JP2002088293A - Solid marker - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new solid marker which undergoes no excessive reduction in the flowability of an ink in the manufacturing process while eliminating the shortcomings of conventional solid markers, and which is substantially free from the odor of formaldehyde during its manufacture and in writing. SOLUTION: The solid marker contains a coloring agent, a gelling agent, a resinous component and a solvent, wherein the coloring agent comprises a soluble fluorescent pigment carried on a polyamide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel solid marker.

[0002]

2. Description of the Related Art Conventionally, various solid markers have been known. These are, depending on the properties and quality required for the solid marker, generally a fluorescent pigment, a gelling agent, an organic solvent, a resin component and other additives are appropriately mixed and melt-mixed, and poured into a predetermined mold, It is manufactured by cooling and solidifying.

However, conventional solid markers include:
There are drawbacks such as that the ink becomes a paste at the time of production, or the ink itself does not have fluidity. Therefore, when pouring the ink into the forming container or the like, it takes a long time to fill the corners of the forming container. On the other hand, reducing the amount of fluorescent pigment used can increase the fluidity of the ink,
As a result, the coloring property is reduced.

[0004] Further, it has a drawback that formaldehyde is fragrant at the time of production and at the time of writing.

[0005]

From the above viewpoints, there has been a strong demand for the development of a solid marker in which the fluidity of the ink is not excessively reduced in the manufacturing process and the aroma of formaldehyde is reduced. Such solid markers have not yet been developed.

SUMMARY OF THE INVENTION Accordingly, it is a main object of the present invention to provide a solid marker in which the fluidity of the ink is not excessively reduced in the production process and the aroma of formaldehyde is reduced during production and writing. And

[0007]

Means for Solving the Problems The present inventor has conducted intensive studies to solve the problems of the prior art, and as a result, found that a solid marker having a specific composition can achieve the above object, and finally completed the present invention. Reached.

[0008] That is, the present invention relates to the following solid markers.

1. A solid marker containing a colorant, a gelling agent, a resin component and a solvent, wherein the colorant is a soluble fluorescent pigment using a polyamide resin as a carrier.

[0010] 2. The solvent has the following properties a) to c): a) the HLB value (X) of the solvent is X ≦ 6.5, b) the HLB value (X) of the solvent is X ≦ 8, and the solubility parameter The value (Y) is Y ≦ 10, or c) the HLB value (X) of the solvent is X ≦ 9 and the solubility parameter value (Y) is Y ≦ 9.5. Item 2. The solid marker according to Item 1.

3. The resin component is at least one selected from butyral resin, vinyl acetate resin, vinyl acetate-vinyl chloride copolymer resin, vinyl acetate-ethylene copolymer resin, cellulose acetate butyrate, ethyl cellulose and acetyl cellulose, and ketone resin and xylene resin. ,
2. The solid marker according to the above item 1, comprising at least one selected from a polyamide resin and an acrylic resin.

4. Item 4. The solid marker for writing on a wet surface according to any one of Items 1 to 3.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION As the coloring agent in the present invention,
It is essential to use a soluble fluorescent pigment using a polyamide resin as a carrier. This is, for example, at the stage of producing a polyamide resin as a matrix or in a polyamide resin already produced, if necessary, dissolve a fluorescent dye together with an ultraviolet absorber, and crush the resulting massive colored substance, It is obtained by further pulverizing as necessary.

Known or commercially available fluorescent pigments can be used. For example, the product name "NKS1
004 ”,“ NKS1005 ”,“ NKS1007 ”
(All manufactured by Nippon Fluorescent Chemical Co., Ltd.) and the like.

In the present invention, a part of the colorant may be replaced with another dye component as long as the effect is not impaired. The pigment component is not particularly limited, and any of known pigments and dyes can be used.

As the pigment, for example, carbon black,
Inorganic pigments such as titanium oxide; insoluble azo such as monoazo and disazo, soluble azo, condensed azo, phthalocyanine, anthraquinone, sulene, perylene, perinone, indigo, thioindigo, quinacridone, dioxazine, isoindo Linone-based, quinophthalone-based, methine-based organic pigments and the like can be used. In addition to metal powder pigments such as aluminum powder, metal complex pigments, brilliant pigments, fluorescent colorants and the like can be used.

On the other hand, oil-soluble dyes can also be suitably used in the present invention. As the oil-soluble dye, known or commercially available products such as a phthalocyanine dye, a pyrazolone dye, a nigrosine dye, an anthraquinone dye, an azo dye, and a chromium-containing metal dye can be used.

The content of the colorant containing a polyamide resin as a carrier in the solid marker may be appropriately changed according to the kind of the dye to be used, etc., but is usually about 0.5 to 60% by weight, preferably 1.0 to 1.0% by weight. What is necessary is just to 40 weight%. If the colorant is excessive, the relative proportion with other components may decrease, and the respective effects may not be exhibited. If the amount of the coloring agent is too small, a sufficient coloring effect may not be obtained.

The gelling agent in the present invention is not particularly limited, and those applied to crayons (gelled crayons) in the prior art can be used. For example,
Examples include dibenzylidene sorbitols, tribenzylidene sorbitols, amino acid-based oil gelling agents, fatty acids, and the like.

