JP6401147B2 - Solid drawing material - Google Patents

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.
Then, this invention makes it a subject to provide what can remove the coating film adhering to a writing surface by this solid drawing material itself. Further, it is an object to provide 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 coating line. And

In view of the above problems, the present invention provides:
10 to 40% by weight of wax having a melting point of 52 to 85 ° C,
10-20% by weight of extender,
15 to 30% by weight of a concealable pigment as a coloring material,
One or more selected from the group consisting of terpene resins, modified terpene resins, maleic acid resin derivatives, coumarone / indene resins, coumarone / indene resin derivatives, styrene resins, isoprene resins, pine resin, rosin esters, and petroleum resins A tackifier that is a mixture of
An ethylene vinyl acetate copolymer of 5 to 30% by weight having a melting point of 62 to 79 ° C. as a substrate;
Look containing a 2 to 15 wt% of the melting point of 30 ° C. or less of the lubricant component,
The ethylene vinyl acetate copolymer has a melt flow rate defined by JIS K7210: 1999 of 400 to 800 g / 10 min .

The “wax” in the present invention refers to what is generally classified as a wax among the constituent components of the solid drawing material . 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, to impart fixing properties to the writing surface and compatible with later tackifier. The melting point of this wax is 52 ~ 85 ° C.. Specifically, paraffin wax, microcrystalline wax, urushi wax, beeswax, molasses, montan wax, hydrogenated castor oil, hardened palm oil, glycerin fatty acid ester, polyglycerin fatty acid ester and the like can be used as the wax in the present invention. Moreover, the compounding quantity is 10 to 40 weight% of the whole.

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. Moreover, the compounding quantity is 10 to 20 weight% of the whole .

Further, the "colorant" in the present invention is Ru is used "hiding pigment". 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, titanium dioxide can be used as a concealing pigment in the present invention. As the “titanium dioxide” in the present invention, any conventionally known titanium dioxide can be used regardless of rutile or atanase. Further, the blending amount is desirably 15 to 30 % by weight of the whole. Examples of other concealing pigments include zinc oxide, carbon black, white resin particles, and colored resin particles. Titanium dioxide is most preferable from the viewpoint of concealing power and the like.

Furthermore, as the “hiding pigment” in the present invention, a “hiding white pigment” can be used. The “concealing white pigment” in the present invention is a component that contributes to concealing the base in white by the coating film obtained from the solid drawing material. Specifically, titanium dioxide can be used as the concealing white pigment in the present invention. As the “titanium dioxide” in the present invention, any conventionally known titanium dioxide can be used regardless of rutile or atanase. Also, when using this hiding white pigment, it may also be a further comprise at least one of organic pigments and inorganic pigments. The blending amount of the concealing white pigment is desirably 15 to 30 % by weight of the whole including the organic pigment or the inorganic pigment. Other examples of the hiding pigment include zinc oxide and white resin particles, but titanium dioxide is most preferred from the viewpoint of hiding power. In addition, as the “organic pigment” in the present invention, all common ones such as azo organic pigments and cyanine organic pigments can be used. In addition, as the “inorganic pigment” in the present invention, all common ones such as petals, ultramarine blue and bitumen can be used.

In addition, as the “concealing pigment” in the present invention, a “concealing black pigment” can be used. The “hiding black pigment” in the present invention is a component that contributes to the coating film obtained from the solid drawing material concealing and coloring with a black background. Specifically, carbon black, graphite, and iron black can be used as the concealing black pigment in the present invention. Further, the amount thereof is 1 5-3 0% by weight of the total has desirable.

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” in the present invention forms 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 melting point of the ethylene-vinyl acetate copolymer as the 6 2 ~ 79 ° C. is used, the amount thereof Ru 5 to 30 wt% der.

Incidentally, before Symbol ethylene-vinyl acetate copolymer is preferably a vinyl acetate monomer is obtained by polymerizing at a ratio of more than 10 wt%.
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. One or a mixture of two or more selected from the group.

