JPH1121493A - Ink composition for oily marking pen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink composition for an oily marking pen, capable of guaranteeing properties for fixing a coated membrane to a nonabsorptive surface such as a metal and a plastic same as or more than the case using a nonpolar solvent such as xylene by using a polar organic solvent. SOLUTION: This ink composition for an oily marking pen is constituted of a coloring agent, a polar organic solvent, an oil-soluble resin and a carboxy- modified silicone having 2,000-20,000 number average molecular weight. The content of the carboxy-modified silicone is 0.01-10 wt.% based on the whole amount of the ink composition. The polar organic solvent includes an alcoholic solvent and a glycol ether-based solvent, and the oil-soluble resin includes at least one kind selected from a ketonic resin, a phenolic resin, a xylene-based resin, a rosin resin, a styrene-organic acid copolymer and a polyacrylic ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition for an oil-based marking pen, and more particularly, to an ink composition for an oil-based marking pen which is excellent in fixability of a coating film when written on a non-absorbing surface such as a metal or a plastic. About things.

[0002]

2. Description of the Related Art Conventionally, non-polar solvents such as xylene have been used as solvents in ink compositions for oil-based marking pens. However, in recent years, polar solvents such as alcohols and glycol ethers have been used in view of safety and the like. It is shifting to use.

However, with the shift from non-polar solvents to polar solvents, the use of metals,
When writing on a non-absorbing surface such as plastic, the fixability of a coating film (handwriting such as prints and images) tends to decrease. This is because the use of a polar solvent weakened the etching action and hydrogen bonding on the non-absorbing surface, which are thought to have been acting on the fixability of the coating film when the non-polar solvent was used. This is considered to be due to impairment of the adhesion and fixability of the coating film to the film.

[0004] Accordingly, by adding a resin or the like to an oil-based marking pen ink composition containing a polar solvent, the fixing property of a coating film on a non-absorbing surface is improved.
As such an attempt, for example, Japanese Patent Laid-Open No.
In JP-A-Hei 3 (1993), an ink composition containing a condensation resin of formaldehyde and toluenesulfonamide is proposed.
JP-A-172366 discloses an ink composition containing a vinyl acetate resin, and JP-A-3-2500073 discloses an ink composition containing a polyamide resin and an alcohol-soluble resin (such as a phenol resin). JP-A-4-139273 discloses an ink composition using a resin having a hydrophilic group such as an acrylic resin and a polyamide resin in combination with a resin having a hydrophobic group such as a ketone resin and a rosin-modified maleic resin. ing. JP-A-4-168169 discloses a rosin-modified maleic resin,
An ink composition using a resin having an acid value of 10 or less, such as a saturated polyester resin, and a resin having an acid value of 80 or more, such as a ketone resin or a polyamide resin, has been proposed.
JP-A-4-227670 discloses an ink composition containing a polyvinyl alkyl ether and a styrene-acrylic acid copolymer, and JP-A-4-239071 discloses a condensation resin of aldehyde and urea and a cationic surfactant. An ink composition containing an agent has been proposed,
No. 975 discloses an ink composition containing a rosin, a rosin-modified resin, a ketone resin, and the like, and a methyl ester of a hydrogenated rosin, a hydrogenated triethylene glycol ester, and the like. Further, JP-A-5-177717 proposes an ink composition containing a ketone resin having a softening point of 60 to 100 ° C and a phenol resin having a softening point of 60 to 100 ° C, which is soluble in ethanol. Discloses an ink composition using a ketone resin, a phenol resin, a rosin resin, a butyral resin, and a polyamide resin,
JP-A-7-118590 discloses an ink composition containing a ketone resin, a phenol resin, a rosin resin, a butyral resin, a polyamide resin, and a phthalate ester.

[0005]

However, even with these ink compositions, a coating film (a handwriting such as a print or an image) is required.
And the fixability to a non-absorbing surface such as metal or plastic is low, and an ink composition having a satisfactory fixability has not yet been obtained.

