JP3160732B2 - Solid cursive for writing board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid writing body for a writing board. More specifically, solid writing for a writing board that can be easily erased by handwriting marked on various writing boards made of enamel, metal, plastic, glass plate, etc. by rubbing with an erasing material such as cloth or soft paper About the body.

[0002]

2. Description of the Related Art Conventionally, several proposals have been disclosed as a solid writing body for a writing board (Japanese Patent Publication No. 55-1847).
No. 5, JP-A-4-139275, etc.). However, the degree of stickiness and stickiness of the handwriting is large, and the handwriting erasability has not always been satisfied.

[0003]

DISCLOSURE OF THE INVENTION The present invention is directed to a solid writing board for a writing board which has no deterioration due to environmental conditions or aging, has a small number of handwritings, and can be easily erased by light rubbing. It is intended to provide the body.

[0004]

Means for Solving the Problems The solid writing material for a writing plate of the present invention is a solid writing material for a writing plate comprising a pigment having a particle diameter of 0.1 μm or more, an excipient and a lubricant. The excipient is a wax selected from fatty acid-based wax, ether-based wax, fatty acid alkylolamide, and silicone-based wax, and the lubricant is represented by the following general formula (1) and / or
Alternatively, the solid writing material for a writing board is a material selected from the ester compounds represented by the general formula (2).

Embedded image

Embedded image Here, R represents an alkyl group having 13 or more carbon atoms, an alkenyl group, a hydroxyalkyl group, or a hydroxyalkenyl group, and R ^′ represents an alkyl group having 1 to 30 carbon atoms,
X represents hydrogen or a methyl group; φ represents an alkylene group having 1 to 34 carbon atoms, an alkynylene group, a phenylene group, a cyclohexylene group or a hydroxyalkylene group, and n represents 2 or 3 Indicates an integer.

The details will be described below. The pigment is crayon,
It is preferable to use a pigment having a particle diameter of 0.1 to 20 μm used for a colored pencil lead or the like. When the particle diameter is 0.1 μm or less, the pigment particles are adsorbed to the writing board when erasing, and the writing board is significantly stained. When the particle diameter is 20 μm or more, a satisfactory color density cannot be obtained.

Specific examples of the pigment include titanium oxide, iron oxide, red iron oxide, chromium oxide, ultramarine, cyanine blue, carmine 6B, carbon black, and a fluorescent pigment comprising a fluorescent dye and a resin solid solution.

As the fluorescent dye, thioflavin (C.I.
I. 49005), fluorescein (CI.453)
50), eosin (CI. 45380), rhodamine 6G (CI. 45160) and the like. Examples of the resin serving as a carrier for these dyes include polymethacrylic acid ester, vinyl chloride-vinyl acetate copolymer, alkyd resin, aromatic sulfamide resin, urea resin, triazine resin, and benzoguanamine resin.

The excipient is selected from fatty acid waxes, ether waxes, fatty acid alkylolamides and silicone waxes, and one or a combination of two or more of these can be used.

The polyol used for the fatty acid wax is
Polyglycerin having a polymerization degree of 10 or less (glycerin, diglycerin, triglycerin, etc.), sorbitol and condensates thereof, sucrose, polyethylene glycol having an average molecular weight of 400 to 10,000 can be used. As the fatty acid, a saturated fatty acid having 14 or more carbon atoms, for example, myristic acid, palmitic acid, stearic acid, arachinic acid, behenic acid, and montanic acid can be used.

Ether waxes include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether and polyoxyethylene behenyl ether, and polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Oxyethylene alkyl phenyl ethers can be used.

As fatty acid alkylolamide, lauric acid diethanolamide, stearic acid diethanolamide, behenic acid diethanolamide, lauric acid monoethanolamide, stearic acid monoethanolamide and the like can be used.

Examples of the silicone wax include an esterification product of an alcohol-modified silicone oil and a saturated fatty acid, an esterification product of a carboxyl group-modified silicone oil and a saturated alcohol, and amidation of an amino group-modified silicone oil with a saturated fatty acid. Products.

Hereinafter, the silicone wax will be described in more detail.

The esterified product of an alcohol-modified silicone oil and a saturated fatty acid is prepared by reacting an alcohol-modified silicone oil represented by the following general formulas (3), (4) and (5) with a saturated alcohol having 12 or more carbon atoms. It is an esterification product with a fatty acid. If the number of carbon atoms is less than 12, lubricity,
Stickiness and compatibility with other compositions are inferior and are not preferred.
The upper limit of the number of carbon atoms is not particularly limited, but is preferably 30 or less, which is easily available industrially. The effective molecular weight of the alcohol-modified silicone oil is 800 or more and 5000 or less on average. The esterification reaction is achieved in the absence of a catalyst or in the presence of a catalyst, in accordance with a usual S-esterification reaction.

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Embedded image

Embedded image However, n shows the integer of 10-60.

