JP3154877B2 - Fluorescent solid writing material and highlight marker - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorescent solid writing material and a highlight marker having excellent drawing properties.

[0002]

2. Description of the Related Art Generally, as a writing instrument for partially highlighting characters and the like displayed on a recording medium such as a document and calling attention thereto,
Ink-type writing instruments are known. Ink-type writing instruments are typically felt pens with a built-in transparent ink containing a fluorescent coloring agent.However, if the tip of the pen is left exposed, the ink dries and writing becomes impossible. The ink penetrates into the fibers of the ink and ink show-through occurs. For this reason, there is a demand for a solid type which does not show off ink and does not worry about drying of the pen tip.

[0003] Conventionally, a mere solid type writing instrument which does not use a fluorescent coloring agent is disclosed in, for example, JP-A-3-22157.
No. 4 publication. In this publication, those comprising a pigment, an olefin resin, a wax, a fatty acid amide, a mineral oil, and an adhesive resin selected from rosin, ester gum, cumarone resin and alkyd resin are mentioned.

[0004] Such a solid writing material has the advantage that it can be drawn smoothly on a smooth paper surface, but if a fluorescent pigment is used as a coloring material because the tackifying resin is dark, the coloring is hindered and writing becomes unclear. There is a problem and it is not satisfactory enough as a fluorescent highlight marker.

[0005] As a solid type using a fluorescent coloring material, those comprising paraffin wax, microcrystalline wax, and liquid paraffin, as described in JP-A-52-58620, are mentioned.

[0006] Such a fluorescent solid writing material has an advantage that it can be drawn smoothly at the time of writing, but it has an insufficient adhesive strength on a smooth paper surface and an insufficient writing density, which is not satisfactory.

The present invention solves the above-mentioned problems, and provides a fluorescent solid writing material and highlight capable of drawing on a smooth paper surface, having good density, good slippage and color tone on the paper surface at the time of drawing, and having no stain on abrasion. It provides a marker.

[0008]

Means for Solving the Problems The present invention provides [1. A fluorescent solid writing material comprising a fluorescent pigment, a wax, a fatty acid which is solid at ordinary temperature, and a tackifying resin having a Gardner value of 4 or less. 2. The tackifying resin is an alicyclic saturated hydrocarbon resin 1
The fluorescent solid writing material according to the item. 3. 3. The fluorescent solid writing material according to claim 1, wherein the wax is a wax selected from paraffin wax and polyethylene wax. 4. 4. The fluorescent solid writing material according to item 1 or 3, wherein the fatty acid is a fatty acid having 12 to 18 carbon atoms. 5. Item 5. The fluorescent solid writing material according to any one of Items 1 to 4, wherein the tackifier resin has an average molecular weight of 300 to 2,000. 6. Item 6. The fluorescent solid writing material according to any one of Items 1 to 5, wherein the tackifying resin is a tackifying resin having a softening point of 150 ° C or lower. 7. Item 7. The fluorescent solid writing material according to any one of Items 1 to 6, further comprising an extender. 8. A highlight marker provided with an exterior material for protecting at least the periphery of a fluorescent solid writing material comprising a fluorescent pigment, a wax, a fatty acid which is solid at ordinary temperature, and a tackifying resin having a Gardner value of 4 or less. 9. 9. The highlight marker according to item 8, wherein a plurality of color cores having different colors are covered side by side with an exterior material. 10. 9. The highlighter marker according to item 8, which has two color cores, and whose writing ends are vertically arranged in opposite directions to be adjacent to each other. 11. 9. The highlighter marker according to item 8, wherein two color cores are arranged in parallel and the writing ends adjacent to each other are arranged in the same direction. 12. 9. The highlight marker according to item 8, wherein a plurality of color cores are arranged radially from the center in the cross section and are adjacent to each other. 13. Item 13. The highlighter marker according to item 12, wherein the color cores are separated by a partition made of wax, fatty acid which is solid at ordinary temperature, and a tackifier resin having a Gardner value of 4 or less. 14.4 color cores are arranged in a cross shape in cross section, and waxes, fatty acids which are solid at normal temperature, and Gardner value 4
The color core was separated by a partition made of the following tackifying resin: 8
Highlight marker according to item. About.

