JPH09123666A - Novel aqueous ink back-flow preventing agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide excellent ink followability, back-flow preventing properties and low-temperature fluidity, low-cost material and to reduce the complexity and cost at the time of manufacturing. SOLUTION: The novel aqueous ink back-flow preventing agent composition is obtained by dissolving crystalline polyolefin having 0.04 to 35g/10min of a melt flow rate in base made of hardly volatile or nonvolatile organic liquid selected from hydrocarbons and the like and further adding adhesive preventing agent thereto.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an aqueous ballpoint pen,
The present invention relates to a water-based ink backflow prevention composition used for marking pens and the like. Specifically, for water-based ballpoint pens and marking pens that directly store ink in the ink storage tube, to prevent volatilization of the water-based ink, to ensure stable storage of ink, and to prevent ink from adhering to the inner surface of the storage tube. The present invention relates to an aqueous ink backflow preventing composition.

[0002]

2. Description of the Related Art In a writing instrument such as a water-based ballpoint pen or a marking pen in which a water-based ink is filled in a polypropylene ink cylinder, the ink filled in the cylinder at the end of the ink cylinder (the side opposite to the writing part) is A high-viscosity material having no compatibility, such as petrolatum, silicone grease, silicone oil, liquid paraffin, or a mixture thereof, is filled in a predetermined amount as an ink backflow preventing agent. The characteristics required of these water-based ink backflow preventive agents are that they move forward in the direction of the pen tip with the consumption of ink by writing, that is, they move following ink consumption, and that the pen is subject to impact and the like. At times, it is possible to prevent the ink from flowing back and scattering from the end portion of the ink cylinder. However, the conventional anti-reflux agent has a large viscosity change with temperature and becomes high temperature in direct sunlight, so the anti-reflux agent itself is softened and deformed, or flows to flow back the ink. Also, when the temperature becomes low in winter, the viscosity rises and it becomes difficult for the ink to move in the ink cylinder, and when ink is consumed, the inside of the ink cylinder becomes depressurized and the outflow of ink stagnates, causing blurring during writing. May occur.

Various proposals have been made as anti-reflux agents to improve the above-mentioned drawbacks, but they are not always satisfactory.
For example, JP-A-57-153070 discloses a composition comprising a hardly volatile organic liquid compound such as dibenzylidene sorbitol and ethylene glycol, and JP-A-57-200472 discloses an amino acid derivative (N −
(Lauroyl-L-glutamic acid-dibutylamide etc.)
Is disclosed in the form of a gel by dissolving the above in a non-volatile liquid such as polybutene or petrolatum. Further, it is disclosed in JP-A 5-270.
Japanese Patent No. 193 discloses a composition in which a non-volatile liquid such as polybutene is mixed with hydrophobic silica as a gelling agent and a surfactant having a fluoroalkyl group.

However, none of these anti-reflux agents is satisfactory. That is, JP-A-57-15
The compositions using dibenzylidene sorbitol, amino acid derivatives and the like described in JP-A No. 3070 and JP-A No. 57-200472 are not necessarily sufficient in impact resistance when dropped from the pen tip. In addition, JP-A-57-20
In the one described in Japanese Patent No. 0472, the compatibility between the non-volatile liquid such as polybutene and the amino acid derivative is not good,
Increasing the amount of amino acid derivative added may cause bleeding at low temperatures. Furthermore, JP-A-5-270193
In the composition described in the publication, not only expensive silica needs to be used, but also the low temperature fluidity tends to be poor due to the addition of silica. In addition, silica is a powdery material and is bulky, and since air is involved during mixing, it is necessary to perform three-roll kneading for defoaming as a post-treatment, and it is also necessary to prevent silica powder from scattering. It is not preferable in terms of time complexity and cost.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a novel water-based ink backflow which is excellent in ink followability, backflow prevention property and low temperature fluidity, is inexpensive in material, and has reduced complexity and cost during production. It is an object to provide an inhibitor composition.

[0006]

Means for Solving the Problems That is, the first aspect of the present invention
Is a base made of a non-volatile or non-volatile organic liquid selected from hydrocarbons, and has a melt flow rate (MF
The present invention relates to a novel water-based ink backflow inhibitor composition obtained by dissolving a crystalline polyolefin having an R of 0.04 to 35 g / 10 min and further adding an anti-adhesion agent. The second aspect of the present invention relates to a novel water-based ink backflow preventive composition characterized by using crystalline polyethylene, crystalline polypropylene or both as the crystalline polyolefin.

