JP2003034098A - Fluid applicator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluid applicator, which is used for writing utensils including a felt-tip pen, a ball point pen excellent in secular stability under highly damp state, a corrector, an adhesive applicator, a toilet set or the like. SOLUTION: In the fluid applicator, in which a fluid applicating liquid including at least one kind or more of organic solvents selected from the group consisting of n-hexane, n-heptane, n-octane, isooctane, cyclohexane, methylcyclohexne, ethylcyclohexane, toluene and xylene is housed in the housing tube of the applicator equipped with the efflux controlling mechanism of the fluid applicating liquid and, at the same time, behind the fluid applicating liquid, a hard-volatile liquid matter incompatible with the fluid applicating liquid is housed under contact state as a terminal movable plug under the state that the space within the housing tube behind the movable plug is open to the air, the movable plug is mainly made of the propylene oxide adduct of diglycerol represented by general formula (I). In formula (I), m+n+o+p =s} is an integer of 2 to 6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluid applicator, and more particularly to a fluid applicator used for a writing instrument including a felt-tip pen and a ballpoint pen, a correction tool, an adhesive applicator, a cosmetic tool and the like.

[0002]

2. Description of the Related Art Conventionally, in order to prevent scattering and volatilization of a fluid, an applicator such as a ballpoint pen having a liquid movable stopper at the end of the fluid in a pipe-shaped container containing the fluid as it is. Is widely known.

However, as the liquid movable plug of the above-mentioned conventional fluid applicator, a non-volatile oil such as mineral oil, silicone oil, ester oil, polybutene, etc. is used as a main component. Ink containing a highly polar volatile liquid has a volatilization-preventing effect, but fluids containing a low-polarity volatile liquid such as xylene, cyclohexane, and methylcyclohexane are compatible with the movable plug. There is a problem of volatilization after passing through the movable plug, which is not practical. In addition, a low-polarity and volatile organic solvent has a fast drawing line and easy drying due to the ink formulation, and has a strong adhesiveness on the non-absorption surface,
When used as a correction liquid, it is preferable in that bleeding of aqueous ink hardly occurs.

Further, in the above conventional fluid applicator,
Solid movable stoppers using silicone rubber, etc. are also known, but as mentioned above, fluids containing a low-polarity volatile liquid do not have sufficient volatilization prevention effect, and the rubber swells so that it cannot move. There was a problem of disappearing.

Therefore, the inventors of the present invention have developed a fluid applicator which solves the above problems. That is, n-hexane, n-heptane, n-octane,
A fluid coating solution containing at least one organic solvent selected from isooctane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene and xylene is contained, and the fluid coating solution is provided behind the fluid coating solution. A non-volatile liquid substance that is incompatible with the above is housed in a contact state as a terminal movable plug, and the inside of the rear housing pipe of the movable plug is released to the atmosphere, and the movable plug is glycerin, polyglycerin, polyethylene glycol, polypropylene glycol, glycerin. A fatty acid ester, polyglycerin fatty acid ester, or a mixture of two or more kinds of alkylene oxide adducts of polyglycerin, and a gel in which structural viscosity is imparted to them in order to improve the performance as a movable stopper. Movable stopper, structural viscosity imparting agent Then, a method of adding fine powder of silica, organic bentonite, 12-hydroxystearic acid and its derivative, alumina, dibenzylidene sorbitol and the like to gel, and impregnating these liquids into an open-cell foam such as polyurethane foam. It has been filed for use in the closed state. (JP 2000-343A
875). It should be noted that the liquid movable stopper defined in the above publication has two features: "It is incompatible with the fluid coating liquid and prevents volatilization of the fluid coating liquid" and "It is difficult for the movable stopper itself to volatilize". Two performances are required.

[0006] However, these substances are certainly incompatible with the fluid coating liquid and prevent volatilization of the fluid. "
And "hard to volatilize" are satisfied, but in fluid applicators whose rear end is open to the atmosphere, these substances are not compatible with solvents but have hygroscopicity. It has been found that when placed in high humidity, moisture absorption causes problems such as volume expansion and viscosity decrease, and further formation of water droplets and water layers.

