JP2002201400A - Solid drawing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid drawing material that has excellent drawing proper ties and erasability. SOLUTION: The objective solid drawing material comprises alcohol-modified silicone and/or polyether-modified silicone as the first erasing component and at least one selected from the following compound as the second erasing component: (a) mono-ester of aliphatic monobasic acid and monohydric alcohol; (b) di-ester of dibasic acid and monohydric alcohol; (c) mono- or poly-ester of aliphatic monobasic acid and polyhydric alcohol; (d) monoester of aliphatic monobasic acid and polyalkylene glycol, and (e) polyoxyalkylene alkyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid drawing material, and more particularly to a solid drawing material excellent in erasability which can be used as a writing instrument for a writing board such as an enamel plate, a plastic plate, a white board, and the like.

2. Description of the Related Art Conventionally, as a writing instrument for a flat board such as a whiteboard, a quick-drying oil-based magic type containing an organic solvent such as a felt-tip pen or a felt-tip pen, or a type containing no organic solvent such as a crayon. Things have been used. The oil-based magic type is excellent in writability (writing taste and the like), but cannot be stored for a long period of time because the colorant sediments. When the pen tip is placed facing upward, writing becomes impossible in a short period of time, and color unevenness may occur even when the pen tip is laid horizontally. Further, there is a problem that the color gradually fades from the beginning of use, and the remaining amount of the ink is not well understood. The crayon type does not show such a decrease in writability, but there is a difference in writability depending on the material, and it cannot be completely erased when wiped off with a soft dry cloth such as felt. In addition, there is a drawback that erasure becomes more difficult with time and that the erasability is poor. Until now, no solid drawing material has been proposed which has practically satisfactory writing and erasing properties. Also, sealed in a closed container,
A stick type solid drawing material is desired.

[0002]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a solid drawing material having excellent writing and erasing properties.

The present invention has been made based on the finding that the above problems can be solved by using two types of erasability-imparting agents in combination. That is, the present invention provides a solid state containing an alcohol-modified silicone and / or a polyether-modified silicone as a first erasability imparting agent and at least one compound selected from the following group as a second erasability imparting agent. Drawing materials: (a) monoester of aliphatic monobasic acid and monohydric alcohol; (b) diester of dibasic acid and monohydric alcohol; (c) monoester of aliphatic monobasic acid and polyhydric alcohol Polyester; (d) a monoester of an aliphatic monobasic acid and a polyalkylene glycol; and (e) a polyoxyalkylene alkyl ether.

[0003]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The solid drawing material of the present invention contains an alcohol-modified silicone and / or a polyether-modified silicone as a first erasability imparting agent. As the modified silicone that can be used in the present invention, those having a viscosity at 25 ° C. of 20 to 10,000 CS are preferable.
Those having a size of from 00 to 5000 CS are particularly preferred. In the modified silicone that can be used in the present invention, the modifying group includes:
It is preferably contained in an amount of 0 to 70%. When the modified silicone has a hydroxyl group, the content of the hydroxyl group in the silicone is preferably 1 to 3%. When the modified silicone has a polyether group, the content of the polyether group in the silicone is preferably 5 to 70%. Those having hydroxyl groups bonded to both ends are particularly preferred. In general, silicone has a function of weakening the fixing power of a drawing material to a writing board such as a white boat and facilitating wiping, and is particularly effective in enabling wiping with a weak force. This work lasts several weeks after writing. However, the unmodified silicone inhibits the gel formation of the stick, making the stick prone to collapse. On the other hand, the above-mentioned modified silicone is preferable because the action of inhibiting formation of a gel is extremely small, and furthermore, the fixing power of the drawing material is weakened and wiping is facilitated. Such modified silicones are available, for example, from Toray Dow Corning Silicone under the trade names SF8427, SF8428, SH
It is commercially available at 8700. The amount of the modified silicone is 1 to 15% based on the total mass of the solid drawing material of the present invention.
Is more preferable, and more preferably 3 to 10%. When the compounding amount is within such a range, drying on the writing board is quick, and when erasing, dirt is not spread on the board, and the effect can be sufficiently exerted. In this specification, "%" means% by mass unless otherwise specified.