Also includes 2 to 15 wt% of an oil Melting point 3 0 ° C. hereinafter as a lubricating component. Examples of such oil include jojoba oil, liquid paraffin, squalane, squalene, and liquid paraffin.

Since the present invention is configured as described above, the present invention provides a solid drawing material that can remove the coating film adhered to the writing surface by adjusting the force at the time of rubbing. Is possible. Furthermore, when using concealable pigments as coloring materials, the concealability is high, and the paper surface and coated paper surface of the writing surface can be covered like a correction tape, and written on the coating line with another writing instrument. It is possible to provide a solid drawing material that can be used.
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” is an abbreviation for “ethylene vinyl acetate copolymer”. The unit of the numerical value described as “melt flow rate” is “g / 10 min”.

(1) Examples 1 to 5
(1-1) Composition and production method of Examples and Comparative Examples (1-1-1) 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 (melting point: 82 ° 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.

(1-1-2) Example 2
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 (terpene phenol resin (melting point 80 ° C., trade name: YS Polystar T80, Yasuhara Chemical)): 15% by weight
Oil (liquid paraffin): 5% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 1.

(1-1-3) Example 3
Substrate (EVA (melting point: 73 ° C., melt flow rate: 800, trade name: EV577, 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 (melting point: 82 ° C.)): 15% by weight
Oil (liquid paraffin): 5% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 1.

(1-1-4) Example 4
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.)): 5% by weight
Wax (Caster wax (melting point 85 ° C.)): 5% by weight
Constitutional material (talc): 10% by weight
Concealment pigment (titanium dioxide): 20% by weight
Tackifier (ester gum (melting point: 82 ° C.)): 15% by weight
Oil (liquid paraffin): 15% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 1.

(1-1-5) Example 5
Except that the blending amount of the base material EVA (EV210) is 10% by weight, the extender (talc) is blended by 20% by weight, and the concealable pigment (titanium dioxide) is blended by 30% by weight. In the same manner as in Example 1, a white solid drawing material 10 having a diameter of 10.0 mm as shown in FIG. 1 was obtained.

(1-1-6) Comparative Example 1
The same procedure as in Example 1 was conducted except that 30% by weight of polyethylene (melting point: 115 ° C., melt flow rate: 2, trade name: Novatec LF448K, Nippon Polyethylene) was used instead of EVA (EV210) as the base material. A white solid drawing material 10 having a diameter of 10.0 mm as shown in FIG. 1 was obtained.

(1-1-7) Comparative Example 2
Example 1 except that 30% by weight of EVA (melting point: 40 ° C., melt flow rate: 65, trade name: EV40LX, Mitsui / DuPont Polychemical) was used instead of EVA (EV210) as the base material. Thus, a white solid drawing material 10 having a diameter of 10.0 mm as shown in FIG. 1 was obtained.

(1-1-8) Comparative Example 3
Example 1 except that 30% by weight of EVA (melting point: 92 ° C., melt flow rate: 12, product name: P1207, Mitsui / DuPont Polychemical) was used instead of EVA (EV210) as the base material. Thus, a white solid drawing material 10 having a diameter of 10.0 mm as shown in FIG. 1 was obtained.

(1-1-9) Comparative Example 4
Base material (EVA (melting point 62 ° C., melt flow rate: 400, trade name: EV210, Mitsui / DuPont Polychemical): 85% by weight
Wax (Caster wax (melting point 85 ° C.)): 5% by weight
Constitutional material (talc): 2% by weight
Concealment pigment (titanium dioxide): 3% by weight
Tackifier (ester gum (melting point: 82 ° C.)): 5% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 1.

(1-1-10) Comparative Example 5
Base material (EVA (melting point: 62 ° C., melt flow rate: 400, trade name: EV210, Mitsui / DuPont Polychemical): 50% by weight
Constitutional material (talc): 20% by weight
Concealment pigment (titanium dioxide): 30% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 1.

(1-1-11) Comparative Example 6
Substrate (EVA (melting point: 62 ° C., melt flow rate: 400, trade name: EV210, Mitsui / DuPont Polychemical): 30% by weight
Constitutional material (talc): 20% by weight
Concealment pigment (titanium dioxide): 30% by weight
Tackifier (ester gum (melting point: 82 ° C.)): 15% by weight
Oil (liquid paraffin): 5% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 1.