Therefore, the inventors of the present invention provided a gel movable plug B composed of water and a structural viscosity imparting agent, and further provided a nonvolatile oil such as mineral oil, silicone oil, ester oil and polybutene at the rear end thereof and a structural viscosity imparting agent. Gel-like movable stopper C
An application has been filed for a fluid applicator including a double (two-layer type) movable stopper composed of (1) (Japanese Patent Laid-Open No. 2000-343879). The effect of this two-layer movable plug is excellent, but it is difficult to assemble such as management of difference in specific gravity of three layers including fluid, removal of trapped air, and filling method.
There are some issues in that they cause secondary issues.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is intended to solve the problems, such as xylene, cyclohexane, and methylcyclohexane, which cannot be achieved by the prior art. In a coating tool in which a fluid coating liquid containing a low-polarity, highly volatile solvent is directly stored in a storage tube whose rear end is open to the atmosphere, one of the problems of the conventional movable stopper is It is an object of the present invention to provide a fluid applicator provided with a movable stopper having excellent stability over time.

[0009]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems of the prior art, the inventors of the present invention have a coating solution outflow control mechanism at the front end and a rear end portion which is open to the atmosphere. As a result of various studies on the combination of the fluid coating liquid and the liquid movable stopper to be housed in the storage tube of the, it has high polarity and low volatility that is not easily affected by humidity for a long period of time and is incompatible with the fluid coating liquid. As a liquid movable stopper, a main component of diglycerin is 2 to 6 mol of propion oxide, particularly,
The inventors have found that the 4-mol addition product is the most preferable, and completed the present invention. That is, the present invention is as follows.
It exists in (1)-(4). (1) n-hexane, n-heptane, n-octane, in a container of an applicator having a fluid coating liquid outflow control mechanism,
A fluid coating solution containing at least one organic solvent selected from isooctane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene and xylene is contained, and the fluid coating solution is provided behind the fluid coating solution. A fluid applicator in which a non-volatile liquid material that is incompatible with the above is housed in a contact state as a terminal movable stopper and the inside of the rear accommodation pipe of the movable stopper is released to the atmosphere, and the movable stopper has the following general formula ( A fluid applicator comprising a propylene oxide adduct of diglycerin represented by I) as a main component.

[Chemical 2] (2) A fluid applicator characterized in that the movable stopper according to (1) above is an adduct of propylene oxide (4 mol) with diglycerin (s = 4). (3) A fluid applicator, wherein the movable plug according to (1) or (2) above has a structural viscosity due to a mixture of silica and alumina. (4) A fluid applicator characterized in that the movable plug having the structural viscosity described in (3) above contains 5 to 10% by weight of a mixture of silica and alumina with respect to the total amount of the movable plug.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. In the fluid applicator of the present invention, n-hexane, n-heptane, n-octane, isooctane, cyclohexane, methylcyclohexane, ethylcyclohexane, and toluene are provided in a container of the applicator having a fluid application liquid outflow control mechanism. And a fluid coating liquid containing at least one or more organic solvent selected from xylene, and behind the fluid coating liquid, a non-volatile liquid material that is incompatible with the fluid coating liquid. Is a fluid movable tool which is accommodated as a terminal movable stopper in a contact state and is open to the atmosphere in the rear accommodation pipe of the movable stopper, wherein the movable stopper is a diglycerin propylene oxide addition represented by the following general formula (I). It is characterized by having an object as a main component.

[Chemical 3]