[0004] The solid drawing material of the present invention contains, as a second erasability imparting agent, at least one compound selected from the following group: (a) a monofunctional mixture of an aliphatic monobasic acid and a monohydric alcohol; (B) diester of dibasic acid and monohydric alcohol; (c) mono- or polyester of aliphatic monobasic acid and polyhydric alcohol; (d) monoester of aliphatic monobasic acid and polyalkylene glycol And (e) a polyoxyalkylene alkyl ether.

(A) Monoester of aliphatic monobasic acid and monohydric alcohol In the present specification, the monoester of aliphatic monobasic acid and monohydric alcohol is 6 to 38 carbon atoms, preferably 8 to 18 carbon atoms.
20 saturated or unsaturated aliphatic monobasic acids and 2 to 3 carbon atoms
0, preferably a monoester with 3 to 16 monohydric alcohols. Specifically, isopropyl myristate,
Octyl palmitate, cetyl isooctanoate, isocetyl stearate, isocetyl isostearate, butyl stearate, octyl stearate, isodecyl isononanoate, hexyl laurate, ethyl linoleate,
Examples include isoaraky neopentanoate, isocetyl 12-stearoyl stearate, cholesteryl stearate, phytosteryl isostearate and the like.
Of these, isopropyl myristate, octyl palmitate, cetyl isooctanoate, isocetyl stearate, isocetyl isostearate, butyl stearate, octyl stearate, and isodecyl isononanoate are preferred. Monoesters of such aliphatic monobasic acids and monohydric alcohols are, for example, trade names CIO, ICIS, ICS-R from Nikko Chemical and trade names I from Nihon Yushi.
PM-R, Unistar MB816, trade name Exepearl BS from Kao, trade name IOS from higher alcohol industry,
It is commercially available as KAK109.

(B) Diester of dibasic acid and monohydric alcohol In the present specification, the diester of dibasic acid and monohydric alcohol is a saturated or unsaturated compound having 4 to 12 carbon atoms, preferably 6 to 10 carbon atoms. A diester of a dibasic acid and a monohydric alcohol having 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples include diisopropyl adipate, dioctyl adipate, diethyl sebacate, dibutyl sebacate, dioctyl sebacate, dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, and the like.
Of these, diisopropyl adipate, dibutyl sebacate, and dioctyl sebacate are preferred. Such diesters of dibasic acids and monohydric alcohols are commercially available, for example, under the trade names DID and DIS from Nikko Chemical and under the trade name DBS from Daihachi Chemical.

(C) Mono or polyester of aliphatic monobasic acid and polyhydric alcohol In the present specification, mono or polyester of aliphatic monobasic acid and polyhydric alcohol has 6 to 38 carbon atoms, preferably A mono- or mono-acid of 8 to 20 saturated or unsaturated aliphatic monobasic acid and a polyhydric alcohol having 2 to 38, preferably 3 to 30 carbon atoms and having 2 to 20, preferably 2 to 12 hydroxyl groups Or polyester. In particular,
Propylene glycol didecanoate, glycerin trioctanoate, propylene glycol monocaprylate, tri-2
-Glyceryl ethylhexanoate, decaglyceryl heptastearate, decaglyceryl decastestearate, decaglyceryl decaisostearate, trimethylolalkane fatty acid triester (the carbon number of the alkane portion is 4 to 2)
0, having 8 to 18 carbon atoms in the fat portion) and fatty acid triglycerides (8 to 18 carbon atoms in the fat portion). Among them, decaglyceryl heptastearate, hexaglyceryl pentastearate, propylene glycol didecanoate, glycerin trioctanoate, trimethylolalkane fatty acid triester (carbon number of alkane portion of 4 to 4)
20, a fatty portion having 8 to 18 carbon atoms, and a fatty acid triglyceride (a fatty portion having 8 to 18 carbon atoms) are preferred. Such mono- or polyesters of aliphatic monobasic acids and polyhydric alcohols are, for example, Nikkol PDD, Decaglyn7-S, hexagulin 5-S from Nikko Chemical, Exepearl TGO from Kao, trade name from Nippon Yushi. It is commercially available as Unistar H334R, Unistar H327R, and Panassate 810.

