JPH09202869A - Water-soluble solid drawing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-soluble solid drawing material good in water solubility, when a drawing is corrected with a brush containing water, good in the extensibility of the dissolved drawing material and large in the breakage strength of the drawing material. SOLUTION: This water-soluble solid drawing material comprises at least 3-40wt.% of a known inorganic or organic pigment, 5-50wt.% of an animal or vegetable wax or a mineral or synthetic wax, 10-40wt.% of a surfactant for solubilizing the drawing material in water, and 1-15wt.% of a water-soluble thermoplastic polyesterpolyol resin and/or polyethyleneoxide resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble solid drawing material capable of obtaining a drawing surface such as a watercolor paint by drawing on a surface to be drawn such as drawing paper and then adding with a brush containing water.

[0002]

2. Description of the Related Art Conventionally, this type of water-soluble solid drawing material has been filed in Japanese Patent Application Laid-Open Nos. 3-153778 and 63-199775. JP-A-3-153778 discloses a watercolor pencil lead characterized by using a water-soluble binder, a lubricant, a pigment, and a surfactant as main components, and containing polyethylene glycol as at least a part of the lubricant. JP-A-63-199775 discloses that a colorant is mixed with a base consisting of waxes solid at room temperature, a nonionic surfactant having an HLB value of 10 or more, and a wax having a hydroxyl value of 80 or more. A water-soluble solid drawing material characterized by the following is disclosed.

[0003]

However, the watercolor pencil lead described in the above-mentioned Japanese Patent Laid-Open No. 3-153778 has the following problems.
After drawing on a drawing paper, when drawing with a brush containing water, the dissolved drawing material does not spread well, and there are problems that the drawing marks dissolved in water penetrate into the drawing paper and the drawing surface becomes mottled. In the production of a watercolor pencil lead, water is added to the raw material of the pencil lead, and the mixture is kneaded and molded. Therefore, the pencil lead is dried for a long time, which is also a problem in the production process. Further, the water-soluble solid drawing material described in JP-A-63-199775 has good water solubility, but the drawing material is fragile and the breakage strength is weak.
There was a problem that the drawing paper etc. was stained.

[0004]

DISCLOSURE OF THE INVENTION The gist of the present invention is a water-soluble solid drawing material comprising at least a pigment, a wax, a surfactant, and a polyester polyol resin and / or a polyethylene oxide resin.

Hereinafter, the present invention will be described in detail. The pigment used in the water-soluble solid drawing material of the present invention is used as a coloring material, and is conventionally known, such as carbon black, titanium oxide, iron black, ultramarine blue, rouge, zinc oxide, phthalocyanine blue, and phthalocyanine green. It is possible to use inorganic pigments such as Watching Red, Carmine 6B, and Hansa Yellow, and organic pigments, and they may be used alone or in combination of two or more kinds. Although the amount used varies greatly depending on the type of pigment, it is preferably 3 to 40% by weight based on the total amount of the water-soluble solid drawing material in consideration of color development and drawability.

The wax used in the water-soluble solid drawing material of the present invention is used for improving the coating performance of the water-soluble solid drawing material, and is an animal system such as beeswax, spermaceti, and white wax. Wax, candelilla wax, carnauba wax, plant wax such as wood wax, montan wax,
Natural wax such as mineral wax such as ozokerite, paraffin wax, petroleum wax such as microcrystalline wax, Fischer-Tropsch wax, low molecular weight polyethylene and their derivatives, montan wax, paraffin wax, each derivative of microcrystalline wax, cetyl Examples thereof include alcohols, stearic acid, polyethylene glycol stearate, and synthetic waxes such as castor wax, which may be used alone or in combination of two or more. The amount used is preferably 5 to 50% by weight based on the total amount of the water-soluble solid drawing material.
Incidentally, petroleum-based and low-molecular-weight polyethylene and their derivatives may cause aggregation when used in combination with some inorganic pigments. Therefore, it is preferable to appropriately combine them so that aggregation does not occur.

The surfactant used in the water-soluble solid drawing material of the present invention is used for solubilizing the water-soluble solid drawing material in water. Specifically, the surfactant is an anionic alkyl phosphate. Salt, polyoxyethylene alkyl ether phosphate, nonionic glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, poly Examples thereof include oxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and polyoxyethylene / polyoxypropylene alkyl ethers. These may be used alone or as a mixture of two or more. The amount used is preferably 10.0 to 40.0% by weight based on the total amount of the water-soluble solid drawing material. If it is less than 10.0% by weight, the effect may not be sufficiently obtained, and if it is more than 40.0% by weight, stickiness is likely to occur on the surface of the drawing material. Among the above-mentioned surfactants, in particular, the polyoxyethylene alkyl ether having 20 to 50 moles of polyoxyethylene and the alkyl group having 16 to 22 carbon atoms has a more preferable balance between moisture absorption and water solubilization, The water-soluble solid drawing material using this surfactant has an advantage that it hardly absorbs water even under high humidity and its change with time is small.

