JP5438881B2 - Marking pen ink composition for wet surfaces - Google Patents

Description

  The present invention relates to an ink composition for a marking pen that enables writing on a surface of various articles containing a non-absorbent material without any trouble even in a wet state.

  The marking pen can be easily written on the surface of non-absorbent materials such as metal, plastic, glass, ceramic, and various coating films in addition to the surface of absorbent materials such as paper and cloth with an ink penetrating writing core. Because of this advantage, it is widely used not only for educational and office purposes but also for industrial purposes. Various ink-based and water-based compositions are known as inks for such marking pens, and so-called paint markers using oil-based inks with a colorant as a pigment are quick-drying and excellent in handwriting fastness.

  However, with a conventional general marking pen, it is difficult to write or fix even an oil-based paint marker on the surface of an article wetted with water, of course. Therefore, for example, at construction sites such as buildings, bridges, plants, etc., and outdoor material storages associated with them, letters and codes are assigned to the material surface and construction site in order to sort the materials and indicate the use site and installation order, etc. However, in places where it is unavoidable to rain, the writing work during the rain must be interrupted, and if the wetness does not dry even after the rain, wipe off the water adhering to the surface with a cloth. Therefore, the work efficiency is poor and the construction period is delayed.

Therefore, in recent years, as a marking pen ink that can be written on the surface of an article wet with water, a resin and an oxide wax soluble in an organic solvent composed of an isoparaffin hydrocarbon having 6 to 10 carbon atoms and / or an alkylcyclohexane are used. Dissolved oil-based ink (Patent Document 1), oil-based ink (Patent Document 2) in which a dye having a phenyl group and / or a dye bonded to an alkylphenol resin and an alkylphenol resin are dissolved in an isoparaffin hydrocarbon having 6 to 10 carbon atoms, An ink composition (Patent Document 3) in which an alkylphenol resin having a contact angle between a resin coating film and water of 90 ° or more and an oil-soluble dye are dissolved in an isoparaffin solvent, an alkylphenol resin having an alkyl group having 5 or more carbon atoms And oil-soluble three primary color dyes dissolved in aliphatic hydrocarbon solvents Composition (Patent Document 4) it has been proposed.
JP 2004-99819 A JP 2004-231726 A JP 2006-56947 A JP 2006-56946 A

  However, in the marking pen using the proposed ink composition, although it is possible to write on the surface of an article wet with water, it is difficult to write continuously and repeatedly, and it is difficult to write on the surface of the article. It is inferior in stickiness of the handwriting, easily disappears when the hand and the clothes touch the handwriting, and because it is dye ink, it is poor in weather resistance and light resistance, especially in an environment exposed to sunlight outdoors, it fades in a short time. At the same time, there is a problem that white ink cannot be prepared.

  In view of the above-described circumstances, the present invention is a marking pen ink composition that can be clearly and repeatedly written on various article surfaces including non-absorbent materials even when wet with water, without any problem. In addition to being able to adhere to the surface of the wet article, the handwriting has good stickiness, it is difficult to disappear even if it is touched by hands or clothes, and it is difficult to cause discoloration even in an environment exposed to sunlight outdoors. It is an object of the present invention to provide what can be prepared.

In order to achieve the above object, the invention of claim 1 is a marking pen ink composition for a wetted surface for writing on the wetted surface, and is represented by Solvent Polarity / Polarizability (solvent polarity / polarizability). 30 to 100 parts by weight of a binder resin soluble in this solvent and 20 to 150 parts by weight of a coloring pigment with respect to 100 parts by weight of an aliphatic hydrocarbon solvent having 5 to 11 carbon atoms having a characteristic value of 0.60 or less Part and 0.2 to 10 parts by weight of hydrophobic silica fine particles are blended.

Further, in the marking pen ink composition for a wetted surface according to claim 1, the invention according to claim 2 is based on 100 parts by weight of the aliphatic hydrocarbon solvent, and the dispersant for the coloring pigment is 0.02 to 10% by weight. The composition in which the parts are blended, and the invention of claim 3 employs a structure containing titanium oxide as a coloring pigment.