As used herein, the term "average molecular weight" as used herein means the number average molecular weight, and the "softening point" is a measurement based on the ring and ball method.
The “Gardner value” is based on JIS-K-5400, and represents the color depth by the closest number of a Gardner color number standard solution having a similar color. Gardner color number standard solution is a colorless and transparent glass tube with a color number from 1 to 18
In this set, a potassium chloroplatinate solution and an iron-cobalt solution were prepared with predetermined compositions in tubes with respective color numbers.

The fluorescent solid writing material used in the present invention comprises a tackifier resin having a Gardner value of 4 or less and a fatty acid which is solid at ordinary temperature.

A tackifying resin having a Gardner value of 4 or less is excellent in transparency, does not hinder the coloring of the fluorescent pigment, gives an adhesive force on a smooth paper surface, and has an excellent effect of improving the density of handwriting.

The tackifying resin having a Gardner value of 4 or less used in the present invention has an average molecular weight of 3 to obtain good tackiness.
The temperature is preferably from 2000 to 2000 and a softening point of 150 ° C. or less. If the average molecular weight is less than 300, the composition becomes semi-solid, and although the tackiness is provided, the tackifying power is inferior, and if it exceeds 2,000, the cohesive strength is increased and the tackifying effect is inferior. 300 ~
A range of 1000 is optimal.

The fluorescent solid writing material of the present invention is partially semi-solidified by writing pressure and frictional heat and becomes writable. However, if the softening point exceeds 150 ° C., the cohesive force becomes too large to make it semi-solid and it becomes difficult to semi-solidify. The imparting effect becomes inferior. Therefore, the softening point is preferably in the range of 130 ° C. or less. From the experimental results,
The amount of the tackifier resin may be in the range of 1 to 20% by weight, but 1 to 15% by weight gives a preferable result.

The tackifying resin used in the present invention includes:
Examples include aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, terpene resins, xylene resins, modified products and derivatives thereof. As the aliphatic hydrocarbon resin, Marcarez R-10
0B (manufactured by Maruzen Petrochemical Co., Ltd.) and the like, and as the alicyclic hydrocarbon resin, Alcon P-70 (manufactured by Arakawa Chemical Industries), Alcon P-90 (manufactured by the company), Alcon P-100 (manufactured by the company), Archon P-115 (manufactured by the company), Archon P-1
20 (manufactured by the company), Alcon P-125 (manufactured by the company), Alcon P-140 (manufactured by the company), Quinton 1325 (manufactured by Zeon Corporation), Quinton 1345 (manufactured by the company), Escolets 5380 (manufactured by Tonex Chemicals), Escolets 5300 (manufactured by the company), Escolets 5320 (manufactured by the company), S-Crystal A-100 (manufactured by Nippon Steel Chemical Co., Ltd.),
S-crystal A-120 (manufactured by the company), S-crystal A-100S (manufactured by the company), S-crystal A-120S
(Made by the company), Rigalight R-100 (made by Rika Hercules), Rigalight S-100 (made by the company), Rigalight R-90 (made by the company), Rigalight R-125 (made by the company)
Etc. As terpene-based hydrocarbon resins, YS Resin TO-105 (manufactured by Yasuhara Yushi Kogyo Co., Ltd.) and Clearon P-
85 (manufactured by the company), Clearon P-105 (manufactured by the company), Clearon P-115 (manufactured by the company), Clearon P-125
(Manufactured by the company), Clearon M-105 (manufactured by the company), Clearon M-115 (manufactured by the company), and the like. As xylene resins, Nicanol H (manufactured by Mitsubishi Gas Chemical), Nicanol HH (manufactured by the company), and Nicanol L ( Nikonol LL (Nikon), Nikanol LLL (Nikon), Nikanol H-80 (Nikon), and Nicanol M (Nikon). Preferably, an alicyclic saturated hydrocarbon resin selected from tackifying resins having a Gardner value of 1 or less is good. These can be used alone or in combination.

