JP2002192877A - Marking pen excellent in cap-off performance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a marking pen excellent in a cap-off performance and realizing an excellent writing performance even when a penpoint is left in the air for a long time. SOLUTION: The marking pen contains at least a colorant, a solvent and a resin as ink constituents, while the penpoint formed of a fibrous or plastic core is coated with a coating agent constituted of a substance giving cap-off properties thereto. The coating agent contains petroleum wax or the like constituted mainly of a hydrocarbon having a side chain.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a marking pen excellent in cap-off performance having good writing performance even when the pen tip is left in the air for a long period of time.

[0002]

2. Description of the Related Art Conventionally, a marking pen which penetrates an ink into a pen tip made of a fiber core or a plastic core for writing is widely used. However, when the cap is removed and the pen tip is left in the atmosphere for a long time, there is a problem that the pen tip is dried and writing failure occurs.

Conventionally, as a marking pen which is excellent in cap-off performance for suppressing drying at a pen tip, for example, a higher fatty acid ester of polyglycerin or the like is added to ink (Japanese Patent Publication No. 62-34352), or a pen. Paraffin wax which can be deposited on the front surface to form a thin film is added to the ink (Japanese Patent Publication No. 1-35028), or hexaglyceryl tristearate is added to the ink (JP-A-2-232).
No. 277), and lecithin is added to ink (Japanese Patent No. 2594457).

However, many additives having a high evaporation suppressing effect have low solubility (less than 10% by weight) in an ink solvent, and have a problem in that the solubility is low. In particular, the solubility at 0 ° C. is further increased. It is low (less than 5% by weight). It is stored at low temperature, or the additive is precipitated in the ink by repeated low and high temperature, causing clogging in the ink flow path and lowering writability. However, there is a problem that the cap-off performance is deteriorated with time and the cap-off performance is not yet effective.

The applicant of the present invention has applied for a writing implement such as a marking pen, a felt-tip pen, and a brush pen having excellent cap-off performance by coating a pen tip made of a fiber core or a plastic core with a substance imparting cap-off properties. (PCT Publication WO2000 / 37265). Writing implements formed by coating a substance imparting cap-off property to a pen tip made of these fiber cores or plastic cores are excellent in cap-off performance, but writing implements with even higher cap-off performance are required. It is the present situation.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has been made to solve the problem. It is an object of the present invention to provide a marking pen having excellent cap-off performance for realizing performance.

[0007]

Means for Solving the Problems The present inventors have made intensive studies on the above-mentioned problems of the prior art and found that hydrocarbons having a side chain are the main component among the substances which impart cap-off properties. Petroleum waxes are low in crystallinity, so when forming a film, the wax is finely spread, it becomes a film without gaps, and it is found that a marking pen for the above purpose that can realize good cap-off performance can be obtained. The present invention has been completed. That is, the present invention resides in the following (1) to (3). (1) A marking pen comprising, as an ink component, at least a colorant, a solvent and a resin, and a coating agent comprising a substance imparting cap-off properties coated on a nib comprising a fiber core or a plastic core. A marking pen excellent in cap-off performance, characterized in that the coating agent contains petroleum waxes mainly composed of a hydrocarbon having a side chain. (2) A marking pen containing at least a colorant, a solvent, and a resin as an ink component and having a nib composed of a fiber core or a plastic core, wherein the ink component mainly includes a hydrocarbon having a side chain. A marking pen excellent in cap-off performance characterized by containing petroleum wax as a component. (3) The petroleum wax containing a hydrocarbon having a side chain as a main component has a melting point of 63 ° C. or less, and is excellent in cap-off performance according to the above (1) or (2), which is a solid at ordinary temperature. Marking pen.

[0008]

Embodiments of the present invention will be described below in detail. The marking pen excellent in cap-off performance of the first invention comprises at least a coloring agent, a solvent, and a resin as an ink component, and is made of a substance that imparts a cap-off property to a pen tip made of a fiber core or a plastic core. A marking pen coated with a coating agent, characterized in that the coating agent contains petroleum waxes mainly composed of hydrocarbons having side chains. Further, the marking pen excellent in cap-off performance of the second invention is a marking pen having at least a coloring agent, a solvent and a resin as an ink component, and having a nib composed of a fiber core or a plastic core, The ink component contains a petroleum wax containing a hydrocarbon having a side chain as a main component. In the following, the “present invention” refers to the above-mentioned first invention and second invention.

