JP6022190B2 - Solid drawing material and solid drawing tool - Google Patents

Description

  The present invention is a solid drawing material in which kneading by a roll mill or the like is not required at the time of production, and the heated and melted material is mixed and dispersed only by stirring, and is not limited to normal high-quality paper, drawing paper, copy paper, and other papers. The present invention relates to a solid drawing material capable of smoothly and moderately drawing even on a smooth non-absorbing surface such as paper, plastic, metal, glass and whiteboard. Here, “moderately” means that the drawn background is not completely invisible, but can be discriminated thinly, and if the drawn portion is covered with a translucent sheet, the background is erased in the copy. I mean. In more detail, it is possible to draw on a transparent plate such as transparent plastic or glass in a moderately dark and clear manner, and when drawn on these non-absorbing surfaces, it can be easily done with paper such as cloth, tissue paper, whiteboard eraser, etc. The present invention relates to a solid drawing material that can be erased. Further, the present invention relates to a solid drawing tool in which a protective sheet is wound around the outer periphery of the solid drawing material, which can be used by cutting with a pencil sharpener like a conventional pencil.

The conventional solid drawing material adjusts hardness by adding oil, resin, etc. to the compound which consists of a wax, a pigment, and an extender as needed. However, when the amount of oil is increased for the purpose of softening the solid drawing material, the strength is lowered and the material tends to be broken. In such a case, it becomes impossible to perform thin drawing or sharpen the tip and cut, and fine drawing is impossible. Further, when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc., there is a problem in that it cannot be drawn in a soft and dark manner because it slips on the surface.
On the other hand, if the amount of resin is increased in order to increase the strength, it is hard even if it can be thinly molded, so it cannot be drawn on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc. There is a problem.

  For example, a composition of a soft color core having excellent colorability containing a mixture of glycerin fatty acid ester and / or pentaerythritol fatty acid ester having a melting point of 65 ° C. or less and rosin and / or a rosin modified product as a non-baked colored pencil is disclosed. (Patent Document 1). The purpose of this is to melt the drawing on the canvas with oil for oil painting to obtain an oil painting-like work, such as coated paper, plastic, metal, glass, whiteboard, etc. The purpose is different from that of the solid drawing material to be drawn.

  In addition, as a solid drawing material, it contains pigment, wax and mineral oil, and also contains a certain proportion of amorphous poly α-olefin and rosin, so that it can be drawn smoothly even on non-absorbing drawing surfaces. The composition of a solid drawing material is disclosed (Patent Document 2). However, in this composition, since it is a necessary requirement to contain 5% by weight or more of mineral oil, the strength is low and it cannot be formed into a thin shape. Actually, the examples in the same document do not mention the diameter of the molded body.

  Further, in the solid drawing material as described above, it is a well-known technique to include titanium dioxide as a general extender or pigment (for example, Patent Document 3 and Patent Document 4). Titanium dioxide has a strong hiding power, and there is no problem if you want to hide and overwrite the underlying pattern or characters, but once you want to overwrite it so that you can see the underlying pattern or characters, draw it once It is inconvenient because it is impossible to discriminate unless the lines and filled portions are removed. If you try to form a solid drawing material by blending titanium dioxide particles at a concentration that does not hide the pattern or characters of the ground here, there will be fewer titanium dioxide particles that should work as a build material. The solid drawing material is easily broken.

By the way, in the chemical definition, the wax means “ester of fatty acid and higher monovalent or divalent alcohol”. In this definition, some are liquid at room temperature, such as jojoba oil, and others are solid. However, usually, “solid or semi-solid organic matter at room temperature” and “melting in a temperature range from room temperature to near 100 ° C. and having a low melt viscosity” are collectively referred to as wax (non-patent document). 1). Specifically, in addition to waxes of the above chemical definition, trivalent (glycerin) or tetravalent (pentaerythritol) alcohol and fatty acid esters that are categories of fats and oils, paraffin wax, petrolatum, microcrystalline wax, etc. Petroleum hydrocarbons, fatty acids alone, and other substances are collectively referred to as waxes.
Among those collectively referred to as “waxes”, most of those defined as “fatty acids and higher mono- or dihydric alcohols” have poor compatibility with rosin and rosin-modified products such as glycerin esters of rosin.
On the other hand, trivalent (glycerin) or tetravalent (pentaerythritol) alcohol and fatty acid ester have good compatibility with rosin and rosin modified products such as glycerin ester of rosin.
From the above, in the present application, “a solid or semi-solid organic substance at room temperature” that is “melted in a temperature range from room temperature to near 100 ° C. and has a low melt viscosity”, in particular, the melting temperature (melting point) is Those having a temperature of 110 ° C. or lower are referred to as “wax”.

JP2008-45043 (Claims, Examples, etc.) JP 2010-37434 (Claims, Examples, etc.) JP-A-2002-348516 (Claims, Examples, etc.) WO2012 / 018107A1 (Claims, Examples, etc.)

"Characteristics and application of wax", supervised by Kenzo Fusegawa, Sachishobo, September 10, 1983

  The present invention has been made in view of the above-described problems of the prior art. Specifically, the present invention has a smooth writing taste, and can draw on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, white board, etc. It is an object of the present invention to provide a solid drawing material in which a portion drawn in a copy by a copying machine is not copied when a translucent sheet is covered from above. More specifically, it is an object to provide a solid drawing material that has a mechanical strength such as an excellent bending strength and is not easily broken while being capable of being drawn on a transparent drawing surface such as transparent plastic and glass in a moderately deep and clear manner. To do. It is another object of the present invention to provide a solid drawing material that can be easily erased with paper, such as cloth or tissue paper, a whiteboard eraser, or the like when drawn on the non-absorbing surface. In addition, while covering the outer periphery of such a solid drawing material with a protective sheet, it is possible to wear the solid drawing material without providing a special structure such as a perforation or a cut for separation or separation on the protective sheet. Accordingly, it is an object of the present invention to provide a solid drawing tool capable of newly exposing a tip portion that can be drawn.