The fluid applicator to which the present invention is applicable includes, for example, writing tools including felt-tip pens, ballpoint pens, correction tools, adhesive applicators, cosmetic tools and the like. The tip of these fluid applicators is usually equipped with an outflow control mechanism for the fluid application liquid that prevents the fluid from coming out or becoming difficult to come out during use. For example, when the fluid (ink, etc.) is in the form of gel, a ball-point pen type tip having a structure viscous destruction means, or a valve that urges the resilient valve body to project forward toward the valve seat to block and hold the tip hole The thing provided with the outflow control mechanism, such as an application body or a needle valve, is mentioned. FIG. 1 is a vertical cross-sectional view showing an example in which the fluid applicator of the present invention is applied to a ballpoint pen. In this fluid applicator, as shown in FIG. 1, a container 7 having a ball-point pen type tip 3 as an outflow suppressing mechanism is filled with a fluid application liquid 8, and the end portion of the fluid application liquid 8 is filled. The movable stopper 9 is accommodated in the state of being in contact with. In addition, 1 is a cap body, 2 is a seal rubber, 4 is a ball, 5 is a joint member of a pen tip portion and a housing pipe, 6 is a shaft body, and 10 is a tail plug. The structure of the ball-point pen type chip 3 is not limited to the usual ball-point pen chip structure, but is composed of, for example, a chip having a metal (stainless steel or ceramic) ball and a metal (stainless steel or ceramic) holder at its tip, which is not shown. A structure may be adopted in which the back surface of the ball is pressed by a pressing means composed of a spring member so that the ball comes into close contact with the inner edge of the ball holding portion at the tip of the chip. With this built-in pressing means, the ball sinks during writing, etc., and a clearance part is created between the ball and the ball holding part, at which time the fluid coating liquid in the storage pipe passes through the clearance part. It can be applied to the outside by an appropriate amount of outflow. When the work of writing or the like is completed (in a normal state), the ball is brought into close contact with the inner edge of the ball holding portion at the tip of the chip by the pressing means, and the fluid coating liquid does not flow out.

In these fluid applicators, n-hexane, n-heptane, n-octane, isooctane, cyclohexane, and methylcyclohexane are contained in a storage pipe having an outflow control mechanism, for example, in a storage pipe formed of a pipe-shaped container. , A liquid coating solution containing at least one organic solvent selected from ethylcyclohexane, toluene and xylene. Examples of the fluid coating liquid in the present invention include colorants such as pigments and dyes such as carbon black and titanium dioxide, resins soluble as a solvent, thickeners and binders, and surfactants in the above organic solvents. A substance, a fragrance, and other optional components depending on the application such as a writing instrument, a correction instrument, an adhesive applicator, and a cosmetic instrument are appropriately dissolved or dispersed. Regarding the blending amount of these, for example, the total amount of the fluid coating liquid (1
00% by weight), the organic solvent is 20 to 85% by weight, the coloring material such as a pigment is 10 to 60% by weight, and the resin and other components are 5 to 5% by weight.
It is desirable to use a compounded composition of about 30% by weight. Further, the above-mentioned fluid coating liquid may be used as it is, but it may be used as a gel-like viscous material by adding a viscosity imparting agent such as fine powder silica, alumina, dibenzyl sorbitol to the above fluid coating liquid. . By using this gel-like viscous material, a pigment (titanium oxide, etc.) that is heavy in the fluid coating liquid
It is easy to suppress the sedimentation of these materials even if they are mixed with other coloring materials. In addition, when ink (fluid) is applied to an object to be coated such as paper, it has a structural viscosity, which causes "bleeding" on the object to be coated. Can be suppressed. This gel strength is appropriately adjusted depending on the particle size and specific gravity of the coloring material (pigment or the like) used.

According to the present invention, the fluid coating liquid is contained in the container of the applicator, and the non-volatile liquid which is incompatible with the fluid coating liquid is a movable stopper at the end of the fluid coating liquid. Is accommodated in a contact state, and the inside of the rear accommodating tube of the movable stopper is opened to the atmosphere. As a result, the movable stopper follows the fluid coating liquid as the fluid coating liquid is consumed, and acts as a movable stopper.