As the marking pen in the present invention,
The marking pen is not particularly limited as long as it is a marking pen having a pen tip made of a fiber core or a plastic core. For example, as shown in FIG. 1, the marking pen has an ink tank portion 11 serving as a shaft directly storing ink. And a collector member 12 for temporarily storing the ink, and the lead-out of the ink from the ink tank portion 11 to the pen tip 13 is performed by a relay core 14.
2, a direct liquid type marking pen 10 which is performed via (or directly) has, as shown in FIG. 2, an ink tank 21 serving as a shaft for directly storing ink, and a pen tip 22 from the ink tank 21. The marking pen 20 in which the ink is directly drawn out (or via a relay core) via the valve mechanism 23 has an ink occluding body 32 in which the ink is occluded in a shaft 31 as shown in FIG. And a marking pen 30 in which the ink is directly led out from the ink storage body 32 to the pen tip 33 (or via a relay core).

In the present invention, the material, structure, manufacturing method and the like of the nib made of a fiber core or a plastic core are not particularly limited, and examples thereof include natural fibers, animal hair fibers, polyacetal resins, acrylic resins, and the like. A parallel fiber bundle comprising one or a combination of two or more of a polyester resin, a polyamide resin, a polyurethane resin, a polyolefin resin, a polyvinyl resin, a polycarbonate resin, a polyether resin, and a polyphenylene resin;
Fiber bundles processed from fiber bundles such as felt or these fiber bundles are processed with resin, relay cores or ink-absorbing bodies, plastic cores with ink grooves formed in the axial direction of the above various plastic materials, plastic powders of the above various types, etc. A nib made of a fused porous body or the like is mentioned, and the form thereof is also arbitrary such as a plate-like body, a fiber bundle, a sintered body, and a foam.

The shape of the nib formed of a fiber core or a plastic core to be used is not particularly limited as long as it is a shape usually used for a marking pen. Preferably, when a fiber core is used as the pen tip, a porosity of 30 to 75% and a slit diameter of approximately 1 to 20 μm is desirable. When a plastic core is used as the pen tip, it is preferable. 20-40 μm in slit diameter
Is desirable. In addition, the porosity and the slit diameter can be changed according to each type of marking pen, and are not limited to the above numerical ranges. Furthermore,
The slit diameter is calculated by the following equation. Slit diameter = porosity x radius of yarn / (1-porosity)

It is necessary that the coating agent comprising a substance imparting cap-off performance of the pen tip used in the first invention contains a petroleum wax mainly composed of a hydrocarbon having a side chain. . Examples of the petroleum waxes containing a hydrocarbon having a side chain as a main component in the present invention include, for example, a carbon wax having an alkyl group, a phenyl group, a cyclo ring and the like in the side chain, a molecular weight of 300 to 700, and a carbon number of 20 to 50. Examples include petroleum waxes containing hydrogen as a main component.
In the present invention, the main component is a hydrocarbon having a side chain. Therefore, the content of the hydrocarbon having a side chain is 10% by weight or more, preferably 50% by weight, based on the total amount of petroleum waxes.
%, More preferably 70% by weight or more. If the content of the hydrocarbon having a side chain is less than 10% by weight, the effect of imparting the cap-off property is low, and the effect of the present invention cannot be achieved.

The petroleum wax containing a hydrocarbon having a side chain as a main component preferably has a melting point of 63 ° C. or less and is solid at ordinary temperature, more preferably a melting point of 58 ° C. or less. Particularly preferably, the melting point is 40 to
More preferably, the temperature is 53 ° C. and the temperature is fixed at room temperature. Petroleum waxes having a melting point of 63 ° C. or less, and having hydrocarbons having side chains that become solid at ordinary temperature as a main component, are more excellent in crystallinity, and the wax is spread more finely when forming the film l. Further, the coating film 1 has no gap, and particularly excellent cap-off performance can be realized.