The marking pen ink composition for wetted surfaces according to the invention of claim 1 is a color pigment, a binder resin, and a hydrophobic silica for an aliphatic hydrocarbon solvent having a specific carbon polarity and having a specific solvent polarity. Because it contains fine particles in a specific ratio, when writing on the surface of various articles containing non-absorbent materials wetted with water, the ink itself clearly gets wet with the surface of the article while repelling the water with the tip of the brush. It can be written, and even if it is repeated many times, the writing performance is not easily deteriorated, and water does not get on the surface of the handwriting again. Forms a strong handwriting coating that is hard to disappear even when touched. In addition, marking pens using this ink composition can be labeled with pigments and are excellent in weather resistance and light resistance. Can be provided.

According to the invention of claim 2 , there is an advantage that the above-described marking pen ink composition for water-wetting surface has a good dispersibility for coloring pigments and can be reliably prepared in terms of performance.

According to invention of Claim 3 , what has high concealability is provided as said marking pen ink composition for wet surfaces .

For wet surface marking pen ink composition according to the present invention, as described above, a coloring pigment, Solvent Polarity / Polarizability characteristic value represented by (solvent polarity / polarizability) 0.60 The following aliphatic It contains a hydrocarbon-based solvent, a binder resin soluble in this solvent, and hydrophobic silica fine particles, and belongs to an oil-based pigment ink. In the container of a writing instrument with a valve similar to a conventional paint marker, The ink is stored in a free-flowing state, and the ink penetrating writing core is pressed against the surface of a desired article and written in a valve-opened state. Of course, the writing is not limited to the surface of absorbent materials such as paper, cloth, and wood, the surface of non-absorbent materials such as metal, plastic, glass, ceramic, and various coating films, and also concrete surfaces and asphalt. A rough surface such as a road surface is also possible, and even when the surface of the article is wet, it can be performed without any problem.

  That is, in this ink composition, by using a solvent having a low solvent polarity, the ink is very small in polarity, and in addition to being hydrophobic and having a low surface tension, water repellency is large due to the presence of hydrophobic silica. Therefore, when writing on the surface of an article wet with water, the ink itself is good on the article surface by repelling the water, which is a polar substance, and pushing away the water film to both sides of the brush tip. Since the handwriting coating film is formed by getting wet and water does not reappear on the surface of the handwriting, the handwriting coating film quickly dries and cures and firmly adheres to the article surface. Moreover, in this ink composition, when writing on the surface of a wet article, the resin component does not aggregate inside the ink penetrable writing core, and the ink is not confined. In addition, since the pigment and hydrophobic silica fine particles are dispersed and contained in an appropriate ratio, the water-repellent liquid agent is well-organized, and the ink film spreads or separates in water when writing on the surface of a wet article. In addition, the handwriting and the clothes can be obtained at a stage immediately after writing. It doesn't disappear easily when touched.

  Therefore, according to the marking pen (paint marker) using this ink composition, for example, in the construction site of buildings, bridges, plants, etc. When writing, it can be done without interrupting the writing work even when rain can not be avoided, and it can be directly written without the need to wipe off the water adhering to the surface of the article even when the water wet after raining does not dry The work efficiency is improved and the construction period is shortened. In addition, since this ink composition is a pigment ink using a pigment as a colorant, it has excellent weather resistance and light resistance, even in an environment where it is exposed to sunlight outdoors such as the above construction site or material storage place. , The handwriting is kept clear for a long time without discoloration.

As described above, the solvent used in the present invention has a characteristic value (hereinafter abbreviated as SPP value) represented by Solvent Polarity / Polarizability (0.6) or less. However, even if the SPP value of the solvent used is slightly over 0.60, the ink composition does not repel water when written on the surface of a wet article, and the ink composition can be written. The film is submerged in the adhering water and disturbed, and a clear handwriting cannot be obtained, and the handwriting coating film does not sufficiently adhere to the surface of the article. Further, an ink composition using a solvent having an SPP value greatly exceeding 0.60 cannot be written on the surface of an article wet with water. Incidentally, the SPP value of water is 0.962.