As the hardly volatile liquid substance forming the movable plug in the present invention, as described above, "it is incompatible with the fluid coating liquid and the volatilization of the fluid is prevented" and "the self-volatization is difficult". In addition to the two basic performances of "Koto", the performance of "non-hygroscopic" is required. Movable stoppers that satisfy the above two basic properties have the disadvantage that they have both hydrophilicity and hygroscopicity due to their properties, and in order to avoid this, a balance between hydrophilicity and lipophilicity is appropriate. Need to choose.
Therefore, glycerin and polyglycerin are too hygroscopic. In addition, when an alkyl group having a larger number of carbon atoms than propylene oxide among alkylene oxides having various degrees of polymerization is used, lipophilicity is overwhelmed, and the solvent is volatile by being miscible with the low polar organic solvent. There is a problem that it cannot be suppressed. Therefore, in the present invention, the hardly volatile liquid material forming the movable plug is made hydrophilic by glycerin and polyglycerin, and lipophilicity is imparted by the alkylene oxide adduct to adjust the amphipathic balance. As a result, among alkylene oxide adducts of polyglycerin, propylene oxide 2 to 6 mol adduct of diglycerin represented by the general formula (I) having the above three performances [m + n + o + p (= s) is an integer of 2 to 6] ] As a main component, preferably, this 2 to 6 mol addition product is 80 to 100% by weight with respect to the total amount of the movable stopper (100% by weight),
More preferably, 90 to 100% by weight is selected, and a 4 mol adduct (s = 4) is particularly preferable because it is the best in terms of the balance of the above three performances. In the present invention, the propylene oxide 2 to 6 mol adduct of diglycerin represented by the general formula (I), which constitutes the movable stopper, is contained in an amount of 80% by weight or more based on the total amount of the movable stopper (100% by weight). The effect of the present invention can be exerted by virtue of the fact that it is contained (becomes the main component). In the present invention, other than the above-mentioned propylene oxide 2 to 6 mol adduct of diglycerin, for example, diglycerin propylene oxide adduct of less than 2 mol or more than 6 mol, or diglycerin ethylene oxide adduct, etc. Then, the effect of the object of the present invention cannot be exhibited.

In the present invention, in order to further improve the performance as a movable stopper, that is, in order to prevent backflow when the pen tip is facing upward, fine powder of silica, alumina, a mixture thereof or dibenzylidene sorbitol is used. It is preferable to add the structural viscosity imparting agent to the propylene oxide 2 to 6 mol addition product of diglycerin represented by the general formula (I) and use it in a gelled state. As the structural viscosity imparting material that can be used in the present invention, for example, a material using a mixture of fine powder silica and alumina is the most excellent in terms of usability and temporal stability. The compounding ratio of the mixture of the fine powder silica (S) and alumina (A) is preferably such that S: A is 1: 4 to 9: 1 by weight. Specific examples of the mixture of fine powder silica and alumina include commercially available products such as COK84 manufactured by Nippon Aerosil Co., Ltd. The content of the structural viscosity imparting material is preferably 5 to 10% by weight based on the total amount of the movable stopper. When the content of the structural viscosity imparting material is less than 5% by weight, the structural viscosity is weak and there is a case where the material flows back due to a strong impact. On the other hand, if it exceeds 10% by weight, the structural viscosity becomes strong, and the followability accompanying the consumption of ink may be deteriorated depending on the early writing. It should be noted that any of these amounts does not hinder the desired balance of lipophilicity and hygroscopicity.

In the present invention, the above-mentioned hardly volatile liquid substance may be accommodated as a movable stopper in a state of directly contacting the end portion of the fluid coating liquid as a liquid layer. The height of the liquid layer at this time is preferably about 20 to 30 mm. In addition, a preferable movable plug of the present invention is a case where the above-mentioned structural viscosity-imparting material is added to a hardly volatile liquid material to store it as a gel-like structural viscous material in a state of being in contact with the end portion of the fluid coating liquid. is there. The height of the liquid layer in this case is 10-
About 15 mm is enough, the movable stopper of the gel-like structure viscous substance is less likely to transfer to the fluid coating liquid, the quality of the backflow preventer can be maintained, and the long-term deterioration of the fluid coating liquid can be prevented. Will be demonstrated.

Further, in the present invention, as another method, it is possible to use the non-volatile liquid material constituting the movable plug in a state of being impregnated into an open-cell foam such as polyurethane foam. For example, a height of 1 approx.
A sponge-like continuous porous body having a cylindrical shape of about 0 to 15 mm impregnated therein is accommodated in contact with the end portion of the fluid coating liquid. In this case, the impact resistance of the movable plug is enhanced regardless of the inner diameter of the containing tube, and the flow of the hardly volatile liquid substance is suppressed in the continuous porous body such as sponge. In particular,
The movable stopper does not transfer to the fluid coating liquid, and it becomes more difficult to physically interact with the fluid coating liquid, and the quality as a backflow preventer can be further improved and maintained, and the long-term quality of the fluid coating liquid can be maintained. The effect of preventing deterioration will be exerted.