The esterification product of a carboxyl group-modified silicone oil and a saturated alcohol is an esterification product of a carboxyl group-modified silicone oil represented by the following general formula (6) and a saturated alcohol having 12 or more carbon atoms: If the number of carbon atoms is less than 12, lubricity, stickiness and compatibility with other compositions are inferior, which is not preferable. Although the upper limit of the number of carbon atoms is not particularly defined, it is 7
0 or less is preferable. It is effective that the molecular weight of the carboxyl group-modified silicone oil is 1000 or more and 5000 or less on average. The esterification reaction is achieved in the absence of a catalyst or in the presence of a catalyst according to a usual esterification reaction.

Embedded image However, n shows the integer of 10-60, m shows the integer of 1-10, x shows the integer of 1-10.

The amidation product of the amino group-modified silicone oil and the saturated fatty acid is an amidation product of the amino group-modified silicone oil represented by the following general formula (7) and a saturated fatty acid having 12 or more carbon atoms. If the number of carbon atoms is less than 12, lubricity, stickiness and compatibility with other compositions are inferior, which is not preferable. The upper limit of the number of carbon atoms is not particularly limited, but is preferably 30 or less, which is easily available industrially. The molecular weight of the amino-modified silicone oil is 800 on average.
More than 5,000 is effective. The amidation reaction is achieved according to a usual amidation reaction without a catalyst or in the presence of a catalyst.

Embedded image However, n shows the integer of 10-60.

These excipients are used in an amount of 5 to 80% by weight, preferably 15 to 60% by weight, based on the total composition of the solid cursive. If the amount is less than 5% by weight, the solid writing body is not sufficiently solidified and has insufficient strength. 80% by weight
With the above amount used, it is difficult to obtain a sufficient color density.

Examples of the lubricant include an ester compound represented by the general formula (1) and a diester compound represented by the general formula (2), such as silicone oil, polyalkylene glycol derivative, and high-grade liquid having 14 or more carbon atoms at room temperature. Can be used with either fatty acids or liquid paraffin
You.

Examples of the ester compound represented by the general formula (1) include a higher fatty acid monoester compound having 14 or more carbon atoms. Examples of higher fatty acids include myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, erucic acid, ricinoleic acid, hydroxystearic acid, isopalmitic acid, isostearic acid, and the like.

The diester compound represented by the general formula (2) has a residue of a dicarboxylic acid having 3 to 36 carbon atoms, and specifically includes malonic acid, succinic acid, adipic acid, sebacic acid,
Those having an acid residue such as dodecanediic acid, eicosadic acid, dimer acid, maleic acid, phthalic acid, malic acid and tartaric acid can be mentioned.

As the silicone oil, dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane, alkyl-modified dimethylpolysiloxane, polyether-modified dimethylpolysiloxane, fluorine-modified dimethylpolysiloxane and the like can be used.

As the polyalkylene glycol derivative, polyoxyethylene propylene glycol, polyoxyethylene propylene glycol monoalkyl ether, polyoxypropylene glycol monoalkyl ether and the like can be used.

As the higher fatty acid having 14 or more carbon atoms which is liquid at normal temperature (20 ° C.), oleic acid, erucic acid, palmito oleic acid, linoleic acid, ricinoleic acid, isostearic acid isopalmitate and the like can be used.

These lubricants are used in the range of 3 to 30% by weight, preferably 5 to 20% by weight, based on the total composition of the solid writing body. If the amount is less than 3% by weight, the handwriting and the paint film are strongly adhered to the writing board, and the handwriting is blurred and the desired handwriting cannot be obtained. On the other hand, if the used amount is 30% by weight or more, the solid writing body itself becomes sticky and stains hands and clothes. In addition, the handwriting itself is also sticky, and when erased, the writing board is stained.

[0025] The solidifying agent is used for suppressing the stickiness of the solid writing material and improving the water resistance without impairing the erasability, and is a condensate of hydrogenated castor oil, 5- to 7-valent sugar alcohol and aromatic aldehyde. And dextrin fatty acid esters.

These solidifying agents are used in an amount of 0.5 to 20% by weight, preferably 1 to 10% by weight, based on the total amount of the composition of the solid writing body.

[0027]

The above-mentioned excipient uniformly disperses the pigment and gives a writing performance with a sufficient color density and a smooth writing on a writing board. Then, by the interaction with the lubricant, writing can be performed smoothly, and the handwriting can be easily erased by lightly rubbing with a dry eraser.

[0028]

EXAMPLES Table 1 shows the compositions of the examples.