In the first aspect of the present invention, the substance imparting the cap-off property is constituted by a petroleum wax mainly composed of the above-mentioned hydrocarbon having a side chain, but within a range that does not impair the effects of the present invention. In addition, a substance imparting cap-off properties other than petroleum waxes having this property may be contained (combined use). Other substances that impart cap-off properties that can be used include, for example, glycerin such as diglycerin monostearate, triglycerin monostearate, pentaglyceryl tristearate, hexaglyceryl tristearate, and decaglycerin distearate. Derivatives, alkyl phosphates such as polyoxyethylene stearyl phosphate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, and polyoxyethylene sorbite hexastearate Oxyethylene sorbite fatty acid ester, paraffin wax, microstalin wax, pentaerythritol monostearate, pentaerythritol disis Pentaerythritol derivatives such Areto, lecithin, sucrose esters, polyolefin waxes, ascorbic acid stearate, one or more mixtures selected from such sorbitan acid stearate and the like. The content of these substances is not more than 50% by weight, preferably 0 to
30% by weight is desirable.

In the first invention, a method for coating a substance containing a petroleum wax having the above-mentioned properties on a fiber core or a plastic core may be, for example, dissolving the substance in a solvent that dissolves the substance, and then dissolving the same in the fiber core or plastic. After the core is dipped or sprayed, it can be heated or dried at room temperature. When the solubility is extremely low, it can be dipped in a heated solution and coated by cooling. Also,
Examples of the solvent for dissolving a substance imparting cap-off performance such as petroleum wax having the above characteristics include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol and isopropyl alcohol (i-propyl alcohol), and ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether,
Glycols such as propylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethers such as dimethyl ether and diethyl ether And hydrocarbons such as hexane, isohexane, heptane and methylcyclohexane, and chlorine compounds such as chloroform and methylene chloride.

The amount of the substance (coating agent) imparting cap-off performance coated on the fiber core or plastic core is 0.01 to 20% by weight, preferably 0.01 to 20% by weight, based on the fiber core or plastic core. 0.1-10
%, More preferably 0.3 to 5% by weight. If the coating amount is less than 0.01% by weight, the effect of the coating cannot be achieved, and if it exceeds 20% by weight, a substance having an evaporation suppressing effect on the fiber core or the plastic core is excessively attached. The function that the fiber core or the plastic core should originally exhibit is impaired, for example, it becomes difficult for ink to come out, blurring occurs, and the pen tip collapses as writing progresses, and the amount of stored ink Is not sufficient, for example.

As an ink component for a marking pen used in the present invention, at least a coloring agent, a solvent, a resin, and other additives for a marking pen can be used. Examples of the coloring agent include oil-soluble dyes and pigments. As the oil-soluble dye, almost any general oil-soluble dye that is soluble in an organic solvent can be used. For example, as a dye,
Orazole Yellow 2GLN, Orazole Red 3GL,
Orazol Blue 2GLN, Neon Zapon Blue FL
E, Spirit Black SP, Paris Fast Red 13
08, Oil Blue BA, Oil Yellow 185, Oil Red TR71, Oil Black S, Victoria Blue, R
hodamine 6JHSA, Flex Yellow 105 and the like, and the pigment is not particularly limited, for example, azo pigments,
Organic pigments such as condensed polyazo pigments, phthalocyanine pigments, metal complex pigments, thioindigo pigments, dye lake pigments, fluorescent pigments, and the like, and inorganic pigments such as carbon black and titanium oxide. Pigments, for example, Microlith A type various, A
S black, AS blue, IK red and the like can also be used. These dyes and / or pigments may be used alone or
It is possible to use a mixture of more than one kind, and the amount used varies depending on the type of the colorant and other ink components, but is preferably 1 to 30% by weight, preferably 2 to 15% by weight based on the total amount of the ink. .