  As a result of intensive studies to solve the above-described conventional problems, the present inventor has found that rosin and / or rosin as a resin in a solid drawing material comprising at least a resin, a wax, a pigment, and a white extender. By containing rosin-modified product such as glycerin ester in an amount of 0.5 to 20% by weight and waxes having a melting point of 45 ° C. or higher and / or pentaerythritol fatty acid ester in the range of 8 to 50% by weight, The inventors have found that a solid drawing material for the above purpose can be obtained, and have completed the present invention as described below.

(1) 1st invention In view of said subject, 1st invention of this application is the solid drawing material 20 which does not contain titanium dioxide while containing a resin component, a wax component, a coloring material, and a hollow resin particle at least,
As the resin component, at least one of rosin and rosin modified product is contained in the range of 0.5 wt% or more and 20 wt% or less,
As the wax component, at least one of glycerin fatty acid ester having a melting point of 45 ° C. or higher and pentaerythritol fatty acid ester is included in the range of 8% by weight to 50% by weight ,
It consists only of components having a melting point exceeding 40 ° C.

In the present invention, the rosin and rosin modified product used as the “resin component” are not particularly limited as long as they are generally classified as rosin and rosin modified products, and any of them can be used. It is also possible to use abithienic acid, which is the main component of rosin. Here, “rosin modified product” refers to glycerol ester of rosin and the like.
These can be used alone or as a mixture of two or more types without distinguishing chemical products and natural products, and are appropriately selected depending on the colorability and hardness of the target solid drawing material 20.
The resin component content is in the range of 0.5 wt% to 20 wt%. When this content is less than 0.5% by weight, the fixing property on a smooth surface is inferior, coloring is insufficient, the strength is weak, and it is not practical. On the other hand, if it exceeds 20% by weight, it is hard and the fixing property on a smooth surface is also inferior and coloring becomes insufficient.

  In the present invention, the glycerin fatty acid ester used as the “wax component” is not particularly limited as long as it has a melting point of 45 ° C. or higher and is generally classified as a glycerin fatty acid ester, and any of them can be used. For example, palmitic acid glycerides and stearic acid glycerides having a melting point of 45 ° C. or higher, and monoglycerides, diglycerides, and triglycerides can be used. Further, as other than these, natural products such as molasses such as hazelou and urushiro, which are mainly composed of glycerin fatty acid ester, and smack waxes such as yamahazero and yamaurushirou can be used.

  In the present invention, the pentaerythritol fatty acid ester used as the “wax component” is not particularly limited as long as it has a melting point of 45 ° C. or higher and is generally classified as a pentaerythritol fatty acid ester, and any of them can be used. For example, a pentaerythritol palmitate or a pentaerythritol stearate having a melting point of 45 ° C. or higher, and any of a monopentaeryslit, a dipentaeryslit, a tripentaeryslit, and a tetrapentaeryslit can be used. If the melting point is lower than 45 ° C., the practical strength is too weak, and if the solid drawing material 20 is thinly formed, the solid drawing material 20 is easily broken.

These glycerin fatty acid esters and pentaerythritol fatty acid esters used in the present invention can be used alone or in combination of two or more without distinguishing chemical products and natural products. It is appropriately selected depending on the colorability and hardness.
The content of the wax component is in the range of 8 wt% to 50 wt%. If this content is less than 8% by weight, it is hard, the fixability on a smooth surface is inferior, and coloring is insufficient. On the other hand, if it exceeds 50% by weight, the strength becomes weak and impractical.

As the “coloring material” in the present invention, azo organic pigments such as disazo yellow AAA and pyrazolone orange, cyanine organic pigments such as phthalocyanine blue and phthalocyanine green, higher organic pigments such as quinacridone red, dyes such as final colors, Inorganic pigments such as fluorescent pigments, carbon black, iron black, dials, and bitumen can be used. Further, as will be described later, a fluorescent dye or a fluorescent pigment can be used in some cases.
As the “hollow resin particles” in the present invention, all known extenders such as crosslinked styrene acrylic resin particles can be used.

(2) Second invention In addition to the features of the first invention, the second invention of the present application has a ratio of the resin component to the wax component in the range of 2: 1 to 1:25. It is characterized by.
When the content of the resin component is less than 1:25 with respect to the wax component, the resulting solid drawing material 20 is brittle, and the fixability on a smooth surface is inferior and coloring is insufficient. On the other hand, when the content of the resin component is more than 2: 1 with respect to the wax component, the solid drawing material 20 becomes hard, and the colorability is insufficient.
In short, if the resin component and the wax component are mixed at a suitable ratio (that is, in the range of 2: 1 to 1:25), the solid drawing material 20 having good fixability on a smooth surface and good coloring. Will be obtained.
In addition, the resin component and the wax component can be mixed in advance by melt mixing, and in the production process of the solid drawing material 20, it can also be mixed with another compound in a mixer or the like. The manufacturing method is not particularly limited.

(3) 3rd invention Moreover, 3rd invention of this application is characterized by including 5 weight% or more of hollow resin particles in addition to the characteristic of the said 1st invention.
When the content of the hollow resin particles is less than 5% by weight, it is not preferable because it cannot be drawn on a transparent plate surface such as transparent plastic or glass in a moderately dark and clear manner, resulting in a thin drawing surface. Moreover, even if this hollow resin particle is added too much, it does not help the expected performance improvement, but rather hinders it. The upper limit is usually about 15% by weight in terms of solid content.