The polyester polyol resin and the polyethylene oxide resin used in the water-soluble solid drawing material of the present invention are thermoplastic water-soluble resins and are used for increasing the coating strength and the breakage strength. Commercially available polyester polyol resins include Paogen PP-15 and Egen
P-15 (above, Daiichi Kogyo Seiyaku Co., Ltd. product) can be illustrated. The polyethylene oxide resin is a polymerized product of ethylene oxide, and commercially available products include PEO-1 (average molecular weight: 15 to 400,000) and PEO.
-3 (average molecular weight: 600 to 1.1 million), PEO-8 (average molecular weight: 1.7 to 2.2 million), PEO-15 (average molecular weight: 330 to 3.8 million), PEO-18 (average molecular weight: 430 to 4.8 million) (The above are products of Sumitomo Seika Co., Ltd.). You may use the said resin individually or in mixture. The amount used is preferably 1.0% by weight to 15.0% by weight based on the total amount of the water-soluble solid drawing material. this is,
If the amount is less than 1.0% by weight, the effect may not be sufficiently obtained, and if the amount is more than 15.0% by weight, the solid drawing material becomes hard and the fixing property at the time of drawing is deteriorated or dust is generated. This is because

In addition to the above components, if necessary, an extender or filler, which is a conventionally known extender such as mica, clay, kaolin, talc, calcium carbonate, silica, barium sulfate, etc., may be added to the total amount of the water-soluble solid drawing material. Against 5-5
Of course, 0% by weight can be used in combination.

The water-soluble solid drawing material of the present invention can be manufactured by a conventionally known method for manufacturing a solid drawing material.
For example, the above components are mixed by heating with stirring, and if necessary, kneaded by a kneader such as a kneader or a roll mill, cooled, pulverized and pelletized. A method of molding the pellets as a water-soluble solid drawing material using an injection / press-fitting or extrusion molding machine can be mentioned.

[0011]

The polyester polyol resin and the polyethylene oxide resin used in the water-soluble solid drawing material according to the present invention are thermoplastic water-soluble resins. Since it is a thermoplastic resin, it is easily melted by heat and kneaded and molded easily. Also,
The molded water-soluble solid drawing material is provided with sufficient breakage strength, and the expansion of the drawing marks is suppressed, so that the drawing marks are less contaminated by abrasion of fingers, drawing paper, and the like. When it is water-soluble, it is a water-soluble resin and its long molecular chain prevents it from entering the paper fiber. Therefore, it has the effect of suppressing the permeation of the melted part into the drawing paper and increasing the fixing power to the drawing paper. is there. Therefore, the water-soluble solid drawing material according to the present invention has sufficient breakage strength, has good fixability of drawing marks on drawing paper, etc., and has good water solubility and elongation.

[0012]

Embodiments of the present invention will be described below. Example 1 Ultramarine 20 parts by weight Carnauba wax 35 parts by weight Polyoxyethylene (10) sodium lauryl phosphate 35 parts by weight Paogen PP-15 (polyester polyol resin) 10 parts by weight The above components are heated and mixed with stirring at 100 to 120 ° C. Cool with a cooling belt, crush and pelletize. The pellets were injection molded with an injection molding machine set at 90 to 110 ° C. to obtain a water-soluble solid drawing material having a length of 100 mm and a diameter of 7.3 mm. In addition, the numerical value in () of polyoxyethylene shows the number of moles of polyoxyethylene. same as below.

Example 2 Titanium oxide 6 parts by weight Carmine 6B 10 parts by weight Castor wax 2 parts by weight Candelilla wax 25 parts by weight Polyoxyethylene (15) glycerin monostearate 25 parts by weight PEO-15 (polyethylene oxide resin) 2 parts by weight Parts Calcium carbonate 30 parts by weight The above components were treated in the same manner as in Example 1 to obtain a water-soluble solid drawing material.

Example 3 Titanium oxide 3 parts by weight Phthalocyanine green 7 parts by weight Bovine hydrogenated oil 10 parts by weight 12-Hydroxystearin (wax) 15 parts by weight Polyoxyethylene (40) monostearate 20 parts by weight Paogen EP-15 (polyester) Polyol resin) 13 parts by weight Mica 20 parts by weight Talc 12 parts by weight The above components were processed in the same manner as in Example 1 to obtain a water-soluble solid drawing material.

Example 4 Titanium oxide 1 part by weight Hansa Yellow 8 parts by weight Diheptadecyl ketone (wax) 13 parts by weight Carnauba wax 15 parts by weight Polyoxyethylene (20) stearyl ether 22 parts by weight Paogen EP-15 (polyester polyol resin) ) 7 parts by weight PEO-1 (polyethylene oxide resin) 1 part by weight Calcium carbonate 20 parts by weight Talc 13 parts by weight The above components were processed in the same manner as in Example 1 to obtain a water-soluble solid drawing material.