In the present invention thus constructed, a hardly volatile liquid substance containing a propylene oxide adduct of diglycerin represented by the general formula (I) as a main component is placed in a container such as a pipe-shaped container. The fluid coating liquid is accommodated in contact with the end portion of the fluid stopper to form a movable stopper, and the inside of the rear accommodation pipe of the movable stopper is used as a fluid application tool that is released to the atmosphere. In this case, an accommodation pipe such as a pipe-shaped container. If the inner diameter of the fluid is small (usually 2 mm or less for writing instruments and correction fluid containers), the surface tension of the fluid coating solution and the movable stopper will not affect the structural viscosity of the fluid coating solution and the movable stopper. The fluid applicator can be stably housed in a container such as a pipe-shaped container. In addition, when the inner diameter of the storage tube is increased in order to store a large amount of the fluid coating liquid in the storage tube such as the pipe-shaped container (usually 3 mm or more for writing instrument and correction liquid container use), the pipe-shaped container is sideways, When turned upside down, problems such as the liquid surface of the follower being cut off may occur. In this case, as described above, the movable plug is made to have a structural viscosity, or the movable plug is made by impregnating a sponge-like continuous porous body with a hardly volatile liquid substance, so that the fluid coating liquid and the movable plug are A fluid applicator that can be stably housed in a housing pipe such as a pipe-like container can be provided, and the quality as a backflow prevention structure of the present invention can be maintained, and long-term quality deterioration of the fluid coating liquid can be prevented. The fluid applicator can exert the effect.

[0019]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. "Parts" described below means parts by weight.

[Examples 1 to 17 and Comparative Examples 1 to 7] FIG.
As shown in FIG. 2, about 2 g of the fluid coating solution (fluid A) having the following composition was poured into a pipe-shaped container having an inner diameter of 5 mm, which was equipped with a ball-point pen type tip at the tip. Next, each fluid applicator was manufactured by accommodating the movable stoppers prepared by the following Examples and Comparative Examples, which were accommodated in the end portion of this fluid coating liquid (fluid A) in contact with each other. Each of the resulting fluid applicators was placed in an environment test room at 25 ° C and 60% RH, and the weight change after one month was measured and the appearance of the movable plug was sensory evaluated. Of the movable plug, the backflow property of the movable plug due to dropping, and the volatilization loss at 50 ° C. were evaluated. The results are shown in Table 1 below.

(Composition of Fluid A) The following components were mixed and dispersed to prepare Fluid A. Methylcyclohexane 40 parts Acrylic resin 10 parts Titanium dioxide 50 parts

[Evaluation method of followability of movable plug by quick writing]
It was written with a writing tester at a speed of 9.0 m / min and sensory-evaluated according to the following evaluation criteria. Evaluation Criteria: ◯: Good followability. Δ: The followability is slightly inferior. X: The followability is poor.

[Evaluation Method of Backflow of Movable Plug by Dropping] With the cap of FIG. 1 dropped onto a rubber plate with the pen tip forward from a height of 1.2 m, sensory evaluation was performed according to the following evaluation criteria. did. Evaluation criteria: ◯: There is no reverse flow. B: Slightly reverse-sulfurized. X: Backflow.

[Measurement method of volatilization loss at 50 ° C.] The cap of FIG. 1 was put into an oven at 50 ° C., and the change in weight after one month was measured as the volatilization loss, and the sensory evaluation was performed according to the following evaluation criteria. did. Evaluation criteria: ◯: less than 30 mg △: 30 mg to 50 mg ×: more than 50 mg

[Example 1] 4-mol propylene oxide adduct of diglycerin (SY-P4 manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)
A movable stopper made of (00) was injected with 0.4 g to prepare a fluid applicator. [Example 2] A fluid applicator was produced in the same manner as in Example 1 except that a 2 mol addition product of diglycerin and propylene oxide was used as the movable stopper. [Example 3] A fluid applicator was produced in the same manner as in Example 1 except that a 6-mole propylene oxide adduct of diglycerin was used as the movable stopper. [Example 4] Finely divided silica (manufactured by Nippon Aerosil Co., Ltd., in 95 parts of a 4 mol addition product of propylene oxide to diglycerin)
A fluid applicator was produced in the same manner as in Example 1 except that 5 parts of R972) were mixed and dispersed to form a movable stopper. Example 5 The same as Example 1 except that 5 parts of a mixture of finely powdered silica and alumina (COK84, manufactured by Nippon Aerosil Co., Ltd.) was mixed and dispersed in 95 parts of 4 mol of a propylene oxide 4 mol adduct of diglycerin. Similarly, a fluid applicator was produced. [Example 6] A fluid applicator was produced in the same manner as in Example 1 except that 4 mol of the propylene oxide adduct of diglycerin was changed to 2 mol of the propylene oxide of diglycerin in the above Example 5. [Example 7] A fluid applicator was produced in the same manner as in Example 1 except that in Example 5 the 4 mol adduct of propylene oxide with diglycerin was changed to a 6 mol adduct of propylene oxide with diglycerin.