The cycloaliphatic saturated hydrocarbon resin is cyclopentadiene (CPD) or dicyclopentadiene (DCP).
It is a polymer produced using D) as a raw material or by adding hydrogen to an aromatic petroleum resin, and is represented by, for example, the following structural formula (1), (2) or (3).

[0016]

Embedded image (Where n is 2 to 27)

[0017]

Embedded image (Where m is 1 to 24, n is 1 to 24, and m + n is 2
5 or less)

[0018]

Embedded image (Where R is hydrogen or a methyl group, m is 0 to 16,
n is 0 to 16, m + n is 3 to 16)

Fatty acids which are solid at normal temperature are used as a lubricant. The fatty acid makes the fluorescent solid highlight marker slip on the paper during writing, and suppresses the generation of stains due to scratching of hands and fingers. From the experimental results, it is preferable that the number of carbon atoms is 12 to 18, and the compounding amount be in the range of 5 to 50% by weight. Fatty acids used include lauric acid, myristic acid, palmitic acid, stearic acid and the like.

The fluorescent pigment used as a coloring material is a daylight fluorescent dye such as an acrylic resin, a vinyl chloride resin, a benzoguanamine resin, an alkyd resin, an aromatic sulfonamide resin, a urea resin, a melamine resin and a copolymer thereof. Dissolve in synthetic resin at a concentration that maximizes daylight fluorescence intensity,
It is a fine powder of a fluorescent resin, and the synthetic resin preferably has heat resistance enough to withstand heating, stirring, kneading, extrusion molding, and the like at the time of production. By using a fluorescent pigment using such a heat-resistant synthetic resin, good color formation can be obtained without aggregation of the pigment during production. Examples of such fluorescent pigments include Sinloihi color SB-11 (red / orange), Sinloihi color SB-13 (red), Sinloihi color SB-14 (orange), Sinloihi color SB-15 (yellow), and Sinroihi color. Shinroihi color SB series (manufactured by Shinloihi) such as Color 17 (pink) and Shinroihi color SB-37 (magenta), Epocolor FP-112 (pink), Epocolor FP-113 (red), Epocolor FP-114
(Red), Epocolor FP-115 (red), Epocolor FP-116 (orange), Epocolor FP-1
17 (yellow), Epocolor FP-101 (white), Epocolor FP-10 (pink), Epocolor F
P-20 (red), Epocolor FP-30 (red), Epocolor FP-40 (orange), Epocolor FP-3000 (yellow), Epocolor FP-300
Epocolor FP such as 0G (yellow), Epocolor FP-1007H (green), Epocolor FP-1025H (green), Epocolor FP-1050 (blue)
Series (manufactured by Nippon Shokubai Co., Ltd.) is used,
It may be 40% by weight. If necessary, an organic or inorganic pigment can be added to such an extent that color development is not hindered.

The colorless wax used as the excipient is preferably colorless, and paraffin wax, polyethylene wax and the like are used, and the compounding amount may be 10 to 60% by weight.

If necessary, an extender such as calcium carbonate, talc, clay, kaolin, mica, magnesium carbonate, barium sulfate and the like can be blended.

The solid fluorescent writing material is obtained by heating the above ingredients,
It can be manufactured by extruding after stirring and kneading. The obtained fluorescent solid writing material is solid at normal temperature.

The highlight marker of the present invention includes writing instruments such as pencils and crayons, and is provided in various shapes according to the usage thereof.