(D) Monoester of aliphatic monobasic acid and polyalkylene glycol In the present specification, the monoester of aliphatic monobasic acid and polyalkylene glycol is 6 to 38 carbon atoms, preferably 8 to 8 carbon atoms. A monoester of 20 saturated or unsaturated aliphatic monobasic acids with polyethylene glycol and / or polypropylene glycol. Here, polyethylene glycol and polypropylene glycol include dimers and trimers, and preferably have a mass average molecular weight of 200 to 3500, more preferably 200 to 3000. However, a reaction product of 1 mol of an aliphatic monobasic acid and 1 mol of a polyoxyalkylene glycol is excluded. Specifically, polyethylene glycol monolaurate (2 to 10)
EO), polyethylene glycol monostearate (2
60 EO), polyethylene glycol monooleate (2 to 10 EO); polypropylene glycol monolaurate (2 to 10 PO), polypropylene glycol monostearate (2 to 60 PO), polypropylene glycol monooleate (2 to 10 PO); and polyethylene glycol And fatty acid esters having both propylene glycol. Of these, polyethylene glycol monostearate (2 to 10 EO) is preferred. Further, a polyethylene glycol fatty acid ester and a polypropylene glycol fatty acid ester can be used in combination. Such polyalkylene glycol fatty acid esters are available, for example, from Nikko Chemical under the trade name M
YS-2, MYS-4, MYS-10, and commercially available from Nippon Yushi under the trade names Nonion S-2 and Nonion S-4.

(E) Polyoxyalkylene alkyl ether In this specification, the polyoxyalkylene alkyl ether is a higher alcohol having 6 to 30 carbon atoms, preferably 10 to 20 carbon atoms, ethylene oxide and / or propylene oxide 1
To 50 mol, preferably 2 to 40 mol, obtained by addition polymerization. The weight average molecular weight is 100 to 350
It is preferably 0, more preferably 200 to 3000. As the polyoxyethylene type ether, for example, Nikko Chemical BO-
2 commercially available. The polyoxypropylene type ether is commercially available, for example, from Sanyo Chemical Industry Co., Ltd. under the trade name Newpole LB.

The polyoxyethylene polyoxypropylene type ether is synthesized by block addition or random addition of ethylene oxide and propylene oxide to the above-mentioned higher alcohol. Block adducts are more preferred. More specifically, 1-20 moles of ethylene oxide and 1 mole of propylene oxide are added to 1 mole of cetyl alcohol.
Preferred are those obtained by block addition of 10 to 10 mol, those obtained by block addition of 10 to 30 mol of ethylene oxide and 1 to 10 mol of propylene oxide to 1 mol of decyl alcohol. Among them, those in which the ratio of ethylene oxide to propylene oxide is from 1: 1 to 1: 8 are more preferable. Such a polyoxyalkylene alkyl ether is, for example,
Nikko Chemical PBC31 and PB from Nikko Chemical
It is commercially available as C41.