[0006] Accordingly, an object of the present invention is to provide an ink composition for an oil-based marking pen having high fixability of a coating film even when a polar organic solvent is used as a solvent. Another problem of the present invention is that even when a polar organic solvent is used, the fixability of the coating film is equal to or higher than that when a non-polar organic solvent such as xylene is used, on a non-absorbing surface such as a metal or a plastic. An object of the present invention is to provide an ink composition for an oil-based marking pen that can be secured.

[0007]

Means for Solving the Problems In a conventional ink composition for marking pens using an alcohol-based or glycol ether-based solvent, the fixability between a coating film (handwriting) and a non-absorbing surface of the ink composition is improved. Intensive investigation into the fact that is not always sufficient, focusing on the problem that it was only required to improve the adhesion and fixability between the solid content of the resin and dye in the coating film and the surface of the non-absorbing surface. did. Of course, there is no difference that the adhesion and fixability between the solids such as resin and dye in the coating film and the surface of the non-absorbing surface play an important role in improving the fixability of the coating film.

However, in these methods, the improvement in the adhesion and fixability of the coating film to the surface of the non-absorbing surface leads to the fact that at the same time, other substances that come into contact with the coating film surface easily adhere to the coating film surface. That is, the ease with which other substances in contact with the coating film surface adhere to the coating film surface is proportional to the adhesion and fixability of the coating film to the non-absorbing surface. Therefore, as a measure for improving the fixability between the coating film and the non-absorbing surface, a combination of various resins as a measure for improving the adhesion, the adhesion between the coating film and the non-absorbing surface, the fixing property is improved, but at the same time, The adhesion of other substances to the surface of the coating film also increases, and the coating film easily adheres when rubbed with fingers, cloth, paper, or the like, and does not substantially improve fixability.

The present inventors have conducted intensive studies based on such findings, and as a result, when an ink composition containing a colorant, a polar organic solvent and a resin contains carboxy-modified silicone,
The inventors have found that the fixability between the coating film and the non-absorbing surface can be improved, and have completed the present invention. The carboxy-modified silicone is not completely compatible with the polar organic solvent, and because of the specific surface activity of the carboxy-modified silicone, when it is written on the non-absorbing surface as ink, the carboxy-modified silicone is Move to As a result, the carboxy-modified silicone hardly affects the fixability between the coating film and the surface of the non-absorbing surface, and exhibits the characteristic hard-to-adhere property to other substances on the coating film surface. Therefore, the coating is finger,
Even when rubbed with cloth, paper, etc., the coating film does not adhere easily,
As a result, the fixability on the substantially non-absorbing surface is improved. That is, the coating film formed by the ink composition containing the carboxy-modified silicone has a high level of adhesiveness between the coating film and the surface of the non-absorbing surface, a high level of fixability, and a low level of adhesion to other substances at the same time. . The invention according to claim 1 includes a coloring agent,
An oil-based marking pen ink composition containing a polar organic solvent, an oil-soluble resin, and a carboxy-modified silicone.

[0010] In particular, the ink composition of the present invention uses a carboxy-modified silicone despite the use of a polar organic solvent, and is equivalent to or uses a non-polar solvent such as xylene as a solvent. Further fixing property of the coating film can be secured on the non-absorbing surface of metal, plastic, or the like.

As the carboxy-modified silicone, those having a number average molecular weight of 2,000 to 20,000 can be used optimally. The invention of claim 2 is the ink composition for an oil-based marking pen according to claim 1, wherein the number average molecular weight of the carboxy-modified silicone is from 2,000 to 20,000.

The carboxy-modified silicone is preferably used in an amount of about 0.01 to 10% by weight based on the total weight of the ink composition. According to the invention of claim 3, the carboxy-modified silicone is added in an amount of 0.1% based on the total amount of the ink composition.
The oil-based marking pen ink composition according to claim 1, wherein the ink composition comprises 0.01 to 10% by weight.

