20, V, VC-10 which is a brand name "V series" manufactured by Nippon Vinegar Poval, and JC-25, JF-20, JF-17, JF-17L which are "J series", JF-10, JF-05, and JF-04 can be used.

  PVA is 0.05 wt% to 20 wt%, preferably 0.5 wt% to 10 wt% with respect to the total amount of the coating liquid, based on the coating layer constituting the interface that contacts the oil-based ink. When PVA is less than 0.05 wt% with respect to the total amount of the coating liquid, the self-cleaning property is lowered with respect to the oil-based ink. On the other hand, when PVA exceeds 20 wt% with respect to the total amount of the coating liquid, the viscosity becomes too high and coating is difficult.

  In the present invention, in addition to unmodified PVA (unmodified polyvinyl alcohol), the self-cleaning effect can be more sufficiently maintained even in a temperature environment exceeding room temperature, specifically in a high temperature environment of 40 ° C. or higher. However, in order to ensure storage stability, modified PVA (polyvinyl alcohol) having cationic or anionic properties can be used. That is, PVA (polyvinyl alcohol) containing a lot of —OH groups (hydroxyl groups) and having high polarity (water-soluble) is preferable, and cation-modified or anion-modified PVA (polyvinyl alcohol) close to or completely saponified. For example, a saponification degree of 86.0 or more is preferable. More preferable examples of PVA include the product name “Kuraray Poval KL-118” (anion-modified polyvinyl alcohol, saponification degree 95 to 99 mol%) manufactured by Kuraray Co., Ltd., and the product name “Kuraray Poval CM-318” manufactured by the same company. ”(Cation-modified polyvinyl alcohol, quaternary ammonium-modified PVA, saponification degree: 86 to 91 mol%), manufactured by Nippon Synthetic Chemical Co., Ltd., trade name“ GOHSEFIMAR K210 ”(cation-modified polyvinyl alcohol) and the like. It is done.

  These ion-modified PVAs are 0.05 wt% to 10 wt% (20 wt% or less in combination with unmodified PVA), preferably based on the total amount of the coating liquid, based on the coating layer constituting the interface that contacts the oil-based ink. Is 0.1 wt% to 5 wt%. When PVA is less than 0.05 wt% with respect to the total amount of the coating liquid, the self-cleaning property is lowered with respect to the oil-based ink. On the other hand, when PVA exceeds 20 wt% with respect to the total amount of the coating liquid, the viscosity becomes too high and coating is difficult.

  The fluorosurfactant used in the present invention has solubility in water, but does not dissolve in ink solvents (aliphatic / alicyclic hydrocarbon organic solvents), and has the effect of significantly reducing surface tension. It is important to be. Ionic fluorinated surfactants are preferred. Specific examples include S-111, 112, 113, 121, 131, 132, 141, and 145 of the trade name Surflon series manufactured by Seimi Chemical Co., Ltd. Also, the Neos brand name “Factent” series 100, 150, 300, 400S and Mitsubishi Materials Corporation brand name “F Top” series EF-101, 102, 104, 105, 112 may be mentioned. it can.

  The fluorosurfactant is 0.005 wt% to 1 wt%, preferably 0.03 wt% to 0.5 wt%, based on the total amount of the coating liquid, based on the coating layer constituting the interface that contacts the oil-based ink. include. If the fluorosurfactant is less than 0.005 wt% with respect to the total amount of the coating liquid, it is difficult to lower the surface tension, whereas if it exceeds 1 wt%, the fluorosurfactant is exposed from the interface of the coating layer. Easily dissolves in oil-based inks.

  As the coating liquid for forming the coating layer, it is important that at least polyvinyl alcohol is contained in PVA and the fluorosurfactant, but it is preferable to use it as a coating aqueous solution containing water. Therefore, the coating aqueous solution containing 0.05 wt% to 20 wt% of the PVA with respect to the total amount of the coating solution, and 0.005 wt% to 1 wt% with respect to the total amount of the coating solution when further adding the fluorosurfactant; It is preferable to do. An antifoaming agent, a surface tension adjusting agent, a preservative, etc. may be added to the coating solution.

  The applicator of the present invention is obtained, for example, by the following manufacturing method. That is, the molded accommodation tube is dipped in an aqueous solution of PVA and a fluorosurfactant to form a coating layer of an aqueous solution of PVA and a fluorosurfactant on the inner wall surface of the accommodation tube. Next, it is dried in an oven or at room temperature for 1 day. Next, the accommodation tube is filled with oil-based ink, and further, a backflow preventer (backflow stopper) is filled. Thereby, the applicator of one embodiment of the present invention is obtained.