[0011] These second erasability imparting agents can be used alone or in combination of two or more. Especially, it is preferable to use (c) and another kind together. In particular, it is preferable to use both (c) and (e). The total amount of these compounds is preferably from 10 to 40%, more preferably from 15 to 35%, based on the total weight of the solid drawing material of the present invention. In the present invention, the first erasability imparting agent and the second erasability imparting agent,
It is preferably used in a weight ratio of 1:40 to 3: 2, more preferably in a ratio of 1:12 to 2: 3. When the first erasability-imparting agent is used alone, the erasability is not sufficient, and when the second erasability-imparting agent is used alone, almost sufficient erasability is obtained. Requires some power. The combined use of the first erasability imparting agent and the second erasability imparting agent is preferable because sufficient erasability can be obtained even with a weak force for erasing.

The coloring agent used in the present invention is not particularly limited, and known pigments or dyes can be used if necessary. Examples of the inorganic pigment include iron black, iron yellow, and red iron oxide , Ultramarine blue, navy blue, alumina white, carbon black, aluminum powder, bronze powder, mica and luminous pigments. Organic pigments include nitroso or nitro pigments such as naphthol green and naphthol yellow, lithol red, and lake kit C , Brilliant Carmin 6B, Watching Red, Bordeaux 1
Azo lake pigments such as OB, Fast Yellow, Disazo Yellow, insoluble azo pigments such as pyrazolone orange, para red, lake red 4R, naphthol red, condensed azo pigments such as Chromophtal Yellow, Chromophtal Red, Peacock Blue Lake, Alkaline Blue Lake Dyed lake pigments such as rhodamine lake, methyl violet lake and malachite green lake, phthalocyanine pigments such as phthalocyanine blue, fast sky blue and phthalocyanine green, anthrapyrimidine yellow, perinone orange, perylene red, thioindigo red, indanthrone blue Quinacridone pigments such as sullen pigments, quinacridone red and quinacridone violet, and dioxazine faces such as dioxazine violet , Isoindolinone pigments such as isoindolinone yellow, diketopyrrolopyrrole pigments and fluorescent pigments such as DPP Rett like. Examples of the white pigment include titanium oxide, zinc white, lead white, zinc sulfide, antimony oxide, alumina white, satin white, and barium sulfate. Titanium oxide is particularly preferable.

When the colorant is an inorganic pigment, the compounding amount of the colorant is 1 to 4 with respect to the total mass of the solid drawing material of the present invention.
0% is preferred, more preferably 1 to 30%,
When the colorant is an organic pigment, 1 to 15% is preferable,
More preferably, it is 1 to 10%.

Examples of the gelling agent that can be used in the present invention include dibenzylidene sorbitol and its derivatives or tribenzylidene sorbitol and its derivatives.
It is not particularly limited to these. As a derivative of dibenzylidene sorbitol, a derivative of dibenzylidene sorbitol having 1 to 5 carbon atoms at an arbitrary position of a benzene ring of a benzylidene group of dibenzylidene sorbitol.
Which are mono-, di- or tri-substituted with a halogen atom such as an alkyl group or an alkenyl group, chlorine, bromine or bromine. Among them, those substituted with an alkyl group having 1 to 3 carbon atoms are particularly preferable, and those substituted with a methyl group are more preferable. Specifically, methyl-substituted dibenzylidene sorbitol, bis (ethylbenzylidene) sorbitol, bis (p-ethylenebenzylidene)
Sorbitol, chlor-substituted dibenzylidene sorbitol and the like. Such dibenzylidene sorbitol is available, for example, from EC Chemical Company under the trade name EC-1.
And EC-4 from Shin Nihon Rika Co., Ltd.
D and D are commercially available from Mitsui Toatsu Chemicals, Inc. under the trade name NC-4.