More specifically, the polar organic solvent includes an alcohol-based or glycol ether-based organic solvent. These polar organic solvents are highly safe not only for the human body but also in the method of use. The invention according to claim 4 is the oil-based marking pen ink composition according to any one of claims 1 to 3, wherein the polar organic solvent is an alcohol-based solvent or a glycol ether-based solvent.

The oil-soluble resin (hereinafter sometimes simply referred to as “resin”) includes ketone resins, phenol resins, xylene resins, rosin resins, styrene-organic acid copolymers, polyacrylic acid. Esters and the like. The invention according to claim 5 is the resin according to claims 1 to 4, wherein the resin is at least one selected from a ketone resin, a phenol resin, a xylene resin, a rosin resin, a styrene-organic acid copolymer and a polyacrylate. An ink composition for an oil-based marking pen according to any one of the above items.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION

(Carboxy-modified silicone) A feature of the present invention is that an ink composition containing carboxy-modified silicone is used as an ink composition for an oil-based marking pen. As described above, the carboxy-modified silicone exhibits poor adhesion to other substances on the surface of the coating film (handwriting), so that the fixability of the coating film can be improved. As such a poorly adherent surface layer forming substance, carboxy-modified silicone exhibits extremely high poor adhesion among silicone-based polymer surfactants.

The carboxy-modified silicone is not particularly limited, and a commercially available carboxy-modified silicone oil can be used. As such a carboxy-modified silicone oil, for example, a product name “TSF4” from Toshiba Silicone Co., Ltd.
770 "is commercially available, and the product names" X-22-3710 "and" X-22-162 "are available from Shin-Etsu Chemical Co., Ltd.
A "and" X-22-3701E "are commercially available.

The molecular weight (number average molecular weight) of the carboxy-modified silicone is not particularly limited.
30,000, preferably 2,000 to 20,000,
More preferably, it is about 5,000 to 20,000. If the molecular weight is too low, the water resistance will decrease, and if it is too high, it will be difficult to transfer to the coating film surface, the poor adhesion will be low, and the fixability will sometimes decrease.

The amount of the carboxy-modified silicone used is, for example, 0.01 to 10% by weight, preferably 0.2 to 10% by weight, based on the total amount of the ink, depending on the type of the component and other components (colorant, resin, etc.). About 4.0% by weight. Beyond these ranges, the carboxy-modified silicone migrates not only on the surface of the coating film but also near the coated surface, and rather produces secondary effects such as inhibition of adhesion to the coated surface. On the other hand, when the amount is less than these ranges, poor adhesion of the coating film is low, and fixability is reduced.

(Colorant) The colorant is not particularly limited. As the coloring agent, those having high safety are preferable. In addition, a colorant that is soluble in a polar organic solvent described later or a colorant that can be dissolved in a polar organic solvent using a dissolution aid (solubiliser) can be suitably used. Examples of the colorant include oil-soluble black nigrosine dye (manufactured by Chuo Gosei Kagaku Co., trade name: Oil Black 2030), oil-soluble black dye (manufactured by Orient Chemical Co., trade name: Varifast Black 3810, etc.), oil-soluble Red dye (manufactured by Orient Chemical Co., trade name: Varifast Red 1308, etc.), oil-soluble blue dye (manufactured by BASF, trade name: Neozapon Blue 807, etc.), oil-soluble yellow dye (manufactured by Hodogaya Chemical Co., Ltd., product Oil-soluble dyes such as spin yellow C-GNH). The colorants can be used alone or in combination. The amount of the colorant used is 1 to 15% by weight, preferably 3 to 12% by weight, based on the total amount of the ink.
If the amount of the coloring agent is too large, the viscosity increases and the writability decreases. On the other hand, if it is too small, the handwriting density is low.

