JP2015214633A - Solid drawing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid drawing material which has high concealment, is capable of covering a paper surface and a coat paper surface as a writing surface like a correction tape and allows writing on coating drawn lines with another writing instrument and removal of a coating film adhered to the writing surface by the solid drawing material itself.SOLUTION: A solid drawing material 10 comprising a wax, an extender material and a concealment pigment contains further one of 12-30C dibasic acids and their derivatives, a tackifier and 20-80 wt.% of an ethylene-vinyl acetate copolymer of a melting point of 60-90°C as a base material.

Description

  The present invention relates to a solid drawing material obtained by molding a wax, an extender, and a pigment into a solid.

Conventionally, various types of solid drawing materials such as crayons and crepes have been provided.
For example, the following Patent Document 1 discloses an ethylene vinyl acetate copolymer, a resin such as polyethylene (PE) and polypropylene (PP) 20 to 40%, waxes such as paraffin and hardened wax 20 to 40%, a pigment and an extender. A writable molding composition made of (talc, calcium carbonate, clays) is disclosed, and it is said that it is sufficient in strength even if molded into a complicated shape.

Patent Document 2 below discloses a solid drawing material comprising at least a pigment and an ethylene vinyl acetate copolymer wax, and the concentration is high even when drawn on a smooth paper surface such as art paper or coated paper. Has been.
Further, Patent Document 3 below discloses a solid correction composition containing two types of waxes having different melting points, a film-forming polymer curing agent (such as ethylene vinyl acetate polymer) having a melting point of 65 to 120 ° C., and an opaque pigment (titanium dioxide). It is disclosed to be easily deposited and bonded to the paper surface.

JP 48-35914 A JP-A-4-63880 JP-T-5-501384

In any of the above, the drawn line obtained by writing with a solid drawing material is dark, and there is a problem of fixing to the writing surface. However, no assumption has been made as to whether or not the drawn line once written on the writing surface can be erased and by what means.
Therefore, the present invention is a solid drawing material that has high concealability, can be coated on a paper surface or a coated paper surface as a writing surface like a correction tape, and can be written with another writing tool over a coated line. Furthermore, another object of the present invention is to provide a coating film that can remove the coating film adhered to the writing surface with the solid drawing material itself.

In view of the above problems, the present invention is a solid drawing material containing a wax, an extender, and a concealing pigment,
Further, C: 12-30 dibasic acid or derivative thereof, tackifier, and ethylene vinyl acetate copolymer, ethylene acrylic acid copolymer, ethylene ethyl acrylate having a melting point of 60-90 ° C. as a base material It contains 20 to 80% by weight of any copolymer and / or a mixture.
The “wax” in the present invention refers to what is generally classified as a wax among the components of the solid drawing agent. The wax as a component of the solid drawing material contributes to shape retention when not in use, but quickly collapses when a force is applied to impart lubricity during writing. Further, it is compatible with a tackifier that will be described later and imparts fixability to the writing surface. This wax preferably has a melting point of about 45 to 100 ° C. and a low melting temperature. Specifically, paraffin wax, microcrystalline wax, urushi wax, beeswax, molasses, montan wax, hardened castor oil, hardened palm oil and the like can be used as the wax in the present invention. The blending amount is preferably 50% by weight or less.

The “extension material” in the present invention is a component that contributes to improving the strength and writing performance of a solid writing instrument. Moreover, the auxiliary | assistant effect | action of the concealment pigment mentioned later is also exhibited. Specifically, talc, kaolin, mica, boron nitride, calcium carbonate, potassium titanate whisker, and the like can be used as the constitution material in the present invention. The blending amount is desirably 10 to 50% by weight of the whole.
The “concealing pigment” in the present invention is a component that contributes to concealing the foundation by the coating film obtained from the solid drawing material. Specifically, a concealing white pigment or a concealing black pigment can be used. As the concealable white pigment, titanium dioxide, which is an inorganic pigment, is most suitable as the present invention. It is. The blending amount is desirably 10 to 50% by weight of the whole. Other examples of the hiding white pigment include zinc oxide and white resin particles, but titanium dioxide is most preferable from the viewpoint of hiding power. Specifically, carbon black, graphite, and iron black can be used as the hiding black pigment.

  In the present invention, C: 12-30 dibasic acid or a derivative thereof is used to improve the fixing property and hiding property on the writing surface. Here, “C: a dibasic acid of 12 to 30” is a chain organic compound having carboxyl groups at both ends, as shown in the following chemical formula 1, and a chain portion other than carbon of the carboxyl groups at both ends. (R in Chemical Formula 1 below) has 12 to 30 carbon atoms.