Example 5 Carbon black 7 parts by weight Ultramarine blue 2 parts by weight Montan wax 18 parts by weight Rice wax 15 parts by weight Polyoxyethylene (25) oleyl ether 15 parts by weight Polyoxyethylene (30) behenyl ether 5 parts by weight Paogen PP- 15 (polyester polyol resin) 10 parts by weight Clay 28 parts by weight The above components were treated in the same manner as in Example 1 to obtain a water-soluble solid drawing material.

Example 6 Titanium oxide 5 parts by weight Phthalocyanine blue 8 parts by weight 130 ° F paraffin wax 2 parts by weight Candelilla wax 20 parts by weight Polyoxyethylene (20) nonylphenyl ether 25 parts by weight Paogen EP-15 (polyester polyol resin) ) 8 parts by weight PEO-3 (polyethylene oxide resin) 1 part by weight Calcium carbonate 20 parts by weight Talc 6 parts by weight Stearic acid 5 parts by weight The above components were processed in the same manner as in Example 1 to obtain a water-soluble solid drawing material.

Comparative Example 1 A water-soluble solid drawing material was obtained in the same manner as in Example 1 except that the paogen PP-15 was omitted.

Comparative Example 2 A solid drawing material was obtained in the same manner as in Example 2 except that polyethylene resin was used instead of PEO-15.

Comparative Example 3 A water-soluble solid drawing material was obtained in the same manner as in Example 3 except that polyethylene glycol was used instead of Paogen EP-15.

Comparative Example 4 In Example 4, the paogens EP-15 and POE-1 were used.
A solid drawing material was obtained in the same manner as in Example 4 except that the above was omitted.

Comparative Example 5 A water-soluble solid drawing material was obtained in the same manner as in Example 5, except that the paogen PP-15 was omitted.

Using the water-soluble solid drawing materials obtained in Examples 1 to 6 and Comparative Examples 1 to 5, water solubility test, elongation test, and breakage strength test were conducted. The results are shown in Table 1.

Water solubility test: The above water-soluble solid drawing material was used as a drawing paper, and the coating pressure was 300 gf ± 100 gf and the width was 2 c.
It is applied to a section having a length of m and a length of 5 cm. Using a paintbrush containing water (No. 10 paintbrush, manufactured by Pentel Co., Ltd.), a 3 cm up and down section is reciprocated 3 times with respect to a drawing mark having a width of 2 cm.
After the drawing paper is dried, a color computer (Mode
The Y value of each part was measured with 1SM-4, manufactured by Suga Test Instruments Co., Ltd., and the water solubility was calculated according to the following formula. A: Y value of a part which was traced with the above-mentioned paintbrush and melted in the drawn part. B: Y value of a portion which is not traced by the above-mentioned paintbrush in the drawn portion. C: Y value of the drawing paper itself. Water solubility = ((CB) / (CA)) x 100
(%) Incidentally, the larger the value of the water solubility, the better the water solubility.

Elongation test: The above water-soluble solid drawing material is used as a drawing paper, and the composition is applied once in the vertical and horizontal directions at an application pressure of 300 gf ± 100 gf in a section of 3 × 3 cm. The drawing trace was reciprocated up and down 3 times using a paintbrush containing water (No. 10 paintbrush, Pentel Co., Ltd.), and then applied while vertically moving the lid within a width of 3 cm ± 1 cm. Move 20 cm to the right of the section. After the test, the degree of color spread was evaluated by visual inspection of the colored part in the extended part. A: The color is deep to the end and the elongation is very good. ◯: The color is slightly thin, but the elongation is good. Δ: The color becomes pale and the elongation is poor. X: Color penetrates the drawing paper.

Breaking strength test: The above water-soluble solid drawing material was supported at a distance of 40 mm between fulcrums, a breaking jig having a radius of 5 mm and a width of 5 mm was used at the center thereof, and the speed was 2 cm.
A load is applied to the water-soluble solid drawing material at a speed of 5 / min, and five loads when the water-soluble solid drawing material is broken are measured, and the average value is obtained.

[0027]

[Table 1]

[0028]

As described in detail above, the water-soluble solid drawing material according to the present invention has sufficient breakage strength, good water solubility and good elongation, and exhibits excellent properties as a water-soluble solid drawing material. It is a thing. In particular, the water-soluble solid drawing materials obtained in Examples 4 and 5 have a very low moisture absorption rate even under high humidity as compared with the other Examples, and show excellent quality with respect to stability over time. It was

Claims (1)

[Claims] 1. A water-soluble solid drawing material comprising at least a pigment, a wax, a surfactant, and a polyester polyol resin and / or a polyethylene oxide resin.