[Embodiment 8] A fluid B prepared by adding 1 part of finely divided silica to the fluid A obtained in Example 1 and mixing and dispersing the resulting mixture is used as a fluid B.
A fluid applicator was produced in the same manner as in Example 1 except that the above was used. [Example 9] A fluid applicator was produced in the same manner as in Example 1 except that the fluid A was changed to the fluid B in Example 2. [Example 10] A fluid applicator was produced in the same manner as in Example 1 except that the fluid A was changed to the fluid B in Example 3. [Example 11] A fluid applicator was produced in the same manner as in Example 1 except that the fluid A was changed to the fluid B in Example 4. [Example 12] A fluid applicator was produced in the same manner as in Example 1 except that the fluid A was changed to the fluid B in Example 5. [Example 13] A fluid applicator was produced in the same manner as in Example 1 except that the fluid A was changed to the fluid B in Example 6.

Example 14 Fluid A in Example 7
A fluid applicator was produced in the same manner as in Example 1 except that the fluid B was used. [Example 15] In Example 5, 90 parts of a 4 mol addition product of propylene oxide of diglycerin was added to finely divided silica,
Alumina mixture (COK84, manufactured by Nippon Aerosil Co., Ltd.)
Example 1 except that a movable stopper was prepared by mixing and dispersing 10 parts of
A fluid applicator was produced in the same manner as in. [Example 16] In Example 5, 85 parts of a 4 mol adduct of propylene oxide with diglycerin was added to finely divided silica,
Alumina mixture (COK84, manufactured by Nippon Aerosil Co., Ltd.)
Example 1 except that a movable stopper was prepared by mixing and dispersing 15 parts of
A fluid applicator was produced in the same manner as in. Example 17 In Example 5, 96 parts of propylene oxide 4 mol adduct of diglycerin was added to finely divided silica,
Alumina mixture (COK84, manufactured by Nippon Aerosil Co., Ltd.)
A fluid applicator was produced in the same manner as in Example 1 except that 4 parts of 4 were mixed and dispersed as a movable stopper.

[Comparative Example 1] Example 1 except that glycerin was used as the 4 mol adduct of propylene oxide with diglycerin.
A fluid applicator was produced in the same manner as in. [Comparative Example 2] A fluid applicator was produced in the same manner as in Example 1 except that 4 mol of propylene oxide adduct of diglycerin was changed to 13 mol of ethylene oxide of diglycerin. [Comparative Example 3] A fluid applicator was produced in the same manner as in Example 1 except that 4 mol of propylene oxide adduct of diglycerin was changed to 9 mol of propylene oxide of diglycerin. [Comparative Example 4] A fluid applicator was produced in the same manner as in Example 1 except that diglycerin was used as the propylene oxide 4 mol adduct of diglycerin. [Comparative Example 5] A fluid applicator was produced in the same manner as in Example 8 except that glycerin was used as the propylene oxide 4 mol adduct of diglycerin. [Comparative Example 6] A fluid applicator was produced in the same manner as in Example 8 except that 4 mol of propylene oxide adduct of diglycerin was changed to 13 mol of ethylene oxide of diglycerin. Comparative Example 7 A fluid applicator was produced in the same manner as in Example 8 except that 4 mol of propylene oxide adduct of diglycerin was changed to 9 mol of propylene oxide of diglycerin.