Examples of the solvent that can be used include lower alcohols such as ethyl alcohol, propyl alcohol and isopropyl alcohol, aromatic hydrocarbons such as toluene and xylene, and methyl ethyl ketone and methyl isobutyl ketone. Lower aliphatic ketones, lower alcohol esters of lower fatty acids such as ethyl acetate and butyl acetate, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane and ethylcyclohexane, and alkyl alcohols of glycol and propylene And glycol ethers such as glycol monomethyl ether. The solvents having these properties can be used alone or in combination of two or more, and the amount of the solvent used is 50 to 90% by weight, preferably 70 to 85% by weight based on the total amount of the ink. % Is desirable.

The resin is a resin that is soluble in a solvent, and is used as a film-forming agent, an adhesive to a surface to be coated, a viscosity modifier for ink, and a dispersant for a coloring agent. Various types of natural resins and synthetic resins that can be used, for example, rosin, ester gum, maleic acid-modified rosin, rosin-based resins such as phenol-modified rosin, ethyl cellulose, cellulose resins such as nitrocellulose,
Vinyl resins such as polyvinyl butyral, vinyl chloride-vinyl acetate copolymer resins, petroleum resins, ketone resins, acrylic resins, condensates of aldehydes and urea, maleic acid resins, and the like. It is possible to use a mixture of the above, and the use amount is 0.1 to 30% by weight, preferably 1 to 20% by weight based on the total amount of the ink.
% By weight is desirable. Other additives for marking pens, for example, anionic, nonionic, cationic surfactants, preservatives, fungicides, rust inhibitors, lubricants,
pH adjusters and the like. The ink component of the present invention does not contain an erasability-imparting agent used in a marking pen for a writing board such as a whiteboard.

In the marking pen according to the first aspect of the present invention, the fiber core or the plastic core is coated with a petroleum wax having the above-mentioned properties as a coating agent, so that the surface of the fiber core or the plastic core is coated. Petroleum waxes are finely spread, and a brittle film without gaps can be formed, and this film prevents evaporation of a solvent that is a volatile component contained in the ink component, and the film is broken by writing pressure during writing, Although it is possible to write on it, and the formation of the coating is slightly different depending on the amount of the coating, petroleum mainly composed of the hydrocarbon having the side chain coated on the fiber core or the plastic core of the nib. When the necessary amount of wax and the like dissolves again into the ink and the pen tip is exposed to air, To form a new coating to the pen tip surface interaction, this film-forming → writing → film forming → writing ......
.. Indicate a repetitive effect many times, that is, a regenerated film that is always reproduced at the pen tip and breaks during writing. This effect is repeated until the ink components filled in the ink tank portion or occluded by the ink occlusion member are used up.

Next, the marking pen with excellent cap-off performance according to the second aspect of the present invention can be used without coating a coating agent made of a substance imparting cap-off properties on a pen tip made of a fiber core or a plastic core. An ink component, that is, at least the pigment described above,
The desired cap-off performance is exhibited by incorporating a petroleum wax containing a hydrocarbon having a side chain having the above characteristics as a main component into an ink component containing a solvent and a resin. Since the ink component used in the second invention and the petroleum wax mainly containing a hydrocarbon having a side chain to be contained in the ink component are the same as the ink component and the petroleum wax described in detail in the first invention, , The description of which is omitted. The content of the petroleum wax containing a hydrocarbon having a side chain as a main component is 0.03 to 10% by weight, preferably 0.05 to 8% by weight based on the total amount of the ink component.
%, More preferably 0.1 to 5% by weight.
If the content of the petroleum wax is less than 0.01% by weight, the effects of the present invention cannot be achieved,
If the content exceeds 0% by weight, the ink is stored at a low temperature, or precipitates in the ink due to repeated low and high temperatures, causing clogging in the ink flow path, reducing the writability, and deteriorating the cap-off performance over time. It is not preferable, for example.