(Polar Organic Solvent) The polar organic solvent replaces non-polar solvents such as benzene and toluene, which have conventionally been problematic in terms of safety, and examples thereof include alcohol solvents and glycol ether solvents. It is not something to be done. As the alcohol-based solvent, particularly one having 1 to 4 carbon atoms.
Aliphatic alcohols such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, and tert-butyl alcohol are preferred.
Examples of glycol ether solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether. Ethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobumethyl ether acetate and the like can be mentioned. Preferred glycol ether solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, and dipropylene glycol monomethyl ether.

The polar organic solvent can be used alone or in a mixture of two or more.
% By weight, preferably about 64 to 92% by weight. If the amount of the polar organic solvent is too large, the density of the handwriting decreases. On the other hand, if the amount is too small, the viscosity increases and the writability decreases, and the solubility of the coloring agent, the oil-soluble resin, and the like is low.

(Resin) The resin is not particularly limited as long as the resin is soluble in the polar organic solvent. Preferably, it is required to be safe. Examples of the resin include a ketone resin, a phenol resin (eg, an alkylphenol resin, a phenol resin, a rosin-modified phenol resin, etc.), a xylene resin (eg, an alkylphenol-modified xylene resin, a rosin-modified xylene resin, etc.), a rosin resin, Styrene-organic acid copolymers (e.g., styrene-acrylic acid copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, etc.), polyacrylates, and the like are preferably used. The resins can be used alone or in combination. The amount of the resin used is, for example, 3 to 25% by weight based on the total amount of the ink,
Preferably, it is about 5 to 20% by weight. If the amount of the resin used exceeds these ranges, the viscosity increases and the writability decreases. On the other hand, if it is less than these ranges, the adhesion of the coating film (handwriting) to the coated surface is low.

In addition, the ink composition of the present invention may contain various additives such as a viscosity modifier, a structural viscosity imparting agent, a dye solubilizing agent, and a drying agent.
Various additives are not particularly limited, and known additives can be widely used.

(Production method) The ink composition of the present invention can be prepared by mixing the above-mentioned components (colorant, polar organic solvent, resin, carboxy-modified silicone, etc.). The method for preparing the ink composition is not particularly limited. For example, a polar organic solvent and a resin are mixed under heating (for example, at 50 ° C.).
Then, a colorant and, if necessary, various additives are added, and the mixture is stirred and mixed under heating (for example, at 50 ° C.). After stirring and mixing, a method in which heating is stopped, a carboxy-modified silicone is added, and the mixture is stirred and mixed can be exemplified.

The ink composition of the present invention has a non-absorbing surface (a metal plate such as a tin plate, a writing surface such as a plastic film or sheet such as a film or sheet formed of polyethylene or polypropylene) as an ink, It is useful as an ink composition for oil-based marking pens because it has excellent fixability of the coating when written on a surface that hardly absorbs ink.

[0026]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. (Raw materials) The following colorants, polar organic solvents, oil-soluble resins, carboxy-modified silicones, and the like were used as raw materials. (Coloring agent) Oil-soluble black nigrosine dye: Trade name “Oil Black 2030” (manufactured by Chuo Gosei Chemical Co., Ltd.) Oil-soluble red dye: trade name “Varifast Red 1308” (manufactured by Orient Chemical Company) Oil-soluble blue dye: Trade name "Neozapon Blue 807" (manufactured by BASF) Oil-soluble yellow dye: trade name "Spiron Yellow C-GNH" (manufactured by Hodogaya Chemical Co.) (polar organic solvent) ethanol isopropyl alcohol propylene glycol monomethyl ether: trade name "Dowanol PM" (manufactured by Dow Chemical Company) Ethylene glycol monobutyl ether: trade name "Dowanol EB" (manufactured by Dow Chemical Company) Dipropylene glycol monomethyl ether: trade name "Dowanol DPM" (manufactured by Dow Chemical Company) (oil-soluble Resin) Alkyl phenol resin: Product name NOR 510 "(Arakawa Chemical Industries) Ketone resin: Trade name" Hilac 111 "(Hitachi Chemicals) Alkylphenol-modified xylene resin: Trade name" Nicanol HP-100 "(Mitsubishi Gas) Styrene-maleic acid resin : Trade name "Alastar 700" (Arakawa Chemical Industries) Polyacrylic acid ester: Trade name "Dianal BR101" (Mitsubishi Rayon) Acrylic-styrene resin: Trade name "John Krill 683" (Johnson Polymer) Rosin resin: Trade name “Rosin WW” (manufactured by Tokushima Seiyaku Co., Ltd.) (carboxy-modified silicone) Silicone 1: trade name “X-22-3710” (manufactured by Shin-Etsu Chemical Co., Ltd.) Silicone 2: trade name “TSF4770” (Toshiba Silicone) (Other company) Nigrosine dye solubilizer (oleic acid)