(1-1-12) Comparative Example 7
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): 15% by weight
Concealment pigment (titanium dioxide): 30% by weight
Oil (liquid paraffin): 5% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 1.

(1-2) Evaluation Method For the solid drawing materials of Examples 1 to 5 and Comparative Examples 1 to 7, writing property (paper surface), writing property (coated paper), concealing property, self-erasing property, overwrite property, writing property. Evaluation and confirmation of (PET), writability (glass), writability (SUS), fixability (PET), fixability (glass), fixability (SUS), heat resistance writability (SUS), break strength φ10 and bleed did.

(1-2-1) Writability (paper surface) and writability (coated paper)
The solid drawing materials according to each of the above examples and comparative examples were used as they were and drawn on black drawing paper and black coated paper, respectively, and the state of the drawn lines at that time was scored in 5 stages of 1 to 5 points. The scoring criteria were as follows.
5: The drawn line is dark and clearly visible.
4: Distorted lines are visible, but not unsightly.
3: The drawn line is drowning and unsightly.
2: The strokes are drowning and cannot be seen without care.
1: The drawn line is hardly visible or cannot be drawn.

(1-2-2) Concealment A commercially available copy paper on which characters “Mitsubishi Pencil” are printed in multiple colors is prepared and concealed from above the characters using the solid drawing materials according to each of the above examples and comparative examples. Then, the situation at that time was scored in 5 stages of 1 to 5 points. The scoring criteria were as follows.
5: The background color and characters are completely hidden and cannot be seen.
4: The background color and characters are almost concealed and cannot be seen without care.
3: The background color and characters appear faint.
2: The background color and characters are clearly visible.
1: The color and characters of the groundwork are almost visible (however, when the evaluation of (1-2-1) was 1 or 2, this evaluation was used).

(1-2-3) Self-erasing property The lines drawn on the paper surface in (1-2-1) above are lightly rubbed with the solid drawing material used for each drawing, and the erasability at that time is 1 to 5 points in 5 stages Scoring at. The scoring criteria were as follows.
5: It disappears well and no trace is left.
4: Disappears but leaves a trace.
3: The shape of the drawn line remains without disappearing.
2: Almost disappears.
1: Not disappeared at all (however, when the evaluation of (1-2-1) was 1 or 2, this evaluation was used).

(1-2-4) Overwriting property Writing on SX-150-05 (ink color: black, trade name: Jetstream) made by Mitsubishi Pencil from the top of the coating film concealed in (1-2-2), The scribing line and the state of the paint film were scored in 1 to 5 points. The scoring criteria were as follows.
5: The drawn lines are not cut or peeled off, and the overwritten characters are clearly visible.
4: Although the drawn line may be scraped or peeled off, the overwritten character can be seen.
3: There is a part where the drawn line is scraped or peeled off, and the overwritten character is difficult to see.
2: The drawn line is easily cut off or peeled off, and overwriting is difficult.
1: The drawn line is shaved or peeled off and cannot be overwritten (however, when the evaluation in (1-2-2) was 1 or 2, this evaluation was used).

(1-2-5) Writability (PET), Writability (glass) and Writability (SUS)
The solid drawing materials according to each of the above Examples and Comparative Examples were used as they were and drawn on a PET film, a glass plate, and a SUS plate, and the state of the drawn lines at that time was scored in 5 stages of 1 to 5 points. . The scoring criteria were as follows.
5: The drawn line is dark and clearly visible.
4: Distorted lines are visible, but not unsightly.
3: The drawn line is drowning and unsightly.
2: The strokes are drowning and cannot be seen without care.
1: The drawn line is hardly visible or cannot be drawn.

(1-2-6) Fixability (PET), Fixability (Glass), and Fixability (SUS)
The drawn lines drawn in the above (1-2-5) were each lightly rubbed with fingers, and the remainder of the drawn lines at that time was scored in 1 to 5 points. The scoring criteria were as follows.
5: The drawn line does not disappear at all.
4: Almost disappears.
3: The shape of the drawn line remains without disappearing.
2: It disappears, but a trace remains.
1: Completely disappeared and no trace remained (however, this evaluation was made when the evaluation in (1-2-5) was 1 or 2).