  Here, “—R—” may be a straight chain as shown in the following chemical formula 2 or a branched chain as shown in the following chemical formula 3, and a double bond as shown in the following chemical formula 4 is formed in the middle. You may have.

  The “derivative” refers to a derivative obtained by chemically modifying the carboxyl groups at both ends. For example, ester compounds such as diglycidyl ester (following chemical formula 5) and methyl ester (following chemical formula 6), diol (Substitution formula 7 below) and diamine (substitution formula 8 below), polymer such as polyacid polyanhydride (following formula 9), sodium salt (following formula 10) and amine salt (following formula 11) There are such salts.

  When the melting point of the C: 12-30 dibasic acid or derivative thereof exceeds 70 ° C., the effect of improving the fixing property and the hiding property is hardly exhibited, and it is desirable that the melting point is 70 ° C. or less. Furthermore, when the above-mentioned quality improvement effect is calculated | required, it is desirable that content of C: 12-30 dibasic acid or its derivative (s) is the range of 1-12 weight% with respect to the whole solid drawing material. If the amount is less than 1% by weight, the effect of improving the colorability is not exhibited. On the other hand, if the amount exceeds 12% by weight, the colorability is not further improved and the writing quality is deteriorated. More preferably, the weight ratio of C: 12-30 dibasic acid or its derivative and the total waxes contained in the solid drawing material is such that the dibasic acid or its derivative: the wax = 2: 100- A range of 20: 100 is desirable. This is because when the dibasic acid or its derivative is less than 2: 100, the effect of improving the quality in the previous period is not exhibited, whereas when it exceeds 20: 100, the quality is not further improved and the writing quality is deteriorated.

The “tackiness imparting agent” in the present invention is used for the purpose of improving the fixability of a drawn line by a solid drawing material to a writing surface.
The “ethylene vinyl acetate copolymer”, “ethylene acrylic acid copolymer”, and “ethylene ethyl acrylate copolymer” in the present invention constitute the base material of the solid writing instrument of the present invention. When not in use, it gives flexibility to the solid writing instrument as a base material and contributes to shape retention. Further, at the time of writing, it contributes to the concealability by being worn like a coating film by the frictional heat with the writing surface and being fixed to the writing surface. In addition, this component contributes to the so-called “self-erasability”, which is finely crushed and removed by rubbing the film with the solid writing instrument itself. In order to exhibit these properties, the ethylene vinyl acetate copolymer, ethylene acrylic acid copolymer, and ethylene ethyl acrylate copolymer have a melting point of 60 to 90 ° C.
The melt flow rate defined in JIS K7210: 1999 for the ethylene vinyl acetate copolymer, ethylene acrylic acid copolymer, and ethylene ethyl acrylate copolymer is preferably 400 to 800 g / 10 min.

The ethylene vinyl acetate copolymer is preferably a polymer obtained by polymerizing a vinyl acetate monomer at a ratio of 10% by weight or more.
Further, the tackifier comprises a terpene resin, a modified terpene resin, a maleic acid resin derivative, a coumarone / indene resin, a coumarone / indene resin derivative, a styrene resin, an isoprene resin, a pine resin, a rosin ester, and a petroleum resin. It is desirable to be one or a mixture of two or more selected from the group.
As other components, for example, a small amount of oil having a melting point of 45 ° C. or less for the purpose of imparting lubricity can be used as long as it is less than 5% by weight. Examples of such oil include jojoba oil, liquid paraffin, squalane, squalene, and liquid paraffin.

Since the present invention is configured as described above, it has high concealability, and can be coated on a paper surface or coated paper surface as a writing surface like a correction tape. In addition, it is possible to provide a solid drawing material that can be removed by the solid drawing material itself.
In addition, since it does not contain volatile components as components, it is not necessary to wind the paper around, store it in a holder, or attach a cap. I won't follow you. Furthermore, it is supposed to have sufficient strength for writing in a bare core state without providing a reinforcing means such as a holder.

The solid drawing material which concerns on the Example and comparative example of this invention is shown with a perspective view.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, “EVA” means “ethylene vinyl acetate copolymer”, “EAA” means “ethylene acrylic acid copolymer”, and “EEA” means “ethyl ethyl acrylate copolymer”. It is. The unit of the numerical value described as “melt flow rate” is “g / 10 min”.