Next, the present invention will be described with reference to the accompanying drawings. FIG. 1 shows an example of a highlighter marker. FIG. 1 shows a fluorescent solid writing material, that is, an exterior material 2 in which at least the peripheral surface of a color core 1 is a wooden shaft. FIG. 2 shows an enlarged sectional view of the color core 1 shown in FIG.

FIG. 3 shows an exterior material 5 comprising two color cores 3, 4 of different colors, for example, orange and yellow, with writing ends arranged vertically in opposite directions to be adjacent to each other, and a peripheral surface of which is a thread-wrapped paper winding. 2 shows a coated crayon. With such a configuration, it is possible to arbitrarily select and use a necessary color at the time of use. In addition, the thread-containing paper roll itself cuts the cutting line diagonally in a rectangular paper at a certain interval in advance,
A number of small holes are arranged in line at one end of the cutting line, and one cut thread is arranged under each small hole.This is a technology conventionally used in the fields of pencils, crepers and the like. (For example,
Japanese Utility Model Publication No. 35-7803). When such an exterior material 8 is used, it is not necessary to sharpen it with a pencil sharpener, so that the area of the color core end can be used to the maximum.

FIG. 4 is provided with two color cores 6, 7 of different colors, for example, orange and yellow, but they are overlapped in parallel, the writing ends adjacent to each other are in the same direction, and the outer peripheral surface is the same as that of FIG. 3 (not shown). 2) shows a bar-shaped writing instrument covered and protected by a). With such a configuration, it is possible to arbitrarily select and use a necessary color at the time of use.

FIG. 5 shows different colors, for example, orange, yellow, pink, and green color cores 8, 9, 10, and 11, which are arranged radially from the center in the cross section and are adjacent to each other.
2 shows a bar-shaped writing instrument covered and protected with the same exterior material (not shown). With such a configuration, it is possible to arbitrarily select and use colors necessary for use, or to mix and use a plurality of colors at the same time.

FIG. 6 shows different colors, for example orange, yellow, pink and green color cores 12, 13, 14, and 15.
Are arranged radially from the center in the cross section and are adjacent to each other,
The cores are separated by a consumable partition 16 composed of the wax, fatty acid solid at room temperature and a tackifying resin having a Gardner value of 4 or less, and the peripheral surface is covered with the same exterior material (not shown) as in FIG. 3 for protection. 2 shows a rod-shaped writing instrument that has been used. With such a configuration, it is possible to arbitrarily select and use a necessary color at the time of use, and it is possible to reduce color mixing of a plurality of colors even if any of the color cores is consumed by the partition 16.

FIG. 7 shows color cores 17, 18, 1 of different colors.
9 and 20 are arranged in a cross shape in a cross section, and the cores are separated by a consumable partition wall 21 made of the wax, a fatty acid solid at room temperature and a tackifying resin having a Gardner value of 4 or less,
Similarly, a rod-shaped writing instrument whose peripheral surface is covered with the same exterior material (not shown) as in FIG. 3 is shown. Here, the color cores 17 and 18 are pink, the color cores 19 and 20 are green, and the core cross sections of the color cores 18 and 20 are smaller than the color cores 17 and 19. With such a configuration, it is possible to arbitrarily select and use a color and a thick thin line necessary for use, and it is possible to reduce color mixing of a plurality of colors even if one of the color cores is consumed by the partition 21.

In each of the above embodiments, the exterior material is a wooden shaft and a thread-wrapped paper roll. However, the exterior material may be a barrel with a core feeding mechanism such as a knock type, a rotary type, or a slide type. Further, the paper winding need not be threaded.

[0032]

The present invention will be specifically described below with reference to examples. Example 1 After heating, stirring and kneading the following components at 100 to 120 ° C., extrusion molding was performed to produce a color core having a diameter of 4.4 mm, and the periphery of the color core was covered with the thread-containing paper roll used in FIG. . Epocolor FP-116 (orange fluorescent pigment) 15% by weight Paraffin wax 135 ° F. 35% by weight Polyethylene wax (medium density, molecular weight 4000) 10% by weight Myristic acid 20% by weight Alcon-P90 5% by weight Talc 15% by weight

Examples 2 to 21 and Comparative Examples Examples and comparative examples in which the composition is variously changed are shown in a table.