(1-2-7) Heat-resistant writing property (SUS)
In the test of (1-2-5), the SUS plate used for writing property (SUS) was heated to 250 ° C. and drawn thereon, and the state of the drawn lines at that time was scored in 1 to 5 points. The scoring criteria were as follows.
5: The drawn line is dark and clearly visible.
4: Distorted lines are visible, but not unsightly.
3: The drawn line is drowning and unsightly.
2: The strokes are drowning and cannot be seen without care.
1: The drawn line is hardly visible or cannot be drawn.

(1-2-8) Breaking strength (φ10)
When drawing on the paper surface in the test of (1-2-1) above, the state of the solid drawing material according to each example and comparative example when drawing while adjusting the writing pressure was observed, and each solid drawing at that time The state of the material itself was scored in 5 stages from 1 to 5. The scoring criteria were as follows.
5: Even if it writes with force, it does not break (70N or more).
4: Almost no breakage during normal use (60N or more and less than 70N).
3: It may be broken by normal use (50N or more and less than 60N).
2: It is easy to break by normal use (40N or more and less than 50N).
1: Breaks frequently during normal use and is not suitable for practical use (less than 40N).

(1-2-9) Bleed The drawn line drawn on the paper surface in (1-2-1) above is left for 1 day in an environment with a temperature of 25 ° C. and a humidity of 65%, and the presence of bleeding (bleeding) due to oil on the outside of the drawn line Was observed, and the situation was scored in two stages of 1 or 5 points. The scoring criteria were as follows.
5: There was no bleed.
1: There was bleeding.

(1-2-10) Comprehensive evaluation About each Example and the comparative example, the average value of the score of each said evaluation item was made into the score, and the following references | standards evaluated.
A: 4 points or more.
B: 3 points or more and less than 4 points.
C: 2 points or more and less than 3 points.
D: Less than 2 points.

(1-3) Evaluation result The evaluation result about Examples 1-5 and Comparative Examples 1-7 was as follows.

  As above-mentioned, as for the solid drawing material which concerns on Examples 1-5 of this invention, all the evaluation methods showed the favorable result in general, and the comprehensive evaluation was also favorable with A or B. In other words, it is highly concealable, and can be coated on the paper surface or coated paper surface as a correction tape like a correction tape, and can be written with other writing tools over the coating line, and further attached to the writing surface. It was a solid drawing material which can remove a coating film by this solid drawing material itself.

  On the other hand, each comparative example which is outside the scope of the present invention was not good in overall evaluation as C or D. The test results of Comparative Examples 1, 4, 5 and 7 were particularly inferior in writability on copy paper, and therefore in the evaluation of self-erasability. Moreover, in any of the comparative examples, the evaluation of the overwrite performance was extremely bad, and in Comparative Examples 3 and 4, the writing property on the coated paper was inferior.

First, since Comparative Example 1 contains polyethylene instead of EVA, the coating film cannot be adhered to the surface of the copy paper or the surface of the coated paper, and naturally it cannot be used for concealment. It was estimated that.
In Comparative Example 2, the blended EVA has a low melting point of 40 ° C., and although there is a force to adhere the coating film to the paper surface as it is to form a coating film, the power to maintain the coating film (overwriting property) is high. It was weak and the fracture strength was estimated to be extremely low.
On the contrary, in Comparative Example 3, the melting point of the blended EVA was as high as 92 ° C., and the force for adhering to and sticking to the non-absorbing surface to form a coating film was weak, so that the concealing power was estimated to be low.