The solvent having an SPP value of 0.60 or less is not particularly limited, but an aliphatic hydrocarbon solvent having 5 to 11 carbon atoms having the solvent polarity is recommended in terms of availability and stability. Is done. Preferable specific examples of such aliphatic hydrocarbon solvents include pentane ( SPP value 0.507), hexane (0.519), heptane (0.526), octane (0.542), Nonane (0.552), decane (0.562), linear aliphatic hydrocarbons such as dodecane (0.571), 2-methylbutane (0.479), trimethylpentane (0.533) ), A branched aliphatic hydrocarbon such as cyclopentane (0.535), cyclohexane (0.557), methylcyclohexane (0.563), ethylcyclohexane (0.548), n-propylcyclohexane ( 0.571) and cyclooctane (0.590), and isomers thereof. And these solvents can also use 2 or more types together.

  The binder resin of the ink composition is not particularly limited as long as it can be dissolved in the solvent used. Thus, suitable binder resins in the case of using an aliphatic hydrocarbon solvent include, for example, rosin, rosin ester, maleic acid resin, aliphatic hydrocarbon resin, hydrogen terpene resin, aromatic modified terpene resin, terpene phenol resin. , Phenol resins and the like, and two or more of these may be used in combination.

In order to obtain the above-described effects, the amount of the binder resin needs to be larger than that in the case of a general writing instrument ink, and is 30 to 100 parts by weight with respect to 100 parts by weight of the solvent. The range . If the blending amount is too small, the resin component will agglomerate in contact with water inside the ink penetrable writing core even if it can be written by repelling water for the first few times in writing on the wet surface. As a result, the ink is confined inside the writing core and writing becomes difficult, and the sticking property of the handwriting on the wet surface becomes insufficient. On the other hand, if the amount is too large, the writing property is deteriorated due to excessive viscosity of the ink. In addition, the blending amount of the binder resin in a general paint marker ink is usually about 10 parts by weight with respect to 100 parts by weight of the solvent.

  As the color pigment used in the ink composition, various organic pigments can be used in addition to inorganic pigments such as titanium oxide and carbon black. However, organic pigments that are basically excellent in fastness are preferable. For example, all commercially available products are chromofine red, chromofine magenta, chromofine yellow, chromofine blue, and seica first red manufactured by Dainichi Seika Kogyo Co., Ltd. Seica First Yellow, Seika First Carmine, Cyanine Blue and the like are recommended as suitable. In addition, these color pigments may be used in combination of two or more for color matching of the ink. In particular, in the case of an organic pigment, it is recommended to use it together with titanium oxide in order to increase the hiding power of the ink.

  The optimum range of the color pigment content in the ink composition varies depending on the type, but should be within the range of 20 to 150 parts by weight with respect to 100 parts by weight of the solvent. On the other hand, if the amount is too large, the writing property deteriorates and the writing core is easily clogged.

  Hydrophobic silica fine particles used in the ink composition may be blended as an anti-settling agent in paint systems containing solid particles such as pigments. In the composition of the present invention, it is important as a water repellent aid and a viscosity imparting agent. Demonstrate the function. In other words, the ink composition, as a result of the addition of the hydrophobic silica fine particles, increases the overall water repellency and also increases the viscosity. In addition to being able to demonstrate it, the water-repellent liquid agent is better organized, it can form clear handwriting, and it can reliably avoid water getting on the surface of the handwriting with strong water repellency. It quickly dries and cures and firmly adheres to the surface of the article.

  The blending amount of such hydrophobic silica fine particles should be in the range of 0.2 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the solvent. . If the blending amount is too small, the above-mentioned effects are not sufficiently exhibited, and the writing property on the surface of the wet article is lowered. On the contrary, if the blending amount is too large, the writing property is deteriorated due to excessive viscosity of the ink. In addition, as a suitable commercial item of hydrophobic silica fine particle, the brand name Mizukazil made from Mizusawa Chemical Co., Ltd., the brand name Aerosil made from Nippon Aerosil Co., Ltd., etc. are mentioned.

The marking pen ink composition for water-wetting surface according to the present invention includes the above-described solvent having an SPP value of 0.60 or less, a binder resin, a color pigment, and hydrophobic silica fine particles as basic components. Depending on the amount, other additive components, for example, a dispersant corresponding to the pigment component to be used, can be appropriately blended in a small range. The optimum amount of the dispersing agent varies depending on the type and the blending amount of the pigment, but it is preferably in the range of 0.02 to 10% by weight with respect to 100 parts by weight of the solvent. If it is not expressed and is too much, the effect of other compounding ingredients will be inhibited.