Test Using the heat-sensitive paper (manufactured by Fuji Photo Film Co., Ltd.), the highlight markers of Examples and Comparative Examples were tested for density, slippage on writing, color tone, stickiness, and stains due to abrasion. The test results were as shown in the table.

(Test Method) (1) Concentration: In the sensory measurement, a large handwriting density was indicated by ◎, a sufficient density was indicated by ○, and a slightly insufficient density was indicated by △. (2) Slippage on the paper surface during writing: を indicates good slippage in sensory measurement, ○ indicates normal slippage, △ indicates slight difficulty, and × indicates no slippage. (3) Color tone: The color which does not hinder the color development of the fluorescent pigment in the sensory measurement was evaluated as ○. (4) Stickiness: The presence or absence of stickiness was observed by sensory measurement. (5) Dirt due to rubbing: Stain was observed when handwriting was rubbed by hand.

[0036]

[Table 1]

[Table 2] Here, (Note 1) to (Note 7 ) mean the following. (Note 1): Orange fluorescent pigment manufactured by Nippon Shokubai Co., Ltd. (Note 2): Medium density, molecular weight 4000. (Note 3): Arakawa Chemical Industries, Ltd., softening point 70 ° C, average molecular weight 610, Gardner value 1 or less. (Note 4): Arakawa Chemical Industries, softening point 90 ° C, average molecular weight 570, Gardner value 1 or less. (Note 5): Arakawa Chemical Industries, Ltd., softening point 125 ° C, average molecular weight 750, Gardner value 1 or less. (Note 6): manufactured by Tonex Chemical Co., Ltd., softening point 85 ° C., average molecular weight 340, Gardner value 1 or less. (Note 7): Nippon Steel Chemical Co., Ltd., softening point 100 ° C, average molecular weight 800, Gardner value 1 or less.

Example 18 The components used in Example 1 and the following components were separately
After heating, stirring and kneading to 0 to 120 ° C., two colors are arranged in a semicircular cross section as shown in FIG.
A color core having a diameter of 4.4 mm was formed, and the periphery of the color core was covered with the thread-containing paper roll used in FIG. When the obtained highlight marker was tested in the same manner as in the above example, the same results as in example 1 shown in Table 1 were obtained. (Yellow) Fluorescent pigment Epocolor FP-117 (Yellow) 20% by weight Paraffin wax 135 ° F. 35% by weight Polyethylene wax (medium density, molecular weight 4000) 10% by weight Myristic acid 20% by weight Arcon-P90 5% by weight Talc 10% by weight

Example 19 The two components used in Example 18 and the following components were separately heated to 100 to 120 ° C., stirred and kneaded, and then, as shown in FIG. They were arranged and extruded to form a color core having a diameter of 4.4 mm, and the periphery of the color core was covered with the paper core containing the thread used in FIG. When the obtained highlight marker was tested in the same manner as in the above example, the same results as in example 1 shown in Table 1 were obtained. (Pink) Fluorescent pigment Epocolor FP-112 (Pink) 15% by weight Paraffin wax 135 ° F. 35% by weight Polyethylene wax (medium density, molecular weight 4000) 10% by weight Myristinic acid 20% by weight Archon-P90 5% by weight Talc 15% by weight (Green) Fluorescent pigment Epocolor FP-1025H (Green) 15% by weight Paraffin wax 135 ° F. 35% by weight Polyethylene wax (medium density, molecular weight 4000) 10% by weight Myristic acid 20% by weight Alcon-P90 15% by weight Talc 15% by weight

[0039]

According to the present invention, as is apparent from the above-mentioned comparative test, it is possible to draw on a smooth paper surface, and the density, the slip on the paper surface at the time of drawing, the color tone are good, there is no stain on abrasion, and the present invention is applied to an exterior material. A protected fluorescent solid writing material and a highlight marker are provided. INDUSTRIAL APPLICABILITY The present invention is particularly suitable for writing implements that can replace ink-type highlight markers, and has excellent operational effects.