In Comparative Example 4, the blending amount of EVA was excessively 85% by weight, and the cohesive force of the solid drawing material itself was superior. Therefore, it was presumed that the coating film could not be formed by adhering to the paper surface.
In Comparative Example 5, since neither the tackifier or the wax is blended, the adhesive force to the paper surface cannot be exhibited, and the solid drawing material itself cannot collapse and be used for drawing. It was speculated that could not be formed.
In Comparative Example 6, since no wax was blended, the solid drawing material itself collapsed and could not be used for drawing, so it was presumed that the coating film could not be formed.
Since the comparative example 7 was not mix | blended with the tackifier, since it was not able to exhibit the adhesive force to a paper surface, it was estimated that the coating film could not be formed.

(2) Examples 6 to 10
(2-1) Composition and production method of Examples and Comparative Examples (2-1-1) Example 6
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): 15% by weight
Red No. 202: 5% by weight
Tackifier (ester gum (melting point: 82 ° 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 pink solid drawing material 10 was obtained.

(2-1-2) Example 7
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
Carbon black (trade name: MA100, Mitsubishi Chemical): 20% by weight
Tackifier (terpene phenol resin (melting point 80 ° C., trade name: YS Polystar T80, Yasuhara Chemical)): 15% by weight
Oil (liquid paraffin): 5% by weight
A black solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 6.

(2-1-3) Example 8
Substrate (EVA (melting point: 73 ° C., melt flow rate: 800, trade name: EV577, 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
Carbon black (trade name: MA100, Mitsubishi Chemical): 20% by weight
Tackifier (ester gum (melting point: 82 ° C.)): 15% by weight
Oil (liquid paraffin): 5% by weight
A black solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 6.

(2-1-4) Example 9
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.)): 5% by weight
Wax (Caster wax (melting point 85 ° C.)): 5% by weight
Constitutional material (talc): 10% by weight
Carbon black (trade name: MA100, Mitsubishi Chemical): 20% by weight
Tackifier (ester gum (melting point: 82 ° C.)): 15% by weight
Oil (liquid paraffin): 15% by weight
A black solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 6.

(2-1-5) Example 10
Except that the amount of the base material EVA (EV210) is 10% by weight, the amount of the extender (talc) is 20% by weight, and the amount of the concealable pigment (titanium dioxide) is 25% by weight. In the same manner as in Example 6, a pink solid drawing material 10 having a diameter of 10.0 mm as shown in FIG. 1 was obtained.

(2-1-6) Comparative Example 8
As in Example 6, except that 30% by weight of polyethylene (melting point: 115 ° C., melt flow rate: 2, trade name: Novatec LF448K, Nippon Polyethylene) was used instead of EVA (EV210) as the base material. A pink solid drawing material 10 having a diameter of 10.0 mm as shown in FIG. 1 was obtained.

(2-1-7) Comparative Example 9
Example 6 except that 30% by weight of EVA (melting point: 40 ° C., melt flow rate: 65, trade name: EV40LX, Mitsui / DuPont Polychemical) was used instead of EVA (EV210) as the base material. Thus, a pink solid drawing material 10 having a diameter of 10.0 mm as shown in FIG. 1 was obtained.

(2-1-8) Comparative Example 10
The same as Example 6 except that 30% by weight of EVA (melting point: 92 ° C., melt flow rate: 12, product name: P1207, Mitsui / DuPont Polychemical) was used as the base material instead of EVA (EV210). Thus, a pink solid drawing material 10 having a diameter of 10.0 mm as shown in FIG. 1 was obtained.

(2-1-9) Comparative Example 11
Base material (EVA (melting point 62 ° C., melt flow rate: 400, trade name: EV210, Mitsui / DuPont Polychemical): 85% by weight
Wax (Caster wax (melting point 85 ° C.)): 5% by weight
Constitutional material (talc): 2% by weight
Carbon black (trade name: MA100, Mitsubishi Chemical): 3% by weight
Tackifier (ester gum (melting point: 82 ° C.)): 5% by weight
A black solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the blended composition in the same manner as in Example 6.

(2-1-10) Comparative Example 12
Substrate (EVA (melting point 62 ° C., melt flow rate: 400, trade name: EV210, Mitsui / DuPont Polychemical): 40% by weight
Wax (Urushiro (melting point 52 ° C.)): 10% by weight
Constitutional material (talc): 20% by weight
Concealment pigment (titanium dioxide): 20% by weight
Red No. 202: 10% by weight
A peach-colored solid drawing material 10 having a diameter of 10.0 mm as shown in FIG.