Hereinafter, the present invention will be described in detail. The hydrocarbons used as a base in the present invention are hardly volatile or non-volatile liquids. Specifically, the number average molecular weight is 300 to
4,000 polybutenes; liquid paraffin; oligomers or cooligomers of α-olefins such as propylene and butene-1; spindle oils; petroleum jelly; white oils, etc., which may be used alone or in admixture of two or more. Can be used. Those having a molecular weight of less than 300 are not preferable because they have high volatility. On the other hand, 4.0
Those having a molecular weight of more than 00 have low volatility but high viscosity, so that the followability is deteriorated and the handling becomes difficult during production, which is not preferable.

Next, M which is a unique component in the present invention
The crystalline polyolefin having FR of 0.04 to 35 is an olefin polymer such as polyethylene and polypropylene. Examples of the olefin include ethylene, propylene, butene-1, hexene-1, 4-methyl-pentene-1, octene-1 and the like. Further, these copolymers, for example, copolymers of ethylene and butene-1, hexene-1, 4-methyl-pentene-1, octene-1, etc., random or block copolymers of propylene and ethylene are also included. Be done. Since these are crystalline, they are clearly distinguished from so-called hydrocarbon wax.

More specifically, as polyethylene,
Crystalline polyethylene obtained by polymerizing ethylene alone or ethylene and a comonomer such as butene-1 by a medium pressure method, a low pressure method or a high pressure method is used. As the polypropylene, propylene alone, or a small amount of non-crystalline polypropylene obtained by polymerizing propylene and a comomer such as ethylene, or an isotactic structure obtained by removing non-crystalline polypropylene with a solvent from a polymer as appropriate It is a crystalline polypropylene.

The MFR of the crystalline polyolefin is 0.0
It must be in the range of 4-35g / 10min. MF
When R is less than 0.04g / 10min, high temperature and long time is required for melting, while when R is more than 35g / 10min, the shape retention is poor and therefore the performance in drop test showing impact resistance is poor. It is not preferable because there are concerns.

The crystalline polyolefin is added in the amount of the base 1
The amount is 0.5 to 30 parts by weight, preferably 1 to 10 parts by weight, based on 00 parts by weight. If the amount is less than 0.5 parts by weight, the effect of the present invention is difficult to be exhibited, and even if the amount exceeds 30 parts by weight, the performance is not improved corresponding to the amount added, which is uneconomical, which is not preferable.

In the present invention, an anti-adhesion agent is further added. The anti-adhesion agent is not particularly limited as long as it reduces the adhesion of the composition of the present invention to an ink cylinder made of synthetic resin, for example, crystalline polypropylene, and it is soluble in hydrocarbons as a base material. Thus, a well-known surfactant which is sparingly soluble or insoluble in water can be used. For example, polyoxyethylene sorbitan monolaurate and other polyoxyethylene sorbitan fatty acid esters and polyoxyethylene derivatives such as polyoxyethylene alkyl ethers disclosed in Japanese Patent Publication No. 6-33024;
Glucerin fatty acid esters such as glycerin dioleate disclosed in 15277, polyethylene glycol fatty acid esters such as polyethylene glycol diisostearate; sorbitan such as sorbitan monooleate disclosed in Japanese Patent Publication No. 6-33025. Fatty acid esters; pentaerythritol fatty acid esters such as pentaerythritol stearate disclosed in JP-B No. 5-82840; N-polyoxyethylene alkylamines disclosed in JP-A No. 62-148581; Polyoxyethylene hydrogenated castor oil disclosed in JP-A 6-33026; Fluorinated alkyl groups such as fluorinated alkyl group-based surfactants (for example, fluoroalkyl (C ₂ -C ₁₀ ) carboxylic acid salts) disclosed in JP-A-5-270193. Having a surfactant Alternatively, the polyether-modified silicone disclosed in JP-A-5-270192 may be used.

The above-mentioned anti-adhesion agents can be used alone or in combination, and the addition amount thereof is in the range of 0.01 to 10 parts by weight, preferably 100 parts by weight of hydrocarbons as a base. It is in the range of 0.01 to 5 parts by weight. 0.0
If it is less than 1 part by weight, the anti-adhesion ability is insufficient,
On the other hand, if the amount is more than 10 parts by weight, the adhesion is not improved correspondingly, and it is uneconomical, which is not preferable.