  In addition, in the applicator of the present invention, in order to form the interface of the inner surface of the storage tube, in addition to forming the coating layer by the above dipping, the coating layer is formed by coating directly in the storage tube, and extrusion molding or injection molding An inner layer having an interface containing at least polyvinyl alcohol among PVA and a fluorosurfactant can be formed on the inner surface of the containing tube simultaneously with the forming of the ink containing tube by a known molding method. Further, after the ink containing tube is molded, an inner layer having an interface containing at least polyvinyl alcohol among PVA and a fluorosurfactant can be molded inside as a molded body. Alternatively, PVA and fluorine can be molded. Among the system surfactants, an inner layer having an interface containing at least polyvinyl alcohol can be molded as a molded body, and then the main body of the ink containing tube can be molded as a molded body on the outside thereof.

  Alternatively, at least polyvinyl alcohol is contained in PVA and a fluorosurfactant in the resin of the ink containing tube selected from the group of nylon resin, polyethylene terephthalate resin and polybutylene terephthalate resin to prevent oil-based ink and backflow It is also possible to configure the interface in contact with the body as an interface containing at least polyvinyl alcohol among PVA and a fluorosurfactant.

A specific embodiment of the present invention is an applicator in which an oil-based ink and a backflow prevention body in contact with the ink are accommodated in an ink storage tube, wherein the ink storage tube is in contact with the oil-based ink and the backflow prevention body. has, on the surface, applicator that contains the polyvinyl alcohol even without low. Moreover, the applicator in which polyvinyl alcohol and a fluorochemical surfactant are contained in the said interface is mentioned.

  The ink containing tube is not particularly limited, but is preferably made of a resin selected from the group of nylon resin, polyethylene terephthalate resin, and polybutylene terephthalate resin. These are preferred in that they are not attacked by aliphatic or alicyclic hydrocarbon solvents and do not absorb liquids, and are preferred in that they are not attacked by a polar substance backflow prevention substrate (backflow prevention body). Specifically, 4,6-nylon, 6-nylon, 6,6-nylon, 6,10-nylon, 6,12-nylon, 11-nylon, 12-nylon, PET (polyethylene terephthalate), PBT (poly) Butylene terephthalate) is preferred. Nylon in general and PET are suitable in that the remaining amount can be confirmed from the outside.

  The oil-based ink is preferably an applicator containing a colorant, a resin, an organic solvent, and a gelling agent.

  In the case of a correction tool such as a correction pen, it is desirable that the oil-based ink contains titanium oxide as a colorant (masking material), and the oil-based ink includes an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon. It is preferable to include at least one of organic solvents.

  Furthermore, the gelling agent is a soluble gelling agent having a solubility in the organic solvent (20 ° C.) of 0.1 to 20% by weight, and the viscosity of the ink has a shear rate of 0.1 (1 / s ) Is 700 mPa · s or more, and when the shear rate is 100 (1 / s), it is preferably 500 mPa · s or less, and it is desirable to include metal soap as a specific gelling agent. In particular, it is desirable to contain aluminum 2-ethylhexanoate.

  The viscosity was measured under the condition that a shearing force was applied to the ink by rotation of the ball using a correction pen having a pen tip with a tip having a diameter of 1.0 mm held with a gap of 60 μm. The viscosity is shown on the basis of mPa · s. The viscosity of the oil-based ink shown in the present invention is a value measured with a Z20 DIN rotor at 20 ° C. using a rheometer RS-75 manufactured by HAAKE.

  Furthermore, as the backflow preventer, an aqueous backflow preventer (such as an aqueous backflow preventive composition) can be used. Specifically, a known follower or a backflow prevention composition such as a base material based on at least one of diglycerin ethylene oxide adduct and diglycerin propylene oxide adduct is used. And a polyglyceric acid having a molecular weight of 1,000,000 or more is preferably contained in an amount of 0.1 to 3% by weight based on the total amount of the backflow preventer. . In addition, fine particle silica can also be used. As the diglycerin ethylene oxide adduct, trade names, SC-E2000, SC-E1500, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. can be used. As the diglycerin propylene oxide adduct, trade names, SC-P1000, SC-P750, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. can be used. Moreover, fine particle silica can also be used, for example, a product name, R972, R976, R812, 200, 380 made by Nippon Aerosil Co., Ltd. can be used.

  The applicator is equipped with an ink storage tube in the outer cylinder and a refill structure applicator with a pen tip on one end of the ink storage tube, and a pen tip on one end of the ink storage tube. And the applicator which has a pressurization apparatus which pressurizes at least oil-based ink accommodated in the said ink accommodating tube at the other end side can also be used.

  A transparent ink containing tube having a diameter (inner diameter) of 4 mm molded with 11-nylon resin was dipped in each coating aqueous solution shown in Table 1. The coating aqueous solution is composed of the treatment liquid composition shown in Table 1. For example, in the applicator of Example 1, 5 wt% of PVA with respect to the total amount of the coating liquid and 0.15 wt% of the fluorosurfactant in solid content are included. It is prepared as follows. Next, each of the ink storage tubes was taken out from each of the aqueous solutions and air-dried at room temperature for 1 day to form a coating layer containing PVA and a fluorosurfactant on the inner wall surface of each of the ink storage tubes. In the same manner in other examples and comparative examples, the coating layer was formed on the inner wall surface of each ink containing tube.