(2-1-11) Comparative Example 13
Substrate (EVA (melting point: 62 ° C., melt flow rate: 400, trade name: EV210, Mitsui / DuPont Polychemical): 30% by weight
Constitutional material (talc): 20% by weight
Concealment pigment (titanium dioxide): 20% by weight
Red No. 202: 10% by weight
Tackifier (ester gum (melting point: 82 ° C.)): 15% by weight
Oil (liquid paraffin): 5% by weight
A peach-colored solid drawing material 10 having a diameter of 10.0 mm as shown in FIG.

(2-2) Evaluation Method The solid drawing materials of Examples 6 to 10 and Comparative Examples 8 to 13 were evaluated and confirmed in the same manner as (1-2).

(2-3) Evaluation result The evaluation result about Examples 6-10 and Comparative Examples 8-13 was as follows.

  As above-mentioned, as for the solid drawing material which concerns on Examples 6-10 of this invention, all the evaluation methods showed the favorable result, and the comprehensive evaluation was also favorable with A or B. In other words, it is highly concealed, and can be coated like a correction tape on a paper surface or a coated paper surface as a writing surface. It was a solid drawing material which can remove a coating film by this solid drawing material itself. However, bleed was observed only in Example 9 in which the content of oil (liquid paraffin) was higher than the others.

  On the other hand, each comparative example which is outside the scope of the present invention was not good in overall evaluation as C or D. The test results of Comparative Examples 8 and 11 were particularly inferior in writability on copy paper .2, and therefore in the evaluation of self-erasability. In Comparative Example 9, the evaluation of overwriting performance was extremely bad.

First, since Comparative Example 8 is blended with polyethylene instead of EVA, the coating film cannot be adhered to the surface of the copy paper or the surface of the coated paper, and naturally it cannot be used for concealment. It was estimated that.
In Comparative Example 9, the blended EVA has a low melting point of 40 ° C., and although there is a force to adhere the coating film to the paper surface as it is to form a coating film, it has the ability to maintain the coating film (overwriting property). It was weak and the fracture strength was estimated to be extremely low.
On the contrary, in Comparative Example 10, the melting point of the blended EVA was as high as 92 ° C., and the force for adhering on the non-absorbing surface to form a coating film was weak, so that the hiding power was estimated to be low.

In Comparative Example 11, it was presumed that the blending amount of EVA was excessive as 85% by weight and the cohesive force of the solid drawing material itself was superior, so that it was unable to adhere to the paper surface and form a coating film.
In Comparative Example 12, since no tackifier was blended, it was presumed that the coating film could not be formed because the adhesive force to the paper surface could not be exhibited.
In Comparative Example 13, since no wax was blended, the solid drawing material itself collapsed and could not be used for drawing, so it was presumed that the coating film could not be formed.

(3) Examples 11-16
(3-1) Composition and production method of Examples and Comparative Examples (3-1-1) Example 11
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.)): 15% by weight
Wax (paraffin wax (melting point: 66 ° C.), trade name: 155F, Japanese wax): 8% by weight
Constitutional material (talc): 10% by weight
Concealment pigment (titanium dioxide): 20% by weight
Tackifier (gum rosin (melting point 120 ° C.)): 15% by weight
Oil (liquid paraffin): 2% 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.

(3-1-2) Example 12
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.)): 8% by weight
Wax (paraffin wax (melting point: 58 ° C.), trade name: 135F, Japanese wax): 15% by weight
Constitutional material (talc): 10% by weight
Concealment pigment (titanium dioxide): 20% by weight
Tackifier (terpene phenol resin (melting point 80 ° C., trade name: YS Polystar T100, Yasuhara Chemical)): 15% by weight
Oil (liquid paraffin): 2% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 11.