[0029]

[Table 1]

As is clear from the results in Table 1 above, Examples 1 to 17, which fall within the scope of the present invention, have an environment of 25 ° C. and 60% RH, as compared with Comparative Examples 1 to 7, which fall outside the scope of the present invention. The amount of change in weight after one month under the conditions is small, the appearance of the movable plug does not change, the followability of the movable plug due to quick writing is good, and there is no backflow of the movable plug when dropped. It was found that the volatilization loss at 50 ° C was also small.
Specifically, in Examples 1 to 3, diglycerin of the present invention has a propylene oxide 2 mol adduct, a 4 mol adduct, and a 6 mol adduct as movable plugs, respectively. Nos. 4 to 7 are gel movable stoppers in which a structural viscosity imparting material made of fine powder silica is added to each mole adduct of propylene oxide of diglycerin of the present invention to form a gelled movable plug. 14 is a gel-like viscous body of the fluid of Examples 1 to 7, and Examples 15 to 15
No. 17 is a gel-like movable plug in which a structural viscosity imparting material composed of a mixture of fine powder silica and alumina is added to the 4 mol addition product of propylene oxide of diglycerin of the present invention and gelled. In case of 25 ℃, 60
The amount of change in weight after one month under the environmental conditions of% RH is small, the appearance of the movable plug does not change, and the followability of the movable plug due to quick writing is good. It was found that there was no property and the volatilization loss at 50 ° C was small. Therefore, it was found that the present invention provides a fluid applicator having excellent stability over time even under high humidity.
In contrast, Comparative Example 1 uses glycerin as a movable stopper, Comparative Example 2 uses diglycerin with 13 mol of ethylene oxide as a movable stopper, and Comparative Example 4
Is a movable stopper made of diglycerin, Comparative Example 5 uses the gel fluid of Example 8 as a fluid, and uses glycerin as a movable stopper, and Comparative Example 6 makes a fluid. The gel fluid of Example 8 was used, and 13 mol of ethylene oxide adduct of diglycerin was used as a movable stopper. In Comparative Example 7, the gel fluid of Example 8 was used as the fluid. Glycerin Propylene Oxide 9
In the case of Comparative Examples 1, 2 and 4 to 6, the mole addition product was used as a movable stopper, and the weight change amount after one month was large under the environmental conditions of 25 ° C. and 60% RH. The appearance state is such that water floats or becomes a water layer, and in Comparative Examples 3 and 7, it is 50 ° C. as compared with Examples 1 to 17.
It was found that the amount of volatilization loss was large. Therefore, by using the configuration of the present invention (Examples 1 to 17),
It was found that the fluid applicator has excellent stability over time even under high humidity. In this embodiment, a white fluid applicator using titanium dioxide as a coloring material has been described as an example, but in the present invention, even a fluid colored with a dye / pigment such as carbon black or red / blue does not matter. There is no problem in the function, and the intended function and effect of the present invention can be exhibited.

[0031]

According to the present invention, there is provided a fluid applicator having excellent stability over time even under high humidity.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view showing an example of a fluid applicator of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 11/16 B43K 8/02 Z (72) Inventor Hitoshi Nakamura 1091 Tateishi, Fujioka-shi, Gunma Mitsubishi Pencil Co., Ltd. Gunma R & D Center F-term (reference) 2C350 GA03 GA04 NA10 NC01 NC10 NC17 NC23 NC24 4F042 FA22 FA30 FA43 4J039 BA13 BA21 BC01 BC02 BC03 BC13 BE23 GA26 GA27

Claims (4)

[Claims] 1. An accommodating tube of an applicator equipped with a fluid coating solution outflow control mechanism is provided with n-hexane, n-heptane, and n-hexane.
A fluid coating solution containing at least one organic solvent selected from octane, isooctane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene and xylene is contained, and the fluid is provided behind the fluid coating solution. A fluid applicator in which a non-volatile liquid substance that is incompatible with the coating liquid is accommodated as a terminal movable stopper in a contact state and the inside of the rear accommodation pipe of the movable stopper is exposed to the atmosphere. A fluid applicator comprising a propylene oxide adduct of diglycerin represented by the formula (I) as a main component. [Chemical 1] 2. A fluid applicator, wherein the movable stopper according to claim 1 is a propylene oxide 4 mol adduct of diglycerin (s = 4). 3. The movable stopper according to claim 1, wherein the movable stopper is silica,
A fluid applicator characterized by having a structural viscosity due to an alumina mixture. 4. The fluid applicator according to claim 3, wherein the movable stopper having the structural viscosity contains 5 to 10% by weight of a mixture of silica and alumina with respect to the total amount of the movable stopper.