The composition of the present invention may further contain an appropriate amount of tackifying resin, inorganic or organic filler, pigment, dye or the like depending on the purpose of use. In addition, more common antioxidants such as 2,6-di-tert-butyl-4-methylphenol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate], trisnonylphenyl phosphite, tris (2,4-di-ter
t-Butylphenyl) phosphite and the like can be added alone or in combination of two or more kinds. The amount of the antioxidant is arbitrary, but for example, hydrocarbons as a base 1
0.1 to 3 parts by weight can be added to 00 parts by weight.

The above-mentioned components are mixed in a predetermined amount and, for example, 1
The composition of the present invention can be easily produced by stirring and dissolving at a temperature of 30 to 160 ° C. for 3 to 4 hours.
Since it is not necessary to mix powders such as silica, a kneading operation using a triple roll or the like is generally unnecessary, but it can be carried out as necessary. To inject the composition thus produced into an ink cylinder, a method of injecting a predetermined amount from one end of the ink cylinder previously filled with the water-based ink in a low-viscosity state with high fluidity before cooling Is efficient. In particular, when the ink cylinder is made of crystalline polypropylene, it is possible to employ a method of injecting at a relatively high temperature because the ink cylinder has high heat resistance. By cooling after the injection, a pen as a writing instrument can be obtained.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described in detail with reference to Examples.

EXAMPLES First, a method for producing a test ink cylinder and its evaluation test method are as follows. <Test ink cylinder> Ball-point pen ink cylinder (length 100
mm, inner diameter 3 mm, polypropylene) viscosity of 10,0
0.5 ml of a water-based ink of 00 cP is filled, and the water-based ink backflow preventive composition is directly filled so that the end portion thereof has a thickness of 10 mm to obtain a test ink cylinder. <Aging Change Test> The pen tip is left standing in an upright state with the pen tip facing upward and in a horizontal state in a constant temperature bath at 50 ° C. for one week, and the deformation and flow of the antireflux agent composition are observed. <Writing test> Writing at room temperature and at 5 ° C,
The quality of the ink outflow, the followability of the backflow preventive composition to the ink, and the like are observed. <Drop test> For 100 test ink cylinders, the state of ink dispersion and the flow state of the backflow preventive composition when the pen tip is directed downward and dropped from a height of 1 m onto a concrete floor are observed. The judgments of the above tests are all “◯: good, x: inferior”.

Example 1 Polybutene (number average molecular weight 6
30) high-pressure polyethylene (MFR = 5.5g / 10min;
Trade name: Lexulon J40, manufactured by Nisseki Chemical Co., Ltd.) was dissolved, and sorbitan monooleate was added as an anti-adhesive agent, and Irganox 1010 was added as an antioxidant.
Stirring and mixing were carried out at 50 ° C. to obtain a backflow preventing composition. The blending ratio and the test results are shown in Table 1 (the same applies hereinafter).

<Example 2> In Example 1, polyethylene was replaced with polypropylene (MFR = 9.0 g / 10 min; trade name: Nisseki Polypro F150H, manufactured by Nisseki Chemical Co., Ltd.).

<Example 3> The polybutene of Example 1 was replaced with liquid paraffin.

Example 4 In Example 2, polybutene was replaced with liquid paraffin.

<Comparative Example 1> In Example 1, polyethylene is removed.

<Comparative Example 2> In Example 1, polyethylene was replaced with silica (trade name: Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.). After mixing with stirring, three fibers were defoamed. The roll was used for finishing.

<Comparative Example 3> N-lauroyl-L-glutamic acid-dibutyramide was added to polybutene as an amino acid derivative, and other conditions were the same as in Example 1.

<Comparative Example 4> Dibenzylidene sorbitol was added to polyethylene glycol.
Is the same as

[0025]

As is apparent from Table 1, the water-based ink backflow preventive composition of the present invention reliably follows the ink cylinder without adhering to it as the ink is consumed and reduced.
Ink ejection failure is not caused, and the backflow preventing composition does not disappear in the middle of the process. Further, when not in use, the ink is stably held in the ink cylinder and the ink does not scatter. Also, in the aging test, the backflow of the ink is surely prevented, and the writing at low temperature is not blurred.

[Table 1]

Claims (2)

[Claims] 1. A crystalline polyolefin having a melt flow rate (MFR) of 0.04 to 35 g / 10 min is dissolved in a base material composed of a non-volatile or non-volatile organic liquid selected from hydrocarbons. A novel water-based ink backflow preventive composition comprising an anti-adhesion agent. 2. The novel water-based ink backflow preventive composition according to claim 1, wherein the crystalline polyolefin is crystalline polyethylene and / or crystalline polypropylene.