(Examples 1 to 5 and Comparative Examples 1 to 6) In Examples and Comparative Examples, the proportions shown in Table 1 or Table 2 (the amounts of the various components in Tables 1 and 2 were all Parts by weight) to obtain an oil-based marking pen ink composition. Specifically, for each of Examples and Comparative Examples, a polar organic solvent and an oil-soluble resin were mixed while heating and stirring at 50 ° C. for 1 hour, and then a colorant (oil-soluble dye) and various additives were added. Then, the mixture is further heated and stirred at 50 ° C. for 30 minutes. After the mixing, the heating was stopped, the carboxy-modified silicone was charged, and the mixture was stirred and mixed for 10 minutes to obtain an oil-based ink composition for a marking pen.

[0028]

[Table 1]

[0029]

[Table 2]

(Fixability Test) A writing instrument (oil-marker manufactured by Sakura Crepas, trade name) using the ink compositions for oil-based marking pens obtained in Examples 1 to 5 and Comparative Examples 1 to 6 using a felt as a pen tip. "Pen touch"), and using this, a straight line was written on a non-absorbing surface (a tin plate or a polyethylene plate). After drying for 30 minutes, the coating film was rubbed with a cotton swab at a load of 500 g. When the non-absorbing surface was completely exposed by rubbing, x was given, when the coating was scratched, and Δ was given when no change was observed in the coating, and the fixability of the coating was evaluated. The evaluation results are shown in Tables 1 and 2, respectively.

The ink composition for an oil-based marking pen of the present invention can be formed from a coating film (handwriting) from an ink composition for an alcohol-based oil-based marking pen containing no carboxy-modified silicone.
Has high fixability to non-absorbing surfaces.

[0032]

The ink composition of the present invention is an oil-based marking pen ink composition containing a colorant, a polar organic solvent, a resin, and a carboxy-modified silicone. Despite this, the fixability between the coating film and the non-absorbing surface is high. Further, the fixing property of the coating film equal to or higher than that when a non-polar solvent such as xylene is used can be secured on the non-absorbing surface of metal, plastic, or the like. As a result, the fixability of the coating on the non-absorbing surface is excellent,
An ink composition having high safety can be provided.

Claims (5)

[Claims] 1. An oil-based marking pen ink composition containing a colorant, a polar organic solvent, an oil-soluble resin, and a carboxy-modified silicone. 2. The ink composition according to claim 1, wherein the carboxy-modified silicone has a number average molecular weight of 2,000 to 20,000. 3. The ink composition according to claim 1, wherein the carboxy-modified silicone is contained in an amount of 0.01 to 10% by weight based on the total weight of the ink composition. 4. The ink composition for an oil-based marking pen according to claim 1, wherein the polar organic solvent is an alcohol-based solvent or a glycol ether-based solvent. 5. The oil-soluble resin according to claim 1, wherein the oil-soluble resin is at least one selected from a ketone resin, a phenol resin, a xylene resin, a rosin resin, a styrene-organic acid copolymer and a polyacrylate. The ink composition for an oil-based marking pen according to any one of the above items.