(1) Composition and production method of Examples and Comparative Examples (1-1) Example 1
Dibasic acid derivative (diglycidyl ester type; C = 18 (room temperature liquid)): 1.5% by weight
Base material (EVA (melting point 62 ° C., melt flow rate: 400, trade name: EV210 (vinyl acetate content: 28% by weight), Mitsui DuPont Polychemical)): 30% by weight
Wax (Urushiro (melting point: 52 ° C.)): 9.5% by weight
Wax (Caster wax (melting point 85 ° C.)): 9.5% by weight
Body material (talc): 9.5% by weight
Concealment pigment (titanium dioxide): 20% by weight
Tackifier (ester gum (rosin ester, softening point 86 ° C.)): 15% by weight
Oil (liquid paraffin): 5% by weight
Here, in this example, a dibasic acid derivative represented by the following chemical formula 12 was used.

The weight ratio of the dibasic acid derivative to the total waxes is
1.5: (9.5 + 9.5) = 1.5: 19≈7.9: 10
Met.
As shown in FIG. 1 having a diameter of 10.0 mm, the above blended composition is heated and mixed and dispersed with a kneader and then kneaded with two rolls, then heated and melted, poured into a predetermined mold, cooled and solidified. A white solid drawing material 10 was obtained.

(1-2) Example 2
Dibasic acid derivative (diglycidyl ester type; C = 18 (room temperature liquid)): 1.5% by weight
Substrate (EVA (melting point: 62 ° C., melt flow rate: 400, trade name: EV210, Mitsui / DuPont Polychemical): 30% by weight
Wax (cured tallow oil (melting point: 52 ° C.)): 9.5% by weight
Wax (Caster wax (melting point 85 ° C.)): 9.5% by weight
Body material (talc): 9.5% by weight
Concealment pigment (titanium dioxide): 20% by weight
Tackifier (ester gum (rosin ester, softening point 86 ° C.)): 15% by weight
Oil (liquid paraffin): 5% by weight
In this example, the same dibasic acid derivative as in Example 1 was used.
As shown in FIG. 1 having a diameter of 10.0 mm, the above blended composition is heated and mixed and dispersed with a kneader and then kneaded with two rolls, then heated and melted, poured into a predetermined mold, cooled and solidified. A white solid drawing material 10 was obtained.

(1-3) Comparative Example 1
Substrate (EVA (melting point: 62 ° C., melt flow rate: 400, trade name: EV210, Mitsui / DuPont Polychemical): 30% by weight
Wax (Urushiro (melting point 52 ° C.)): 10% by weight
Wax (Caster wax (melting point 85 ° C.)): 10% by weight
Constitutional material (talc): 10% by weight
Concealment pigment (titanium dioxide): 20% by weight
Tackifier (ester gum (rosin ester, softening point 86 ° C.)): 15% by weight
Oil (liquid paraffin): 5% by weight
As shown in FIG. 1 having a diameter of 10.0 mm, the above blended composition is heated and mixed and dispersed with a kneader and then kneaded with two rolls, then heated and melted, poured into a predetermined mold, cooled and solidified. A white solid drawing material 10 was obtained.

(1-4) Comparative Example 2
Substrate (EVA (melting point: 62 ° C., melt flow rate: 400, trade name: EV210, Mitsui / DuPont Polychemical): 30% by weight
Wax (cured tallow oil (melting point: 52 ° C.)): 10% by weight
Wax (Caster wax (melting point 85 ° C.)): 10% by weight
Constitutional material (talc): 10% by weight
Concealment pigment (titanium dioxide): 20% by weight
Tackifier (ester gum (rosin ester, softening point 86 ° C.)): 15% by weight
Oil (liquid paraffin): 5% by weight
As shown in FIG. 1 having a diameter of 10.0 mm, the above blended composition is heated and mixed and dispersed with a kneader and then kneaded with two rolls, then heated and melted, poured into a predetermined mold, cooled and solidified. A white solid drawing material 10 was obtained.

(2) Evaluation method About the solid drawing material of the said Examples 1-2 and Comparative Examples 1-2, writing property (drawing paper), writing property (coat paper), writing property (stainless steel), writing property (PET), concealment property Was evaluated and confirmed.
(2-1) Writability, (drawing paper) writability (coated paper), writability (PET) and writability (stainless steel)
The solid drawing materials according to each of the above Examples and Comparative Examples are used as they are, and drawn on black drawing paper, black coated paper, PET film, and a mirror-like stainless steel plate. Rated by stage.
A: The drawn line is dark and clearly visible.
B: Although the drawing line is disturbed, it is not unsightly.
C: The drawn line is drowning and unsightly.
D: The drawn line is drowning considerably and cannot be seen without care.
E: The drawn line is hardly visible or cannot be drawn.