The derivatives of tribenzylidene sorbitol include tribenzylidene sorbitol at any position of the benzene ring of the benzylidene group having 1 to 5 carbon atoms such as an alkyl or alkenyl group, a halogen atom such as chlorine, bromine or bromine. -Or tri-substituted ones. Among them, those substituted with an alkyl group having 1 to 3 carbon atoms are particularly preferable, and those substituted with a methyl group are more preferable. Specific examples include methyl-substituted tribenzylidene sorbitol, tris (ethylbenzylidene) sorbitol, tris (p-ethylenebenzylidene) sorbitol, chloro-substituted tribenzylidene sorbitol, and the like. Such a tribenzylidene sorbitol is commercially available, for example, from Shin Nihon Rika Co., Ltd. under the trade name Gelol T. Of these, dibenzylidene sorbitol and tribenzylidene sorbitol are preferably used. The compounding amount of the gelling agent is preferably 1 to 20%, more preferably 5 to 20% based on the total weight of the solid drawing material of the present invention.
〜１０10%. It is preferable that the amount of the gelling agent is within such a range, since sufficient gel strength is obtained and the stick is hardly broken.

In the solid drawing material of the present invention, the organic solvent may dissolve the above-mentioned gelling agent when heated, form a gel when the temperature is returned to room temperature, and dissolve a polymer compound capable of forming a film. As far as possible, it can be used without particular limitation. Specific examples include alcohols such as ethanol, propanol, isopropanol, methoxypropanol, n- and i-butanol, octanol, phenoxyethanol, diethylene glycol, and glycerin; aromatic compounds such as toluene and xylene; methyl ethyl ketone and methyl butyl ketone; Aliphatic ketones;
Esters such as ethyl acetate and butyl acetate; ethers such as ethyl ether; glycol ethers such as methyl cellosolve, ethyl cellosolve, ethylene glycol monobutyl ether and dipropylene glycol monomethyl ether; and fatty acids such as oleic acid and lauric acid. Can be Of these, alcohols and glycol ethers are preferable, and i-butanol, methoxypropanol, dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether, and phenoxyethanol are particularly preferable.

By using such an organic solvent, even when the writing pressure is strong, the solid drawing material is less likely to collapse during writing, and as a result, it is difficult for the writing residue that extends during wiping and causes soiling of the whiteboard to appear. This is preferable because the erasability is improved. These organic solvents can be used alone or in combination of two or more.
When two or more kinds are used in combination, the mixing ratio of each organic solvent is arbitrary as long as they are compatible with each other. For example, when phenoxyethanol is used, it is preferable to use phenoxyethanol and another organic solvent at a mass ratio of 1:15 to 1: 1 and particularly preferably 1:10 to 1: 2. Such an organic solvent is commercially available, for example, under the trade name 2-phenoxyethanol from Inoue Corporation, and under the trade name PHE-S from Yokkaichi Gosei Co., Ltd. The amount of the organic solvent used is preferably from 30 to 60%, more preferably from 35 to 50%, based on the total mass of the solid drawing material of the present invention. In particular, when phenoxyethanol is used in combination with another organic solvent,
Preferably, it is used at 15%. When the amount of the organic solvent used is within such a range, drying on a whiteboard is quick and dirt does not spread when erasing, which is preferable.

The polymer compound capable of forming a film that can be used in the solid drawing material of the present invention is not particularly limited as long as it is dissolved in the above-mentioned organic solvent. A strong film can be formed on the surface, but it can be easily and completely erased by gently wiping it with a dry cloth such as felt or soft paper even if it is applied to a writing board such as an enamel plate, plastic, or white board. There must be. Specific examples include polyvinyl acetal resins such as polyvinyl butyral and polyvinyl formal, and cellulose resins such as cellulose acetate butyrate, ethyl cellulose and acetyl cellulose. These polymer compounds can be used alone or in combination of two or more. Among them, polyvinyl acetal resin is preferable, and polyvinyl butyral is particularly preferable. In particular, polyvinyl acetal unit 70 to 83%, polyvinyl acetate 2 to 5%, polyvinyl alcohol unit 15 to 25%, average polymerization degree 200
Polyvinyl butyral of ~ 1000 is preferred. Such a polymer compound capable of forming a film is commercially available, for example, from Denki Kagaku Kogyo Co., Ltd. under the trade name Denkabutyral. The polymerization form of the polymer may be random, block, or graft. The compounding amount of such a film-forming polymer compound is preferably from 5 to 20%, more preferably from 8 to 15%, based on the total mass of the solid drawing material of the present invention.