(4) Fourth invention
Incidentally, glycerin fatty acid ester having a melting point below 45 ° C., and pentaerythritol fatty acid esters, waxes jojoba oil, spindle oil, liquid paraffin, squalane, squalene, alpha-olefin oligomer, a natural or synthetic oils such as silicone oil Can be used as long as it does not affect the preferred content of each component. In particular, a component having a melting point of 40 ° C. or lower (for example, an organic component such as wax or oil having a melting point of 40 ° C. or lower) should be used as long as the content of the solid drawing agent 20 is 4.5% by weight or less. Can do. However, when it is desired to form the solid drawing material 20 into a thin shape or to sharpen the tip, it is desirable not to contain these low melting point components as much as possible from the viewpoint of strength.

( 4 ) Fourth invention In addition to the features of the first invention, the fourth invention of the present application is at least one of polyethylene and an ethylene-vinyl acetate copolymer as an additional resin component other than the resin component. In a range of 20% by weight or less,
As an additional wax component other than the wax component, one or a mixture of two or more selected from the group consisting of paraffin wax having a melting point of 45 ° C. or higher, ozokerite, Fischer-Tropsch wax, polyethylene wax is included in a range of 30% by weight or less. It is characterized by.
That is, as an additional resin component, 20% by weight or less of polyethylene and / or ethylene-vinyl acetate copolymer can be used in combination with the resin component for the purpose of improving strength, adjusting hardness, writing quality, and the like. If this additional resin component exceeds 20% by weight, the moldability and coloring power on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc. are inferior, resulting in thin drawn lines.
In the above case, the total content of the resin component and the additional resin component is the line density and fixability when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc. Considering it, it is preferable to set it as 30 weight% or less.

Further, since the polyethylene and / or ethylene-vinyl acetate copolymer as the additional resin component and the glycerin fatty acid ester and / or pentaerythritol fatty acid ester having a melting point of 45 ° C. or more as the resin component are low in compatibility, As the additional wax component, one or a mixture of two or more selected from the group consisting of paraffin wax having a melting point of 45 ° C. or higher, ozokerite, Fischer-Tropsch wax, and polyethylene wax of 30% by weight or less is used in combination. Yes.
Conventionally known ozokerite, Fischer-Tropsch wax, and polyethylene wax can be used as the additional wax component, but paraffin wax preferably has a melting point of 45 ° C. or higher in terms of strength. The content is preferably 30% by weight or less in terms of the line density and fixability when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard and the like.
The total content of the wax component and the additional wax component is preferably 70% by weight or less, but is preferably 65% by weight or less in terms of strength. Furthermore, in consideration of the drawing density and fixability when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc., it is desirable to set it to 60% by weight or less.

( 5 ) Fifth Invention In addition to the features of the fourth invention, the fifth invention of the present application is selected from the group consisting of low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. One or a mixture of two or more
The ethylene-vinyl acetate copolymer has a vinyl acetate content of 30% by weight or less and a melt flow rate of 2 g / min or more.

That is, the polyethylene used in the present invention has kneadability with other compounding materials, moldability, drawn line density when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, and fixability. In view of the point, it is preferable to select from any one of low density polyethylene, linear low density polyethylene, and ultra low density polyethylene, or a mixture thereof. Furthermore, it is desirable to select from those having a melt flow rate of 2 g / min or more.
The ethylene-vinyl acetate copolymer used in the present invention is kneadable with other compounding materials, moldability, and when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc. In view of the drawn line density and fixability, it is preferable to select from those having a vinyl acetate content of 30% by weight or less and a melt flow rate of 2 g / min or more.

( 6 ) Sixth Invention In addition to the features of the fourth or fifth invention, the sixth invention of the present application has a ratio of the additional resin component to the additional wax component of 3: 1 to 1: It is characterized by being in the range of 20.
Here, when the ratio of the additional resin component is more than 3: 1 with respect to the additional wax component, the solid drawing material 20 becomes hard and the colorability becomes insufficient. On the other hand, when the ratio of the additional resin component is less than 1:20 with respect to the additional wax component, the obtained solid drawing material 20 becomes brittle and is insufficient in strength.

(7) Seventh invention The seventh invention of the present application, in addition to the features of the first invention, characterized in that it comprises a fluorescent dye or fluorescent pigment as the coloring material.
Originally, as the coloring material, dyes, general pigments having a low specific gravity, and pigments other than titanium dioxide can be used as appropriate. However, since the solid drawing material of the present invention is also characterized by the fact that the base can be seen through, it can be used as an underline marker. Therefore, in order to make the applied part stand out, a part of the dye or pigment is used. Alternatively, if the whole is made of a fluorescent dye or fluorescent pigment, it is possible to obtain a solid drawing material that does not conceal the base and can highlight the coated portion.
This highlighted application portion is not completely concealed but is semi-concealed. When a translucent sheet, particularly a translucent sheet of the same color as the solid drawing material, is covered from above, almost completely concealed. Even if copying is performed by a copying machine with this translucent sheet covered, the applied portion of the copied material cannot be seen because the image is erased. Thus, for example, if a part of a textbook or the like is marked with the solid drawing material of the present invention, and a semi-transparent sheet is placed thereon, and a copy is taken, an instant filling problem collection can be created.