In the marking pen according to the second aspect of the present invention, even if a petroleum wax having the above-mentioned properties is contained in the marking pen ink component containing at least the colorant, the solvent and the resin, Without impairing the physical properties of the ink component, the petroleum wax contained in the ink component can form a brittle coating with no gaps on the surface of the fiber core or plastic core. The coating prevents evaporation of a solvent that becomes a volatile component contained in the ink component, and the coating is broken by writing pressure at the time of writing to enable writing on a writing member. The formation is slightly different depending on the content of petroleum waxes contained in the ink component, but when the pen tip is next exposed to the air, a new coating is formed on the pen tip surface due to the interaction with the ink solvent. This film formation → writing → writing → coating → writing... Exhibits an effect that is repeated many times, that is, a regenerated film which is always reproduced at the pen tip and breaks during writing is formed. This effect is repeated until the ink filled in the ink tank portion or the ink occluded body is used up.

The marking pen of the present invention is not limited to the above embodiment, and it goes without saying that the marking pen can be changed to various forms without changing the gist of the present invention. In the first aspect of the present invention, as described above, the pen tip is coated with a coating agent containing petroleum waxes containing hydrocarbons having the above-mentioned side chains as a main component. Similarly to the above, the ink component containing at least the colorant, the solvent, and the resin may contain the above-mentioned petroleum wax mainly containing a hydrocarbon having a side chain. Since the content of the petroleum wax containing hydrocarbons having a side chain as a main component is already coated on the pen tip, the content of the petroleum wax can be smaller than the content of the second invention. It is about 0.01 to 5% by weight based on the total amount. Further, the marking pen of the present invention is a general oil-based marker,
The present invention can be suitably applied to underlines, name pens, paint markers, brush pens, erase pens, and the like.

[0024]

EXAMPLES Next, the present invention will be described more specifically and in detail based on examples and comparative examples, but the present invention is not limited to the following examples.

[Examples 1 to 11 and Comparative Examples 1 to 5] A pen tip made of acrylic fiber sliver as a pen tip, weighing 0.17 g, length 33 mm, and diameter 4.0 mm.
(Porosity of 55%) was used. Further, as the ink for marking pens, each ink having the composition shown in Table 1 below (composition unit: weight%) was used. As a coating substance (coating agent) for imparting cap-off properties, a hydrocarbon having a side chain ratio of 80% (functional group of the side chain: methyl group, cyclopentyl group, phenyl group), a melting point of 65 ° C. and a carbon number of 34 is mainly used. Petroleum wax (molecular weight: 422), side chain ratio 70% (functional group of side chain: methyl group, cyclopentyl group, phenyl group), petroleum wax having a melting point of 62 ° C. and a hydrocarbon having 32 carbon atoms as a main component (molecular weight) : 394), 90% side chain ratio (functional group of side chain: methyl group, cyclopentyl group, methylcyclohexyl group), melting point 50 ° C, petroleum wax containing hydrocarbons having 28 carbon atoms as main components (molecular weight: 450) Petroleum wax (molecular weight: 352) whose main component is a hydrocarbon having 27 carbon atoms, a melting point of 60 ° C., diglycerin monostearate, and a side chain ratio of 5% (functional group of side chain: methyl group). It was used. Incidentally, each of these petroleum waxes was solid at room temperature.

In the coating method, the above-mentioned predetermined amount of the coating substance (petroleum wax having the above-mentioned properties for imparting cap-off properties) is dissolved in methylene chloride as a solvent, and the above-mentioned pen tip is immersed in the prepared solution. Immersion for 2 hours, and then lifted to a mesh container to remove the solvent
What was dried all day and night (24 hours) at ° C was used. The amount of the coating agent adhering to the pen tip was taken as the weight difference between the ink occluding body before and after the treatment, and was shown as a percentage by weight with respect to the pen core weight before the treatment. Each processing rate A to E shown in the margin of Table 2 below
And a (untreated) pen wick were used. The pen core type E is obtained by immersing a pen core in a mixture with the above-mentioned coating agent.

With the above ink (4.5 g) and a pen core,
A batting type marking pen (marking pen) as shown in FIG. 3 was obtained. Using each of the marking pens, cap-off performance, that is, writing performance evaluation based on the change over time of the cap-off time was performed by the following method. The results are shown in Table 2 below.