The solid drawing material of the present invention can contain various components in addition to the above components. For example, when the solid drawing material contains water, a preservative or an antifungal agent is used in 0.1%.
It is preferably contained in an amount of about 005 to 0.1% by mass. In addition, constitutional components such as silica, clay, talc, and calcium carbonate can be contained for increasing the amount, improving the strength of the stick, and improving the writing taste. The silica used in the present invention has a particle size of 0.02 to 15 mμ and a specific surface area of 1 to 700.
These are fine particles of m ² / g. The hydrophobic silica whose surface has been hydrophobized in advance includes Rheosil MT-10 (Tokuyama Soda), Nipsil SS hydrophobic silica (Nippon Silica Industry Co., Ltd.) and Aerosil R-972 hydrophobic silica (Nippon Aerosil Co., Ltd.) And are commercially available. Examples of hydrophilic silica include Tokusil (Tokuyama Soda Co., Ltd.), Silicasil (Bayer), Harmic (Micron Corporation), Aerosil Elsil (Nippon Aerosil Co., Ltd.), and Nipsil (Nihon Silica Kogyo Co., Ltd.) And syloid (Fuji Devison Chemical Co., Ltd.), microsilica (Elchem) and the like. In the present invention, silica is contained in an amount of 1 to 15%, preferably 3 to 10%, based on the total mass of the solid drawing material of the present invention.

The solid drawing material of the present invention is preferably manufactured so that the stick has a bending strength of 0.3 kgf or more, particularly preferably 0.5 kgf or more. It is preferable that the bending strength has such a value because the stick is hard to be broken. The bending strength is measured at room temperature in a bending strength test according to JIS S6026, item 5.6. The solid drawing material of the present invention is manufactured as follows. That is, a butyral resin is dissolved in a predetermined amount of an organic solvent, a pigment is added thereto, and a pigment dispersion is produced using a three-roll mill or a bead mill. As the pigment, a commercially available processed pigment kneaded with butyral resin in advance can be used. Next, the pigment dispersion and the gelling agent were placed in a flask equipped with a stirrer, thermometer, and reflux device, and stirred.
Heat to 0 ° C. to dissolve the gelling agent. The remaining material is added thereto, and the mixture is stirred until it becomes uniform. The obtained material is poured into a container and cooled and solidified to obtain the solid drawing material of the present invention.

According to the present invention, a solid drawing material excellent in both writing and erasing properties can be obtained.

[0021]

EXAMPLES The present invention will be described in more detail and concretely with reference to examples. The solid drawing material of the present invention was produced with the composition shown in Table 1 by the following method. In addition, the compounding amount means% with respect to the total mass of the composition. <Production method> Butyral resin is dissolved in an organic solvent, a pigment is added, a pigment dispersion is produced using a three-roll mill, and the pigment dispersion is gelled in a flask equipped with a stirrer, a thermometer, and a reflux unit. The mixture is heated to 140 ° C. with stirring to dissolve the gelling agent. The remaining material was added thereto, and the mixture was stirred until it became uniform. The obtained material was poured into a payout holder, capped, allowed to cool, and solidified.

[0022]

[Table 1]

Claims (1)

[Claims] 1. A solid drawing comprising an alcohol-modified silicone and / or a polyether-modified silicone as a first erasability imparting agent and at least one compound selected from the following group as a second erasability imparting agent. Materials: (a) monoester of aliphatic monobasic acid and monohydric alcohol; (b) diester of dibasic acid and monohydric alcohol; (c) mono or polyester of aliphatic monobasic acid and polyhydric alcohol (D) monoesters of aliphatic monobasic acids and polyalkylene glycols; and (e) polyoxyalkylene alkyl ethers.