Fluorescent dyes that can be used in the present invention include hydroxytrisulfonic acid (CI Solvent Green 7), flavin (CI Basic Yellow 1), acidic flavin (CI Acid Yellow 7), rhodamine B (CI Basic Violet 10), Rhodamine F4G (CI Basic Red 1), etc. can be used.
Fluorescent pigments include daylight fluorescent dyes such as acrylic resins, vinyl chloride resins, benzoguanamine resins, alkyd resins, aromatic sulfonamide resins, urea resins, melamine resins and their copolycondensation resins. It is a fluorescent resin fine powder that dissolves at a concentration that maximizes strength, and the synthetic resin is preferably heat resistant enough to withstand heating, stirring, kneading, extrusion molding, etc. during production. . By using a fluorescent pigment using such a heat-resistant synthetic resin, good color development can be obtained without aggregation of the pigment during production. Such fluorescent pigments include Sinloi color SB-11 (red / orange), Sinloi color SB-13 (red), Sinloi color SB-14 (orange), Sinloi color SB-15 (yellow), Sinloihi Color 17 (Pink), Thin Loi Color SB-37 (Magenta), etc., Loin Color SB series (Shin Loihi), Epo Color FP-112 (Pink), Epo Color FP-113 (Red), Epo Color FP-114 (Red) ), Epocolor FP-115 (red), Epocolor FP-116 (orange), Epocolor FP-117 (yellow), Epocolor FP-101 (white), Epocolor FP-10 (pink), Epocolor FP-20 (red), Epocolor FP-30 (Red), Epocolor FP Epocolor FP series (40 (orange), Epocolor FP-3000 (yellow), Epocolor FP-3000G (yellow), Epocolor FP-1007H (green), Epocolor FP-1025H (green), Epocolor FP-1050 (blue), etc. Nippon Shokubai Co., Ltd.), NKW-2100E series, NKW-6200E series (Nihon Kogyo Co., Ltd.), Ryudye-Luminous series (Dainippon Ink Co., Ltd.) and the like can be used.

( 8 ) 8th invention Moreover, the solid drawing tool 10 which concerns on the 8th invention of this application is the solid drawing material 20 which concerns on the said 1st invention,
A protective sheet 30 that is wound around the outer peripheral surface of the solid drawing material 20 two or more times and is formed of surface-treated paper, synthetic paper, polyester, nylon, polystyrene, polyvinyl chloride, or biaxially oriented polypropylene. ,
The solid drawing material 20 is characterized by cutting the protective sheet 30 together with a pencil sharpener.
The “protective sheet 30” refers to a sheet-like structure that is wound around the outer peripheral surface of the solid drawing material 20 to prevent dirt on fingers and protect or reinforce the solid drawing material 20.
The “solid drawing tool 10” is obtained by winding the protective sheet 30 around the solid drawing material 20.

The protective sheet 30 wound around the solid drawing material 20 for two or more turns used in the present invention is limited to plastics such as synthetic resins and natural resins, ceramics, metals, paper, wood, etc., as long as they can be cut with a pencil sharpener. Any of these materials can be used, but the material is appropriately selected in consideration of winding two or more times. That is, the material of the protective sheet 30 is preferably paper or synthetic resin in consideration of flexibility, thickness by winding a plurality of times, durability of the sharpener blade when cutting with a pencil sharpener, and machinability. .
In addition, about the paper as the material of the protective sheet 30, in consideration of the fact that the fiber is swollen by moisture absorption and the machinability is deteriorated, a surface processed paper such as art paper or coated paper, or a resin such as polypropylene is blended. Synthetic paper is desirable.

Moreover, about the synthetic resin as a material of the protection sheet 30, if it is a well-known sheet material or film material, it will not specifically limit, It can use. However, considering strength and machinability with a pencil sharpener, it is desirable to use polyester such as polyethylene terephthalate, nylon, polystyrene, polyvinyl chloride, or biaxially oriented polypropylene.
Moreover, it is desirable that an adhesive is applied to a part or all of the inner surface side of the protective sheet 30 in terms of strength and prevention of dust scattering during cutting. The material of the adhesive is not particularly limited as long as it has been used for seals, sheets, films and the like, and any material can be used.

In order to fix the solid drawing material 20 and the protective sheet 30, it is desirable that an adhesive is applied to a portion corresponding to the innermost layer of the protective sheet 30. Moreover, it is necessary to fix the outermost layer of the protective sheet 30 to the layer immediately below with an adhesive. These intermediate portions may or may not be coated with an adhesive, or may be selected as appropriate depending on the required characteristics, such as using an adhesive with weak adhesive strength. Is possible.
In the present invention, the protective sheet 30 is wound around the solid drawing material 20 for two or more turns. Moreover, if it is too thick, it will be easy to make a level | step difference in the part which overlaps with the edge of the innermost layer, it will be hard to wind at normal temperature, and will peel easily over time. Therefore, the thickness of the protective sheet 30 is preferably about 1 μm to 200 μm, more preferably 5 μm to 150 μm.

  Further, if the number of windings of the protective sheet 30 is less than 2 rounds, the strength reinforcing effect is small, but if it is too much, a deviation occurs, which causes a manufacturing problem. Therefore, it is desirable to adjust the diameter of the internal solid drawing material 20 and the thickness of the protective sheet 30 and to wrap around 3 to 20 turns.

( 9 ) Other In addition to the above components, conventionally known carnauba wax, candelilla wax, rice wax, montan wax, microcrystalline wax, ketone wax, polypropylene wax, various fatty acid amide waxes, zinc stearate, Metal soap such as lithium stearate may be appropriately selected and blended.
In this case, the total content of these components and the wax component (or the wax component and the additional wax component) is preferably approximately 70% by weight or less. In view of strength, the amount is preferably 65% by weight or less, and further 60% in consideration of the line density and fixability when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard and the like. % Or less is desirable.
In addition, in the present invention, for the purpose of dissolving or wiping the drawn lines with water, conventionally known various additives such as surfactants and ultraviolet absorbers with water-soluble color pencils, etc. have been described so far. You may mix | blend in the range which does not reduce the characteristics, such as drawing on an absorption surface and easy erasability.