(3-1-3) Example 13
Substrate (EVA (melting point: 73 ° C., melt flow rate: 800, trade name: EV577, Mitsui / DuPont Polychemical): 30% by weight
Wax (beeswax (melting point 63 ° C.)): 15% by weight
Wax (paraffin wax (melting point: 66 ° C.), trade name: 155F, Japanese wax): 8% by weight
Constitutional material (talc): 10% by weight
Concealment pigment (titanium dioxide): 20% by weight
Tackifier (ester gum (melting point: 82 ° C.)): 15% by weight
Oil (liquid paraffin): 2% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 11.

(3-1-4) Example 14
Except that the blending amount of the base material EVA (EV210) is 10% by weight, the extender (talc) is blended by 20% by weight, and the concealable pigment (titanium dioxide) is blended by 30% by weight. example 1 1 in diameter in the same manner as to give a white solid drawing material 10 as shown in Figure 1 of 10.0 mm.

(3-1-5) Example 15
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.)): 5% by weight
Wax (paraffin wax (melting point: 66 ° C.), trade name: 155F, Japanese wax): 5% by weight
Constitutional material (talc): 10% by weight
Concealment pigment (titanium dioxide): 20% by weight
Tackifier (ester gum (melting point: 82 ° C.)): 15% by weight
Oil (liquid paraffin): 15% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 11.

(3-1-6) Example 16
Base material (EVA (melting point 79 ° C., melt flow rate: 2,500, trade name: Ultrasen # 685, Tosoh): 5% by weight
Wax (Urushiro (melting point 52 ° C.)): 20% by weight
Wax (paraffin wax 135F, Nippon Seiki (melting point: 58 ° C.)): 20% by weight
Constitutional material (talc): 10% by weight
Concealment pigment (titanium dioxide): 20% by weight
Tackifier (terpene phenol resin, YS Polystar T80, Yasuhara Chemical (melting point 80 ° C.)): 15% by weight
Oil (liquid paraffin): 10% 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.

(3-1-7) Comparative Example 14
As in Example 11, except that 30% by weight of polyethylene (melting point: 115 ° C., melt flow rate: 2, trade name: Novatec LF448K, Nippon Polyethylene) was used instead of EVA (EV210) as the base material. A white solid drawing material 10 having a diameter of 10.0 mm as shown in FIG. 1 was obtained.

(3-1-8) Comparative Example 15
As in Example 11, except that 30% by weight of EVA (melting point: 40 ° C., melt flow rate: 65, trade name: EV40LX, Mitsui / DuPont Polychemical) was used instead of EVA (EV210) as the base material. Thus, a white solid drawing material 10 having a diameter of 10.0 mm as shown in FIG. 1 was obtained.

(3-1-9) Comparative Example 16
Except for blending 30% by weight of EVA (melting point: 92 ° C., melt flow rate: 12, product name: P1207, Mitsui / DuPont Polychemical) instead of EVA (EV210) as the base material, the same as Example 11 Thus, a white solid drawing material 10 having a diameter of 10.0 mm as shown in FIG. 1 was obtained.

(3-1-10) Comparative Example 17
Base material (EVA (melting point 62 ° C., melt flow rate: 400, trade name: EV210, Mitsui / DuPont Polychemical): 85% by weight
Wax (Urushiro (melting point 52 ° C.)): 5% by weight
Constitutional material (talc): 2% by weight
Concealment pigment (titanium dioxide): 3% by weight
Tackifier (terpene phenol resin (melting point 80 ° C., trade name: YS Polystar T100, Yasuhara Chemical)): 5% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 11.

(3-1-11) Comparative Example 18
Substrate (EVA (melting point 62 ° C., melt flow rate: 400, trade name: EV210, Mitsui / DuPont Polychemical): 40% by weight
Constitutional material (talc): 20% by weight
Concealment pigment (titanium dioxide): 30% by weight
Wax (beeswax (melting point 63 ° C.)): 10% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 11.