[Table 1] The numerical values of the compositions in the examples are expressed by weight%, and the contents of the raw materials are described below according to the note numbers. 1. Ultramarine No. 1900, particle size 1-3 μm [Daiichi Kasei Kogyo Co., Ltd.] 2. MAPICO RED R-110-7, particle size 0.5 to 2 μm [Titanium Industry Co., Ltd.] FA-207, particle size 3.5 to 4.5 μm [Shinloich Co., Ltd.] 4. Nonionic K-230, ether of PEG 3000 and lauryl alcohol [Nippon Oil & Fats Co., Ltd.] 5. Unigri GP-206 [Nippon Oil & Fats Co., Ltd.] 6. REODOL SP-P10 [Kao Corporation] 7. PEG 20-181, ester of PEG 2000 and stearic acid 8. Amizole LME, 1: 1 lauric acid monoethanolamide [Kawaken Fine Chemical Co., Ltd.] Silicone diol montanic acid diester

Embedded image Here, n represents a numerical value such that the average molecular weight becomes about 5000. 10. A monoester compound in which R, X, R ^′ and n in the general formula (1) are groups or numbers shown in Table 2.

[Table 2] 1 1. 1 2. 1 3. Diester compound in which R ^′ , X, n, and φ in the general formula (2) are each a group or a number shown in Table 3.

[Table 3] 1 4. TSF-4440, polyether-modified silicone [Toshiba Silicone Co., Ltd.] 15 . Thixin-R [Wilver Ellis Co., Ltd.] 16 . Leopard KE [Kaihatsu Chemical Co., Ltd.] 17 . Gelall D [Shin Nippon Rika Co., Ltd.]

The solid cursives of Examples 1 to 5 were manufactured according to the following formulation.

The excipients, lubricants and, if necessary, the solidifying agent are uniformly heated and stirred at 70 to 100 ° C. for 1 to 2 hours in the dissolution layer. Next, a pigment and a filler are added, and the mixture is kneaded and dispersed for 1 hour by a kneader while heating is continued. Thereafter, the mixture is poured into a mold, cooled and solidified to obtain a desired shape (φ
(8 × 60 mm).

As a comparative test, a solid writing material 2 of the prior art was used.
Seeds were manufactured. Table 4 shows the composition of the comparative example.

[Table 4] Comparative Example 1 is an example described in JP-B-55-18475, and Comparative Example 2 is an example described in JP-A-4-139275. The numerical values of the compositions in the comparative examples are expressed in terms of% by weight, and the contents of the raw materials are described below according to the note numbers. 1. Chromophtal blue 4GNP, C.I. I. Pigm
ent Blue 15: 3 [Nippon Ciba Geigy Co., Ltd.] 2. Thaitone R-5N [Sakai Chemical Industry Co., Ltd.] 3. MT-CI [Columbia Carbon Co., Ltd.] 4. AC polyethylene ^# 680, emulsified polyethylene wax [Allied Chemical Company] 5. Mitsui High Wax 220P [Mitsui Petrochemical Industry Co., Ltd.] Nonion S-6, PEG 600 monostearate [Nippon Oil & Fats Co., Ltd.] Each comparative example was produced according to the description of each gazette.

Performance Test (Writability and Erasability Test on Writing Board Surface) The solid writing bodies of Examples 1 to 5 and Comparative Examples 1 and 2 were written on an enamel board and a polyester-coated board, and their writability was measured. And erasability.

Table 5 shows the results.

[Table 5] The evaluation symbols in the table are as follows. As a writability test, a predetermined line was drawn at a writing pressure of 500 g and a writing speed of 5 cm / sec. ：: Writing can be performed smoothly without blurring. ×: Faint or unreadable. As an erasability test, the erasing material was rubbed with a load of 200 g using an erasing tool made of felt. ：: Erasable within 10 times. Δ: Erasable in 11 to 20 times. X: Erasing is not possible within 20 times.

[0034]

The solid writing material for a writing board of the present invention can form the intended clear handwriting on the writing board surface at normal writing pressure and writing speed. It can be easily erased by light abrasion with soft paper or the like, satisfying practicality.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-54-115922 (JP, A) JP-A-4-139275 (JP, A) JP-A-2-129278 (JP, A) JP-A 54-115278 88425 (JP, A) Fully open 1986-98089 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 13/00

Claims (1)

(57) [Claims] 1. A solid writing board for a writing board comprising a pigment having a particle diameter of 0.1 μm or more, an excipient and a lubricant, wherein the excipient is a fatty acid wax, an ether wax,
It is a wax selected from fatty acid alkylolamide and silicone wax, and the lubricant is a substance selected from ester compounds represented by the following general formulas (1) and / or (2). Solid cursive for board. Embedded image Embedded image Here, R represents an alkyl group having 13 or more carbon atoms, an alkenyl group, a hydroxyalkyl group, or a hydroxyalkenyl group, and R ^′ represents an alkyl group having 1 to 30 carbon atoms,
Represents a phenyl group or a cyclohexyl group, X represents hydrogen or a methyl group, φ represents an alkylene group having 1 to 34 carbon atoms, an alkynylene group, a phenylene group, a cyclohexylene group, or a hydroxyalkylene group, and n represents 2 or 3
Indicates an integer.