  Next, a pen tip having a ball diameter of 1 mm is assembled to one end of the ink containing tube, and then 50% by weight of titanium oxide, 4% by weight of rosin resin, and 40% by weight of aliphatic hydrocarbon solvent with respect to the total amount of oil-based ink. And an oil-based ink containing 1.5% by weight of a gelling agent (aluminum 2-ethylhexanoate) in the ink containing tube, and then, from above the oil-based ink, a diglycerin ethylene oxide adduct ( Sakamoto Pharmaceutical Co., Ltd., trade name “SC-E2000”) containing 98.5% by weight based on the total amount of the backflow preventer and having a molecular weight of 1,000,000 or more (manufactured by BF Goodrich Co., Ltd., product) The name “Carbopol 940”) was filled with a backflow prevention body containing 0.1 to 3 wt% with respect to the total amount of the backflow prevention body.

  When this ink-containing tube containing the oil-based ink and the backflow preventer is applied to the paper surface, oil-based ink such as a correction liquid does not adhere to the ink storing tube with use, and self-cleaning performance is maintained. In addition, since it is a transparent ink storage tube, the remaining amount can be confirmed clearly. In addition, in the case of an applicator using an ink containing tube treated with an aqueous coating solution containing an ionic fluorosurfactant and a modified polyvinyl alcohol whose ionicity is opposite to that of the surfactant, the applicator is used in a high temperature environment of 50 ° C. In this case, the self-cleaning property is continuously exhibited. In Table 1, in the evaluation of self-cleaning, “initial” indicates the time when the ink was first applied to the paper surface when the ballpoint pen was assembled, and “stored for 3 days” indicates that the paper surface was three days after the ballpoint pen was assembled. The self-cleaning state when applied is shown.

The applicator of the present invention can be used for a correction tool such as a correction pen and other applicators.

Claims (9)

An applicator having at least oil-based ink stored in an ink storage tube,
The ink containing tube has an interface at least in contact with the oil-based ink;
The interface includes at least polyvinyl alcohol and an ionic fluorosurfactant,
The applicator characterized in that the polyvinyl alcohol contains a modified polyvinyl alcohol whose ionicity is opposite to that of the ionic fluorosurfactant . An applicator in which an oil-based ink and a backflow prevention body in contact with the ink are stored in an ink storage tube,
The ink containing tube has an interface in contact with the oil-based ink and the backflow preventer,
The interface includes at least polyvinyl alcohol and an ionic fluorosurfactant,
The applicator characterized in that the polyvinyl alcohol contains a modified polyvinyl alcohol whose ionicity is opposite to that of the ionic fluorosurfactant . The applicator according to claim 1 or 2, wherein the polyvinyl alcohol has a saponification degree of 86.0 or more. The polyvinyl alcohol is coated tool according to claim 1, comprising one or more ionic polyvinyl alcohol selected from mosquitoes thione and anionic groups. The fluorine-based surfactant, according to claim 1 comprising one or more ionic fluorinated surfactant selected from mosquitoes thione and anionic groups Applicator. The polyvinyl alcohol is a cationic modified polyvinyl alcohol, and the fluorosurfactant is an anionic fluorosurfactant,
Or the said polyvinyl alcohol is anionic modified polyvinyl alcohol, and the said fluorine-type surfactant is a cationic fluorine-type surfactant, The applicator of any one of Claims 1-5 . The applicator according to any one of claims 1 to 6, wherein the ink containing tube is made of a resin selected from the group consisting of a nylon resin, a polyethylene terephthalate resin, and a polybutylene terephthalate resin. An applicator in which an oil-based ink and an aqueous backflow preventive body in contact with the ink are stored in an ink storage tube,
The ink containing tube is made of a resin selected from the group of nylon resin, polyethylene terephthalate resin and polybutylene terephthalate resin,
The ink containing tube has an interface in contact with the oil-based ink and the backflow preventer,
The interface includes polyvinyl alcohol and a fluorosurfactant,
An ionic fluorosurfactant as the fluorosurfactant, and a modified polyvinyl alcohol whose ionicity is opposite to that of the surfactant as the polyvinyl alcohol,
The oil-based ink contains a colorant, a resin, an organic solvent and a gelling agent,
As the organic solvent, an aliphatic hydrocarbon solvent, an organic solvent of at least one of alicyclic hydrocarbon solvents is included,
An applicator comprising metal soap as the gelling agent. Having at least an interface in contact with the oil-based ink;
The interface includes at least polyvinyl alcohol and an ionic fluorosurfactant,
The ink containing tube , wherein the polyvinyl alcohol contains a modified polyvinyl alcohol having an ionicity opposite to that of the ionic fluorosurfactant .