[Brief description of the drawings]

FIG. 1 is a front view of a highlight marker according to the present invention.

FIG. 2 is an enlarged sectional view of the color core of FIG. 1;

FIG. 3 is a front view showing another example of the highlight marker of the present invention.

FIG. 4 is a cross-sectional view showing another example of the highlighter color core of the present invention.

FIG. 5 is a sectional view showing another example of the highlighter color core of the present invention.

FIG. 6 is a sectional view showing another example of the highlighter color core of the present invention.

FIG. 7 is a sectional view showing another example of the highlighter color core of the present invention.

[Description of sign]

1, 3, 4, 6, 7, 8, 9, 10, 11, 12, 1
3, 14, 15, 17, 18, 19, 20... 2, 5, ... exterior materials. 16, 21 ... partition walls.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-217090 (JP, A) JP-A-62-262873 (JP, A) JP-A-59-67279 (JP, U) (58) Survey Field (Int.Cl. ⁷ , DB name) C09D 11/00-11/20 B43K 19/00

Claims (14)

(57) [Claims] 1. A fluorescent pigment, a wax, a fatty acid which is solid at ordinary temperature, and an alicyclic hydrocarbon tree having a Gardner value of 4 or less.
Fluorescent solid writing material made of fat . 2. The fluorescent solid writing material according to claim 1, wherein the alicyclic hydrocarbon resin is an alicyclic saturated hydrocarbon resin. 3. The fluorescent solid writing material according to claim 1, wherein the wax is a wax selected from paraffin wax and polyethylene wax. 4. The fluorescent solid writing material according to claim 1, wherein the fatty acid is a fatty acid having 12 to 18 carbon atoms. 5. An alicyclic hydrocarbon resin having an average molecular weight of 30.
The fluorescent solid writing material according to any one of claims 1 to 4, wherein the number is 0 to 2,000. 6. The softening point of the alicyclic hydrocarbon resin is 150 ° C.
The fluorescent solid writing material according to any one of claims 1 to 5, wherein: 7. The fluorescent solid writing material according to claim 1, further comprising a body material. 8. A fluorescent pigment, a wax, a fatty acid which is solid at ordinary temperature, and an alicyclic hydrocarbon tree having a Gardner value of 4 or less.
A highlight marker provided with an exterior material for protecting at least the periphery of a fluorescent solid writing material made of fat . 9. The highlight marker according to claim 8, wherein a plurality of color cores having different colors are covered side by side with an exterior material. 10. The highlight marker according to claim 8, wherein there are two color cores, and the writing ends are vertically arranged in opposite directions to be adjacent to each other. 11. The highlight marker according to claim 8, wherein the number of color cores is two, and the writing ends adjacent to each other are overlapped in parallel and the writing ends are in the same direction. 12. The highlight marker according to claim 8, wherein a plurality of color cores are arranged radially from the center in cross section and are adjacent to each other. 13. A fluorescent pigment or wax, which is solid at ordinary temperature.
Certain fatty acids and tackifier resins with Gardner value of 4 or less
Are arranged radially from the center in the cross section
A highlight marker in which the color cores are separated by a partition made of a wax, a fatty acid which is solid at room temperature, and a tackifying resin having a Gardner value of 4 or less. 14. A fluorescent pigment or wax, which is solid at ordinary temperature.
Certain fatty acids and tackifier resins with Gardner value of 4 or less
Are arranged in a cross shape in cross section, and waxes, fatty acids which are solid at room temperature, and Gardner value 4
A highlight marker in which the color core is separated by a partition made of the following tackifying resin.