(2-2) Concealment Prepare a multi-color printed letter “Mitsubishi pencil” on a commercially available copy paper, conceal it from above the character using the solid drawing material according to each of the above examples and comparative examples, The state at that time was evaluated in the following five stages A to E.
A: The background color and characters are completely hidden and cannot be seen.
B: The background color and characters are almost concealed and cannot be seen unless care is taken.
C: The background color and letters appear light.
D: The background color and characters are clearly visible.
E: The color and characters of the groundwork are almost visible (however, this evaluation was made when the evaluation in (2-1) was D or E).

(2-3) Evaluation results The evaluation results of the above (2-1) and (2-2) are shown in Table 1 below.

As above-mentioned, as for the solid drawing material which concerns on Example 1 and 2 of this invention, all the evaluation methods showed the favorable result. That is, it is a solid drawing material that has high concealability and can cover the paper surface or the coated paper surface as a writing surface like a correction tape. In Example 2, since the beef tallow oil having low toughness was blended as the wax, the evaluation other than the writability on the drawing paper was slightly inferior to that of Example 1.
On the other hand, among the comparative examples that are outside the scope of the present invention, the test results of Comparative Examples 1 and 2 were inferior in writing on a smooth surface compared to any of the Examples.

First, since Comparative Example 1 was formulated with urushi wax having high toughness, it could be drawn on a PET film, but since a dibasic acid derivative was not blended, it was applied to the plate surface when drawing on a stainless steel plate. It was difficult to adhere the film, and it was naturally assumed that it could not be used for concealment.
In Comparative Example 2, since a beef tallow oil having low toughness is blended as a wax, in drawing on a smooth surface such as a PET film or a stainless steel plate, it is difficult to adhere the coating film to the plate surface. It was impossible to provide concealment, and it was estimated that the quality was lower than that of Comparative Example 1.

  INDUSTRIAL APPLICABILITY The present invention can be used as a solid drawing material such as a crayon or a crepa formed by solidifying a wax, an extender, and a pigment.

10 White drawing material

Claims (9)

A solid drawing material containing a wax, an extender, and a concealing pigment,
Further, C: 12-30 dibasic acid or derivative thereof, tackifier, and ethylene vinyl acetate copolymer, ethylene acrylic acid copolymer, ethylene ethyl acrylate having a melting point of 60-90 ° C. as a base material A solid drawing material comprising 20 to 80% by weight of any copolymer and / or mixture thereof.   The solid drawing material according to claim 1, wherein the C: 12-30 dibasic acid or a derivative thereof has a melting point of 70 ° C. or less.   3. The solid drawing material according to claim 1, wherein the content of the C: 12-30 dibasic acid or a derivative thereof is in the range of 1 to 12 wt% with respect to the entire solid drawing material.   The weight ratio of the C: 12-30 dibasic acid or derivative thereof to the total waxes contained in the solid drawing material is the dibasic acid or derivative thereof: the wax = 2: 100-20: 100. The solid drawing material according to any one of claims 1 to 3, wherein the solid drawing material is in a range of.   The melt flow rate defined by JIS K7210: 1999 of the ethylene vinyl acetate copolymer, the ethylene acrylic acid copolymer, and the ethylene ethyl acrylate copolymer is 400 to 800 g / 10 min. The solid drawing material according to any one of the above.   The solid drawing material according to any one of claims 1 to 5, wherein the ethylene vinyl acetate copolymer is obtained by polymerizing a vinyl acetate monomer at a ratio of 10% by weight or more.   The tackifier is selected from the group consisting of a terpene resin, a modified terpene resin, a maleic acid resin derivative, a coumarone / indene resin, a coumarone / indene resin derivative, a styrene resin, an isoprene resin, a pine resin, a rosin ester, and a petroleum resin. The solid drawing material according to claim 1, wherein the solid drawing material is one or a mixture of two or more.   The solid hiding material according to claim 1, wherein the hiding pigment is a hiding white pigment, and further contains at least one of an organic pigment and an inorganic pigment.   The solid hiding material according to claim 1, wherein the hiding pigment is a hiding black pigment.