(Evaluation method of cap-off performance) Each of the marking pens of each of the examples and the comparative examples was left standing, and in a room at a temperature of 25 ° C and a humidity of 65%, the caps of the marking pens were removed in a cap-off state with time. The writing performance at 25 ° C. based on the change was evaluated according to the following evaluation criteria. Evaluation Criteria: ◎: Can be written without blurring 〇: Slightly blurred in writing △: The first line is blurred △△: The second line is blurred ×: Cannot be written

[0029]

[Table 1]

[0030]

[Table 2]

As is evident from the results of Tables 1 and 2, the marking pens of Examples 1 to 11 which are within the scope of the present invention have a longer air-conditioning time than Comparative Examples 1 to 5 which are outside the scope of the present invention. It has been found that a marking pen with excellent cap-off performance that achieves good writing performance even when the pen tip is left inside. When looking at the examples individually, Examples 1 and 2 contain petroleum waxes having the characteristics of the present invention in the ink component, and Examples 3 to 11 show that the pen tip of the present invention It is coated with a coating agent containing a petroleum wax having characteristics. In particular, in Examples 9 and 10, the pen tip was coated with a coating agent containing a substance imparting another cap-off property in addition to the petroleum wax having the properties of the present invention. The ink component contains a petroleum wax having the characteristics of the present invention, and a pen tip is coated with a coating agent containing the petroleum wax having the characteristics of the present invention. On the other hand, looking at the comparative examples, Comparative Examples 1 and 2 are those of a conventional ordinary marking pen mode, and Comparative Example 3 uses an untreated pen tip and adds a side chain to the ink component. Comparative Examples 4 and 5 were coated with a coating agent containing a petroleum wax not containing a hydrocarbon having a side chain at the pen tip as a main component. Things. Comprehensive evaluation of these Examples 1 to 11 and Comparative Examples 1 to 5 shows that the ink component contains petroleum wax having the characteristics of the present invention, or the petroleum wax having the characteristics of the present invention at the pen tip. And a marking pen according to the present invention, which is a composite of these, is a conventional ordinary marking pen mode,
The ink component was simply coated with a petroleum wax not containing a hydrocarbon having a side chain as a main component and a coating agent containing a petroleum wax not containing a hydrocarbon having a side chain at a pen tip as a main component. Compared to things,
It was found that the cap-off performance, which achieves good writing performance even when the pen tip was left in the air for a long time, was excellent.

[0032]

According to the present invention, there is provided a marking pen capable of achieving excellent writing performance even when the pen tip is left in the air for a long time.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing, in a sectional form, an example in which the present invention is applied to a direct liquid type marking pen as an example of the present invention.

FIG. 2 is an explanatory view showing, in a sectional form, an example applied to a marking pen having a valve mechanism as another example of the present invention.

FIG. 3 is an explanatory view showing, in a sectional form, a marking pen of a type in which ink is occluded in an ink occlusion body such as a batting as another example of the present invention.

[Explanation of symbols]

 10 Marking pen 13 Pen tip 14 Relay core

Continued on the front page F-term (reference) 2C350 GA04 HA08 HA15 KA01 KC01 KC11 NC02 NC28 NC29 NC33 NE08 4J039 AB02 AB04 AB05 AB08 AB12 AD05 AD07 AD08 AD10 AD14 AD18 AE01 AE03 BC03 BC04 BC07 BC08 BC13 BC16 BC18 BE01 BE02 BE12 BE22 EA44 GA21

Claims (3)

[Claims] 1. An ink component comprising at least a colorant,
A marking pen containing a solvent and a resin, and a coating agent comprising a substance imparting cap-off property coated on a pen tip made of a fiber core or a plastic core, wherein the coating agent has a side chain. A marking pen excellent in cap-off performance characterized by containing petroleum waxes mainly composed of hydrocarbons. 2. An ink component comprising at least a colorant,
A marking pen containing a solvent and a resin, and having a nib composed of a fiber core or a plastic core,
A marking pen excellent in cap-off performance, characterized in that the ink component contains petroleum waxes mainly composed of hydrocarbons having side chains. 3. The petroleum wax containing a hydrocarbon having a side chain as a main component has a melting point of 63 ° C. or less, and
3. The marking pen according to claim 1, which is solid at ordinary temperature.