(3-1-12) Comparative Example 19
Base material (EVA (melting point: 73 ° C., melt flow rate: 800, trade name: EV577, Mitsui / DuPont Polychemical): 43% by weight
Constitutional material (talc): 20% by weight
Concealment pigment (titanium dioxide): 20% by weight
Tackifier (gum rosin (melting point 120 ° C.)): 15% by weight
Oil (liquid paraffin): 2% by weight
A white solid drawing material 10 as shown in FIG. 1 having a diameter of 10.0 mm was obtained from the above blended composition in the same manner as in Example 11.

(3-2) Evaluation Method The solid drawing materials of Examples 11 to 16 and Comparative Examples 14 to 19 were evaluated and confirmed in the same manner as (1-2).

(3-3) Evaluation result The evaluation result about Examples 11-16 and Comparative Examples 14-19 was as follows.

  As above-mentioned, as for the solid drawing material which concerns on Examples 11-16 of this invention, all the evaluation methods showed the favorable result, and the comprehensive evaluation was also favorable with A or B. That is, it has high concealability, can coat the PET film surface, the glass surface and the SUS surface as a writing surface, and can also draw on the SUS surface heated to 250 ° C. It was a solid drawing material that was not removed by rubbing with fingers. Moreover, it is excellent also in break strength, and it can be put into practical use without providing a protective layer on the surface of the rod-shaped body for strengthening. Moreover, since it is not necessary to provide a protective layer, it is possible to obtain a solid drawing material that can be used immediately in a work place that does not require an operation of removing the protective layer. However, bleeding was observed only in Example 15 in which the content of oil (liquid paraffin) was higher than the others.

  On the other hand, each comparative example which is outside the scope of the present invention was not good in overall evaluation as C or D.

First, since Comparative Example 14 is blended with polyethylene instead of EVA, the coating cannot be adhered to the surfaces of PET, glass and SUS, and naturally it cannot be used for concealment. It was done.
In Comparative Example 15, the melting point of the blended EVA is as low as 40 ° C., and although the coating film is adhered to the surface of PET and glass as it is and has the power to form a coating film, it is applied to a slightly rough SUS surface. It was inferred that the writing property was inferior and the breaking strength was extremely low.
On the contrary, in Comparative Example 16, the melting point of the blended EVA was as high as 92 ° C., and the force to cause adhesion on the non-absorbing surface to form a coating film was weak, so that the fixing force was estimated to be low.

In Comparative Example 17, the amount of EVA is excessively high at 85% by weight, the cohesive strength of the solid drawing material itself is superior, and since no oil is blended, it adheres to the surface of PET, glass and SUS. It was presumed that a film could not be formed.
In Comparative Example 18, because no tackifier was blended and no oil was blended, the adhesive strength to the surfaces of PET, glass and SUS could not be exhibited, and the solid drawing material itself collapsed. It was presumed that the coating film could not be formed because it could not be used for drawing.
In Comparative Example 19, since the wax was not blended, the solid drawing material itself collapsed and could not be used for drawing, so it was presumed that the coating film could not be formed.

  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.

Claims (4)

10 to 40% by weight of wax having a melting point of 52 to 85 ° C,
10-20% by weight of extender,
15 to 30% by weight of a concealable pigment as a coloring material,
One or more selected from the group consisting of terpene resins, modified terpene resins, maleic acid resin derivatives, coumarone / indene resins, coumarone / indene resin derivatives, styrene resins, isoprene resins, pine resin, rosin esters, and petroleum resins A tackifier that is a mixture of
A melting point from 62 to 79 ethylene-vinyl acetate copolymer 5 to 30 wt% a ° C. as a substrate, viewed contains a 2 to 15 wt% of the melting point of 30 ° C. or less of the lubricant component,
A solid drawing material, wherein the ethylene vinyl acetate copolymer has a melt flow rate defined by JIS K7210: 1999 of 400 to 800 g / 10 min .   The solid drawing material according to claim 1, wherein the concealing pigment is a concealing white pigment and further contains at least one of an organic pigment and an inorganic pigment.   The solid drawing material according to claim 1, wherein the hiding pigment is a hiding black pigment. The ethylene-vinyl acetate copolymer according to claim 1, 2 or 3 solid drawing material, wherein the is obtained by polymerization in a proportion of more than 10 wt% of vinyl acetate monomer.

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