In conventional solid drawing materials, the blending ratio of oil and the like has been increased for softening, but as a result, the strength is low, and on a soft surface, it is slippery with oil bleed etc. Was not obtained.
In contrast, in the solid drawing material of the present invention, the content of liquid components such as oil can be reduced to the utmost by the combination and ratio of specific resins and waxes, and as a result, a strong and smooth non-absorbing surface is obtained. A solid drawing material capable of drawing was obtained.
That is, according to the present invention, it has a smooth writing taste, and can be drawn with a moderately high density even on smooth non-absorbing surfaces such as coated paper, plastic, metal, glass, whiteboard, etc. It is possible to highlight a portion, and when a translucent sheet is covered from above, a solid drawing material in which a portion drawn in copying by a copying machine is not copied is provided. More specifically, it is possible to provide a solid drawing material that has a mechanical strength such as an excellent bending strength and is not easily broken while being capable of drawing clearly and clearly on a transparent plate surface such as transparent plastic and glass. Moreover, when drawing on said non-absorbing surface, the solid drawing material which can be erase | eliminated easily with papers, such as cloth and tissue paper, a whiteboard eraser, etc. is provided. In addition, while covering the outer periphery of such a solid drawing material with a protective sheet, it is possible to wear the solid drawing material without providing a special structure such as a perforation or a cut for separation or separation on the protective sheet. Accordingly, a solid drawing tool capable of newly exposing a tip portion that can be drawn is provided.

Among the solid drawing materials according to the embodiment of the present invention, those formed into a quadrangular prism shape (A) and those formed into a columnar shape (B) are respectively shown in perspective views. The solid drawing tool by which the protection sheet was wound around the solid drawing material of FIG. 1 is shown with a perspective view. FIG. 3 shows an enlarged part of the III-III cross section of FIG. 2. The solid drawing tool of FIG. 2 cut by the pencil sharpener is shown in a perspective view.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

(1) Composition and production method of Examples and Comparative Examples (1-1) Example 1
Hazerou (melting point: 52 ° C.): 43% by weight
Rosin: 16% by weight
SX866 (a) (hollow crosslinked styrene acrylic resin particles, manufactured by JSR Corporation, powder): 31% by weight
Disazo Yellow AAA: 2% by weight
Phthalocyanine green: 8% by weight
The above blended composition is heated and mixed with a disper and dispersed, and then poured into a predetermined mold while being heated and melted, and a green solid as shown in FIG. 1 (A) having a cross section of 8.0 mm × 8.0 mm. A drawing material 20 was obtained.

(1-2) Example 2
Stearic acid glyceride (melting point 61 ° C.): 43% by weight
Rosin ester: 16% by weight
SX866 (a) (hollow crosslinked styrene acrylic resin particles, manufactured by JSR Corporation, powder): 30% by weight
Permanent red: 11% by weight
The above blended composition was heated and mixed with a disper and dispersed and then poured into a predetermined mold while being heated and melted to obtain a red solid drawing material 20 having a diameter of 8.0 mm as shown in FIG. .

(1-3) Example 3
Urushiro (melting point 52 ° C): 15% by weight
Rosin ester: 6% by weight
Fischer-Tropsch wax (melting point 110 ° C) 21% by weight
Montan wax: 12% by weight
Low density polyethylene (Sumitomo Chemical): 15% by weight
Kaolin (RC-1, Takehara Chemical Industries): 6% by weight
SX866 (a) (hollow crosslinked styrene acrylic resin particles, manufactured by JSR Corporation, powder): 15% by weight
Disazo Yellow AAA: 10% by weight
The above blended composition was heated and mixed with a disper and dispersed and then poured into a predetermined mold while being heated and melted to obtain a yellow solid drawing material 20 having a diameter of 8.0 mm as shown in FIG. .

(1-4) Example 4
Urushiro (melting point 52 ° C): 22% by weight
Rosin: 9% by weight
Paraffin wax 135F (Nippon Seiwa): 23% by weight
Microcrystalline wax (Nippon Seiwa): 5% by weight
Ethylene-vinyl acetate copolymer: 13% by weight
(Vinyl acetate content: 28% by weight, melt flow rate: 15 g / min)
SX866 (a) (hollow crosslinked styrene acrylic resin particles, manufactured by JSR): 8% by weight
Special No. 1 zinc oxide (Hakusuitec Co., Ltd.): 10% by weight
Ultramarine: 6% by weight
Phthalocyanine blue: 4% by weight
The above blended composition was heated and mixed with a disper and dispersed and then poured into a predetermined mold while being heated and melted to obtain a blue solid drawing material 20 having a diameter of 8.0 mm as shown in FIG. .

(1-5) Example 5
Hazerou (melting point: 52 ° C.): 34% by weight
Rosin ester: 12% by weight
Paraffin wax 155F (Nippon Seiwa): 15% by weight
Low density polyethylene (Sumitomo Chemical): 5% by weight
Ethylene-vinyl acetate copolymer: 3% by weight
(Vinyl acetate content: 28% by weight, melt flow rate: 40 g / min)
SX866 (a) (hollow cross-linked styrene acrylic resin particles, manufactured by JSR Corporation, powder): 21% by weight
Pyrazolone orange: 10% by weight
The above blended composition was heated and mixed with a disper and dispersed and then poured into a predetermined mold while being heated and melted to obtain an orange solid drawing material 20 having a diameter of 8.0 mm as shown in FIG. .

(1-6) Example 6
Stearic acid glyceride (melting point 61 ° C.): 43% by weight
Rosin ester: 16% by weight
SX866 (a) (hollow crosslinked styrene acrylic resin particles, manufactured by JSR Corporation, powder): 30% by weight
Permanent red: 11% by weight
The above blended composition is heated and mixed with a disper and dispersed and then poured into a predetermined mold while being heated and melted to obtain a red solid drawing material 20 having a diameter of 7.0 mm and a length of 120 mm as shown in FIG. It was. A protective sheet 30 made of polypropylene synthetic paper having a thickness of 100 μm, a width of 138 mm, and a length of 120 mm including an adhesive is wound around this five times as shown in FIG. 3, and the diameter is 8.0 mm and long as shown in FIG. A solid drawing tool 10 having a thickness of 120 mm was obtained.

(1-7) Example 7
Except that the protective sheet 30 of Example 6 was replaced with a protective sheet 30 made of biaxially stretched polypropylene having a thickness of 100 μm, a width of 138 mm, and a length of 120 mm including the adhesive, the same production method as in Example 6 above was used. A solid drawing tool 10 having a diameter of 8.0 mm and a length of 120 mm was obtained.