In addition, in the marking pen ink composition for a wetted surface of the present invention, the blending amount of each component is set so that the viscosity of the entire ink is 1 to 50 mPa · S, more preferably 5 to 30 Pa · S at 25 ° C. It is recommended to adjust within the above range. If the viscosity of the ink as a whole is too low, good writing properties on the surface of an article wet with water cannot be obtained. Conversely, if the viscosity is too high, the flowability from the ink penetrating writing core is deteriorated.

  Examples of the present invention will be specifically described below in comparison with comparative examples. In the following, “parts” means parts by weight. The binder resins, color pigments, hydrophobic silica fine particles, and dispersants used in Examples and Comparative Examples are as follows.

Binder Resin A ... Aliphatic Hydrocarbon Resin (Highlets R-100X, Mitsui Petrochemical Industries, Ltd.)
Binder resin B ... terpene phenol resin (YShara Chemical YS Polystar T115)
Binder resin C: Coumarone indene resin (Escron V120 manufactured by Nippon Steel Chemical Co., Ltd.)
Binder resin D: Hydrogen terpene resin (Clearon M manufactured by Yasuhara Chemical)
Binder resin E: Acrylic resin (Beckosol-ODE-230-70 manufactured by Dainippon Ink & Chemicals, Inc.)
Binder resin F ... Maleic acid resin (Marquide No. 8 manufactured by Arakawa Chemical Industries)
Binder resin G ... Vinyl acetate resin (Denkasacanol manufactured by Yamatomi Corporation)
Binder resin H ... Ketone resin (K-90 manufactured by Arakawa Chemical Industries)
Titanium oxide: R-7E manufactured by Sakai Chemical Industry Co., Ltd., rutile carbon black: MA-100 manufactured by Mitsubishi Chemical Corporation
Organic pigment A ... Seika First Red (above)
Organic pigment B ... chromofine yellow (supra)
Hydrophobic silica fine particles A ... Mizusukazil P-73 manufactured by Mizusawa Chemical Co., Ltd.
Hydrophobic silica fine particles B ... Aerosil 300 manufactured by Nippon Aerosil Co., Ltd.
Dispersant A ... Dispersbyk-111 manufactured by BYKChmie
Dispersant B ... SOLSPERSE11200 manufactured by Nihon Lubrizol
Dispersant C ... SOLSPERSE300 manufactured by Nihon Lubrizol

Examples 1-9
Each component described in Tables 1 and 2 below was sufficiently stirred and mixed with a ball mill in the indicated compounding amount (parts by weight) to prepare a marking pen ink composition for a wet surface .

Comparative Examples 1-8
Each component described in Tables 3 and 4 below was sufficiently stirred and mixed with a ball mill in the indicated compounding amount (parts by weight) to prepare an ink composition for a marking pen. The SPP values of the solvents used in Comparative Examples 5 to 8 are 0.617 for p-xylene, 0.795 for ethyl acetate, 0.881 for methyl ethyl ketone, and 0.842 for 2-butanol.

Comparative Example 9
Isoparaffinic solvent (Isopar G manufactured by Exsol Mobil) ... 70.0 parts Isoparaffinic solvent (Isopar E manufactured by Exsol Mobil) ... 30.0 parts Alkylphenol resin (Hitanol 1133 manufactured by Hitachi Chemical Co., Ltd.) -28.0 parts Carbon black (Oil Black 803 manufactured by Orient Chemical Co., Ltd.) ... 14.0 parts The ink components for marking pens were prepared by sufficiently stirring and mixing the above components with a homodisper.

Comparative Example 12
Isooctane: 50.0 parts Isononane: 50.0 parts Alkylphenol resin (supra: Hitanol 1133): 44.0 parts C.I. I. Solvent Black 3 (manufactured by Orient Chemical Co., Ltd.) 12.5 parts The above components were sufficiently stirred and mixed with a homodisper to prepare an ink composition for a marking pen.

  About each ink composition prepared by the above Example and Comparative Example, the ink composition of Examples 1-9 and Comparative Examples 1-8 is a writing instrument with a valve for normal paint markers (bold type: writing core diameter 1). .5 mm) in a free-flowing state, and the ink compositions of Comparative Examples 9 and 10 were impregnated in the batting of the batting type marking pen (bold type: writing core diameter 1.5 mm). In each case, the writing property with respect to the wetted metal surface and the wetted painted surface and the handwriting fixability with respect to these surfaces were evaluated by the following methods. The results are shown in Tables 1-4.

<Writability of wet metal surfaces and wet paint surfaces>
About 5 ml of water is sprayed almost uniformly on the entire surface of a 100 mm vertical and horizontal aluminum plate and the entire coated surface of a steel plate coated with acrylic resin paint of the same size by a household sprayer, so that innumerable water droplets are dense. A writing operation was performed on the adhered surface, and the results were classified as follows.
◎ ・ ・ ・ Can be written clearly by repeating the water over and over again.
○… You can write repeatedly by flipping water, but the handwriting is slightly drowning.
□ ・ ・ ・ Can be written by flipping water, but repeated writing makes it difficult to get ink.
Δ: Can be written several times by flipping water, but cannot be repeated afterwards.
▲ ・ ・ ・ Writing is possible without playing water, but the handwriting is distorted and unclear.
× ・ ・ ・ Plays water, but can't write.
XX: The ink elutes in water and cannot be written.

<Handwriting stickiness>
Five straight lines were written on the aluminum plate and the coated steel plate, and after about 1 minute, the portion with the handwriting was lightly wiped with a towel whose surface was dried, and the state of the handwriting was evaluated in the following three stages. In addition, (-) in the table indicates that writing cannot be performed and stickiness cannot be evaluated.
◎ ・ ・ ・ No change in handwriting.
Δ: A part of the handwriting peeled off.
X: Most of the handwriting was peeled off.

  As is apparent from the results of Tables 1 and 2, the ink composition according to the present invention can be easily and repeatedly written in the form of splashing water on the wetted metal surface and painted surface. A clear and strongly fixed handwriting is obtained. However, as shown in Table 3, in the ink composition not containing the hydrophobic silica fine particles (Comparative Example 1) and the ink composition in which the blending ratio of the binder resin is too small (Comparative Example 3), the water wetted surface In contrast, the ink composition (Comparative Examples 2 and 4) in which the blending ratio of the hydrophobic silica fine particles and the binder resin is excessively high can not be written repeatedly. I understand that.

On the other hand, as shown by the results in Table 4, in the ink compositions (Comparative Examples 6 to 8) using a solvent having an SPP value exceeding 0.60 , the ink is eluted in water and cannot be written. Even in the case of an ink composition (Comparative Example 5) using a solvent whose SPP value slightly exceeds 6.0, even if writing is possible without repelling water, the handwriting is distorted and unclear. It has poor adhesiveness and can be easily peeled off by rubbing in an undried state. Furthermore, in the ink composition using the dye as the colorant (Comparative Examples 9 and 10), it is possible to write by repelling water by using a solvent having an SPP value of 0.60 or less, but it can be written only several times. After that, it becomes impossible to write, and the handwriting film is also easily peeled off. Note that an ink composition using a dye as a colorant is inferior in light resistance and weather resistance, and therefore has a problem that discoloration occurs in a short time, particularly when used outdoors.

Claims (3)

A marking pen ink composition for writing on a wet surface,
A binder soluble in this solvent with respect to 100 parts by weight of an aliphatic hydrocarbon solvent having 5 to 11 carbon atoms and having a characteristic value expressed by Solvent Polarity / Polarizability of 0.60 or less. A marking pen ink composition for water-wetting surfaces, comprising 30 to 100 parts by weight of a resin, 20 to 150 parts by weight of a color pigment, and 0.2 to 10 parts by weight of hydrophobic silica fine particles. The marking pen ink composition for water-wetting surfaces according to claim 1, wherein 0.02 to 10 parts by weight of the dispersant for the coloring pigment is blended with 100 parts by weight of the aliphatic hydrocarbon solvent. The marking pen ink composition for water-wetting surfaces according to claim 1 or 2, comprising titanium oxide as a coloring pigment.