(1-8) Example 8
Except that the protective sheet 30 of Example 6 was replaced with a protective sheet 30 made of art paper having a thickness of 100 μm, a width of 138 mm, and a length of 120 mm including the adhesive, the diameter was set to 8 by the same manufacturing method as in Example 6 above. A solid drawing tool 10 having a thickness of 0.0 mm and a length of 120 mm was obtained.

(1-9) Example 9
Hazerou (melting point: 52 ° C.): 43% by weight
Rosin: 16% by weight
SX866 (a) (hollow crosslinked styrene acrylic resin particles, manufactured by JSR Corporation, powder): 31% by weight
Disazo Yellow AAA: 2% by weight
Phthalocyanine green: 8% by weight
The above blended composition was heated and mixed with a disper, dispersed and then poured into a predetermined mold while being heated and melted to obtain a green solid drawing material 20 having a diameter of 7.0 mm and a length of 120 mm. A protective sheet 30 made of polyvinyl chloride having a thickness of 80 μm, a width of 141 mm, and a length of 120 mm including the adhesive was wound around this 6 times to obtain a solid drawing tool 10 having a diameter of 7.9 mm and a length of 120 mm.

(1-10) Example 10
The same manufacturing method as in Example 9 except that the protective sheet 30 of Example 9 was replaced with a protective sheet 30 made of styrene having a thickness of 80 μm, a width of 141 mm, and a length of 120 mm including the adhesive. The solid drawing tool 10 of 9 mm and length 120 mm was obtained.

(1-11) Comparative Example 1
Hazerou (melting point: 52 ° C.): 43% by weight
Rosin: 16% by weight
Talc: 17% by weight
Titanium dioxide: 14% by weight
Disazo Yellow AAA: 2% by weight
Phthalocyanine green: 8% by weight
The above blended composition is heated and mixed with a kneader and then kneaded with two rolls, then heated and melted, poured into a predetermined mold, cooled and solidified, and the cross section is 8.0 mm × 8.0 mm. A green solid drawing material as shown in 1 (A) was obtained.

(1-12) Comparative Example 2
Hazerou (melting point 52 ° C): 40% by weight
Paraffin wax 155F (Nippon Seiwa): 10% by weight
White mineral oil: 10% by weight
Talc: 16% by weight
Titanium dioxide: 14% by weight
Disazo Yellow AAA: 2% by weight
Phthalocyanine green: 8% by weight
The above blended composition is heated and mixed with a kneader, and then kneaded with two rolls, then heated and melted, poured into a predetermined mold, cooled and solidified, and the cross section is 8.0 mm × 8.0 mm in green. A solid drawing material was obtained.

(1-13) Comparative Example 3
Hazerou (melting point 52 ° C): 15% by weight
Paraffin wax 135F (Nippon Seiwa): 10% by weight
Rosin: 16% by weight
Amorphous poly α-olefin: 0.5% by weight
White mineral oil: 10% by weight
Talc: 24.5% by weight
SX866 (a) (hollow crosslinked styrene acrylic resin particles, manufactured by JSR Corporation, powder): 14% by weight
Disazo Yellow AAA: 2% by weight
Phthalocyanine green: 8% by weight
The above blended composition is heated and mixed with a disper, dispersed and then heated and melted, poured into a predetermined mold, cooled and solidified to obtain a green solid drawing material having a cross section of 8.0 mm × 8.0 mm on a side. It was.

(1-14) Comparative Example 4
Urushiro (melting point 52 ° C): 15% by weight
Fischer-Tropsch wax (melting point 110 ° C.): 21% by weight
Montan wax: 12% by weight
Low density polyethylene (Sumitomo Chemical): 21% by weight
Kaolin: 6% by weight
SX866 (a) (hollow crosslinked styrene acrylic resin particles, manufactured by JSR Corporation, powder): 15% by weight
Disazo Yellow AAA: 10% by weight
The above blended composition was heated and mixed with a disper and dispersed and then poured into a predetermined mold while being heated and melted to obtain a yellow solid drawing material having a diameter of 8.0 mm.

(1-15) Comparative Example 5
Urushiro (melting point 52 ° C): 22% by weight
Paraffin wax 135F (Nippon Seiwa): 23% by weight
Microcrystalline wax (Nippon Seiwa): 5% by weight
Ethylene-vinyl acetate copolymer: 22% by weight
(Vinyl acetate content: 28% by weight, melt flow rate: 15 g / min)
Talc: 8% by weight
SX866 (a) (hollow cross-linked styrene acrylic resin particles, manufactured by JSR Corporation, powder): 10% by weight
Ultramarine: 6% by weight
Phthalocyanine blue: 4% by weight
The above blended composition was heated and mixed with a disper, dispersed and then poured into a predetermined mold while being heated and melted to obtain a blue solid drawing material having a diameter of 8.0 mm.

(1-16) Comparative Example 6
Hazerou (melting point: 52 ° C.): 34% by weight
Paraffin wax 155F (Nippon Seiwa): 15% by weight
Low density polyethylene (Sumitomo Chemical): 15% by weight
Ethylene-vinyl acetate copolymer: 5% by weight
(Vinyl acetate content: 28% by weight, melt flow rate: 40 g / min)
Calcium carbonate: 6% by weight
SX866 (a) (hollow crosslinked styrene acrylic resin particles, manufactured by JSR Corporation, powder): 15% by weight
Pyrazolone orange: 10% by weight
The above blended composition was heated and mixed with a disper and dispersed, and then poured into a predetermined mold while being heated and melted to obtain an orange solid drawing material having a diameter of 8.0 mm.

(1-17) Comparative Example 7
Except that the protective sheet 30 of Example 6 above was replaced with a protective sheet made of high-quality paper including an adhesive and a thickness of 100 μm, width 138 mm, and length 120 mm, a diameter of 8. A solid drawing tool having a length of 0 mm and a length of 120 mm was obtained.

(1-18) Comparative Example 8
The same composition as in Example 6 above was heated and mixed with a disper and dispersed, then kneaded with two rolls, heated and melted, poured into a predetermined mold, red with a diameter of 7.8 mm and a length of 120 mm. A solid drawing material was obtained. A protective sheet made of polypropylene synthetic paper having a thickness of 80 μm, a width of 28 mm, and a length of 120 mm was wound around this, and the mating portion was bonded with an adhesive to obtain a solid drawing tool having a diameter of 8.0 mm and a length of 120 mm.

(1-19) Comparative Example 9
Except that the protective sheet of Comparative Example 7 was replaced with a protective sheet made of art paper having a thickness of 80 μm, a width of 28 mm, and a length of 120 mm, the manufacturing method was the same as that of Comparative Example 7, and the diameter was 8.0 mm and the length was 120 mm. A solid drawing tool was obtained.

(1-20) Comparative Example 10
Urushiro (melting point 52 ° C): 15% by weight
Fischer-Tropsch wax (melting point 110 ° C.): 21% by weight
Montan wax: 12% by weight
Low density polyethylene (Sumitomo Chemical): 21% by weight
Kaolin: 6% by weight
SX866 (a) (hollow crosslinked styrene acrylic resin particles, manufactured by JSR Corporation, powder): 15% by weight
Disazo Yellow AAA: 2% by weight
Phthalocyanine green: 8% by weight
The above blended composition was heated and mixed with a disper and dispersed and then poured into a predetermined mold while being heated and melted to obtain a green solid drawing material having a diameter of 8.0 mm.

(1-21) Comparative Example 11
An adhesive is applied to the outer peripheral surface of the solid drawing material similar to that in Example 6 above, and loaded onto a wooden shaft of an outer diameter of 8.0 mm and an inner diameter of 7.1 to obtain a solid drawing tool having a diameter of 8.0 mm and a length of 120 mm. Obtained.

(2) Evaluation method (Examples 1-5, Comparative Examples 1-6)
The solid drawing materials of Examples 1 to 5 and Comparative Examples 1 to 6 were evaluated and confirmed for strength, colorability and erasability when drawing on paper, PET film, glass, and whiteboard.

(2-1) Strength Three-point bending strength was measured for each solid drawing material at a temperature of 23 ° C. with a fulcrum of 40 mm, and the load (unit: N) when broken was determined.

(2-2) Colorability The solid drawing materials according to Example 1 and Comparative Examples 1 to 3 were sharpened by cutting the tip with a cutter knife. The solid drawing materials according to Examples 2 to 5 and Comparative Examples 4 to 6 were sharpened by cutting the tip with a small mini-sharpener. Each of these was used to draw on copy paper, PET film, glass slope, and whiteboard (WB), and the colorability at that time was evaluated in five stages of A to E. The evaluation criteria were as follows.
A ″: The drawn line was too dark, and the underlying pattern and characters were not visible at all.
A ': The drawn line was too dark and it was difficult to see the pattern and letters on the groundwork.
A: The drawn lines are dark and clearly visible, but the pattern and characters on the ground are well discernable.
B: Although the drawn line was too thin and the marking was difficult to see, the pattern and characters on the base were well discernable.
C: The drawn line is too thin and the marking is difficult to see, and the presence or absence of the marking is unknown.
D: The drawn line is drowning considerably and cannot be seen without care.
E: The drawn line is hardly visible or cannot be drawn.

(2-3) Copying machine erasability Copying in the standard state of black and white copy of IMAGO MP C6001 made by RICOH, covering the drawn line drawn on the copy paper in (2-2) above with a PET film having a light transmittance of 50%. The erasability at that time was evaluated in five stages of A to E. The evaluation criteria were as follows.
A: The characters on the ground completely disappeared and could not be discriminated at all.
B: Some characters on the background were visible but could not be identified.
C: The characters on the base are thin and can be distinguished by careful observation.
D: The characters on the background look a little thin and can be distinguished normally.
E: The characters on the background look normal and can be distinguished without problems.

(2-4) Erasability The drawn lines drawn on the PET film, glass slope, and whiteboard in (2-2) above were rubbed with tissue paper, and the erasability at that time was evaluated in five stages of A to E. The evaluation criteria were as follows.
A: It disappears well and no trace remains.
B: Disappears but leaves a trace.
C: The shape of the drawn line remains without disappearing.
D: It hardly disappears.
E: Not disappeared at all (however, when the evaluation in (2-2) was D or E, this evaluation was used).

(2-5) Evaluation Results Table 1 below shows the evaluation results for the above evaluation methods using Examples 1 to 5 and Comparative Examples 1 to 6.

  As described above, the solid drawing materials according to Examples 1 to 5 of the present invention all showed good results. That is, about intensity | strength, all Examples 1-5 showed numerical value sufficient for practical use. In addition, for any drawing target, A evaluation was obtained for both coloring property, copying machine erasing property and erasing property. However, the erasability when drawn on the whiteboard was slightly inferior to the erasability of the commercially available whiteboard-specific marker, and therefore B was determined.

On the other hand, the test results of Comparative Examples 1 to 6, which are outside the scope of the present invention, resulted in inferior evaluation except for the evaluation of colorability on copy paper, and inevitably resulted in inferior copying machine erasability. It became.
First, since Comparative Example 2 was only hazel but no rosin or the like was added, the tip was easily broken during drawing. Moreover, it slipped with respect to the smooth surface softly, and the result was that it was not possible to draw to the extent that the underlying pattern and characters could be seen.
In Comparative Example 3 , since the amount of oil was large, the tip was easily broken at the time of drawing. Also, when rubbing the drawn lines on a smooth surface, the drawn lines were stretched and difficult to disappear.
In Comparative Examples 4 to 6, the strength was strong, and there was almost no problem when drawing on paper. However, when drawing on a smooth surface, it was impossible to slide and draw.

(3) Evaluation method (Examples 6 to 10, Comparative Examples 7 to 11)
About the solid drawing tools of the above Examples 6 to 10 and Comparative Examples 6 to 11, the strength and the cutting ability with a pencil sharpener were evaluated.

(3-1) Strength Three-point bending strength was measured for each solid drawing material at a temperature of 23 ° C. or 40 ° C. with a fulcrum of 60 mm, and the load (unit: N) when broken.

(3-2) Cutting performance with a pencil sharpener Five monitor monitors were used at room temperature and normal humidity (23 ° C, 50%) using a Mitsubishi pencil mini pencil sharpener (trade name: Pocket Sharpener DPS-101 PLT). After cutting with a sharp tip (see Fig. 4) in an environment and in an environment of high temperature and high humidity (35 ° C, 80%), the cutting performance is functionalized in the following 5 levels: 1-5 The average score was determined.
1: Remarkably bad.
2: Bad.
3: Not good or bad.
4: Good.
5: Remarkably good.

(3-3) Evaluation Results Table 2 below shows the evaluation results for the above evaluation methods using the examples and comparative examples.

  As described above, the solid drawing tools according to Examples 6 to 10 of the present invention showed good results in any of the evaluation methods. That is, the strength of the solid drawing tool itself showed a value of at least 50 N over both 23 ° C. and 40 ° C. temperature conditions. In addition, the machinability was also highly evaluated to exceed 4 points on average in any of the examples under the measurement conditions of normal temperature / normal humidity and high temperature / high humidity. Further, the protective sheet was not peeled off or torn during the cutting.

On the other hand, in the test results of Comparative Examples 7 to 11 which are outside the scope of the present invention, the evaluation results were inferior in each of at least one item.
The high quality paper used as the protective sheet in Comparative Example 7 is hard and easily absorbs moisture. Therefore, in Comparative Example 7 in which this is wound, cutting performance is clearly inferior compared to Example 6 in which the solid drawing material is the same. It was. The result was that the protective sheet was torn especially under conditions of high temperature and high humidity.
In Comparative Examples 8 and 9 , the winding of the protective sheet was weak because it was one turn, and it was easy to break, and the strength was insufficient as a solid drawing tool. Moreover, since the adhesive of the protective sheet was applied only to the overlapping part, the protective sheet was easily peeled off from the solid drawing material. As a result, the machinability was clearly inferior to that of Example 6 using the same solid drawing material.
In Comparative Example 10 , there was no problem with the machinability, but the strength was remarkably weak and it was easy to break, so it seems not suitable for practical use.
Comparative Example 11 1 was more robust and stronger than Example 6 using the same solid drawing material as much as it was provided with a wooden shaft. However, since the thickness of the wood shaft was as thin as 0.1 mm, the adhesive strength with the solid drawing material was weak, and the shaft was cracked particularly under high humidity conditions, and the evaluation of machinability was significantly reduced compared to Example 6. It became a thing.

  In the present invention, not only normal high-quality paper, drawing paper, and copy paper, but also smooth non-absorbing surfaces such as coated paper, plastic, metal, glass, whiteboard, etc. It can be drawn to the extent that it shows moderate concealment when drawn on copy paper, and when drawn on these non-absorbing surfaces, it can be easily used with cloth, tissue paper, whiteboard eraser, etc. The present invention can be used as a solid drawing material that can be erased and a solid drawing tool in which a protective sheet is wound.

DESCRIPTION OF SYMBOLS 10 Solid drawing tool 20 Solid drawing material 30 Protection sheet

Claims (9)

In a solid drawing material containing at least a resin component, a wax component, a color material and hollow resin particles and not containing titanium dioxide ,
As the resin component, at least one of rosin and rosin modified product is contained in the range of 0.5 wt% or more and 20 wt% or less,
As the wax component, at least one of glycerin fatty acid ester having a melting point of 45 ° C. or higher and pentaerythritol fatty acid ester is included in the range of 8% by weight to 50% by weight ,
A solid drawing material comprising only a component having a melting point exceeding 40 ° C.   The solid drawing material according to claim 1, wherein a ratio of the resin component to the wax component is in a range of 2: 1 to 1:25.   The solid drawing material according to claim 1, wherein the hollow resin particles are contained in an amount of 5% by weight or more. While containing at least one of polyethylene and ethylene-vinyl acetate copolymer as an additional resin component other than the resin component in a range of 20% by weight or less,
As an additional wax component other than the wax component, one or a mixture of two or more selected from the group consisting of paraffin wax having a melting point of 45 ° C. or higher, ozokerite, Fischer-Tropsch wax, polyethylene wax is included in a range of 30% by weight or less. The solid drawing material according to claim 1. The polyethylene is one or a mixture of two or more selected from the group consisting of low density polyethylene, linear low density polyethylene and ultra low density polyethylene,
5. The solid drawing material according to claim 4, wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 30% by weight or less and a melt flow rate of 2 g / min or more. The solid drawing material according to claim 4 or 5 , wherein a ratio of the additional resin component and the additional wax component is in a range of 3: 1 to 1:20.   The solid drawing material according to claim 1, wherein the coloring material contains a fluorescent pigment or a fluorescent dye. A solid drawing material according to claim 1;
The sheet is wound around the outer peripheral surface of the solid drawing material two or more times, and includes a protective sheet formed of surface-treated paper, synthetic paper, polyester, nylon, polystyrene, polyvinyl chloride, or biaxially oriented polypropylene ,
Solid drawing tool said solid drawing material is characterized in that it is intended to cut in unit sharpener each said protective sheet. The solid drawing tool according to claim 8 , wherein an adhesive is applied to a part or all of the inner surface side of the protective sheet.

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