The dibenzylidene sorbitols include
For example, in addition to dibenzylidene sorbitol, a compound (dibenzylidene sorbitol derivative) in which a benzylidene group of dibenzylidene sorbitol is substituted with an alkyl group having 1 to 3 carbon atoms at an arbitrary position of a benzene nucleus can be exemplified. -(P-methylbenzylidene)]-sorbitol, [di- (m-ethylbenzylidene)]-sorbitol, [di- (p-chlorobenzylidene)]-sorbitol and the like.

Examples of the tribenzylidene sorbitol include, for example, tribenzylidene sorbitol, and a compound in which an alkyl group having 1 to 3 carbon atoms is substituted at an arbitrary position of the benzene nucleus of the benzylidene group of tribenzylidene sorbitol (tribenzylidene sorbitol derivative). Specific examples include [tri- (p-methylbenzylidene)]-sorbitol, [tri- (m-ethylbenzylidene)]-sorbitol, [tri- (p-chlorobenzylidene)]-sorbitol and the like. .

Examples of the amino acid-based oil gelling agent include N
-Acylglutamine diamide, N-lauroylglutamic acid di-n-butylamide and the like.

Examples of the fatty acids include fatty acids such as stearic acid, myristic acid and 12-hydroxystearic acid, hydroxy fatty acids, and metal salts (such as alkali metal salts and ammonium salts) of these fatty acids.

Among these, it is preferable to use 12-hydroxystearic acid, dibenzylidene sorbitols, and tribenzylidene sorbitols.

The content of the gelling agent in the solid marker can be appropriately set according to the type of the gelling agent used. Among them, usually about 2 to 12% by weight is preferable, and more preferably 3 to 8% by weight. If the amount of the gelling agent is too large, the gel hardness may be too high and the coloring property or the like may decrease. If the amount of the gelling agent is too small, gelation may be difficult.

As the resin component, those conventionally used in the production of gelled crayons can be used and are not particularly limited. In the present invention, it is particularly preferable to use two kinds of resins, that is, a resin for forming a film and a resin for improving adhesion.

The resin for film formation is not particularly limited as long as it can increase the hardness of the solid marker and can form a strong film on the coated surface. For example, at least one selected from butyral resin, vinyl acetate resin, vinyl acetate-vinyl chloride copolymer resin, vinyl acetate-ethylene copolymer resin, cellulose acetate butyrate, ethyl cellulose, acetyl cellulose and the like can be used. Among these, it is preferable to use butyral resin.

The resin for improving the adhesion is not particularly limited as long as it can enhance the adhesion to the coated surface. For example, at least one selected from a ketone resin, a xylene resin, a polyamide resin, an acrylic resin, and the like can be used. Examples of the ketone resin include a condensate of cyclohexanone and formaldehyde. Examples of the xylene resin include a condensate of meta-xylene and formaldehyde. The polyamide resin is, for example, a thermoplastic resin obtained by polycondensation of dimer acid and di or polyamine, and has a molecular weight of 4000 to 9000.
To the extent. As the acrylic resin, for example, a thermoplastic acrylic resin or the like can be used.

The content of the resin component in the solid marker varies depending on the type of the resin component used and the like.
It may be about 40% by weight, preferably 6 to 35% by weight. If the resin component is in excess, the gel hardness may increase and the colorability or the like may decrease. If the amount of the resin component is too small, gelation may be difficult.

The mixing ratio of the film-forming resin and the adhesion-improving resin can also be appropriately determined in relation to other components such as a coloring agent. Is about 1: 0.1-4 by weight ratio,
Preferably, it should be 1: 0.2 to 2.

The solvent in the present invention is not particularly limited as long as it does not hinder the dissolution of the soluble fluorescent pigment using the polyamide resin as a carrier, and a known organic solvent can be used.
For example, monohydric alcohols such as 3-methyl-3-methoxybutanol and 3-methoxy-1-butanol; glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and hexylene glycol; methyl ethers of the above glycols Glycol ethers such as ethyl ether, propyl ether, butyl ether, phenyl ether, methyl ether acetate, and ester compounds thereof.

Specifically, for example, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol butyl ether, propylene glycol propyl ether, dipropylene glycol propyl ether , Dipropylene glycol butyl ether, tripropylene glycol butyl ether, propylene glycol phenyl ether, and the like.

Among them, the following properties a) to c): a) The HLB value (X) of the solvent is X ≦ 6.5, b) The HLB value (X) of the solvent is X ≦ 8, And the solubility parameter value (Y) is Y ≦ 10, or c) the HLB value (X) of the solvent is X ≦ 9 and the solubility parameter value (Y) is Y ≦ 9.5. Are preferred.

Regarding the above a), if the HLB value (X) of the solvent is X ≦ 6.5, the value of the solubility parameter is not particularly limited.
It is preferably in the range of 6.5.

Regarding b) above, the HLB value (X) of the solvent is X ≦ 8 and the value of the solubility parameter (Y) is Y ≦
It may be 10 or less. There is no limitation on the lower limit of the HLB value (X) and the solubility parameter value (Y).
5, it is preferable that Y ≧ 7.

Regarding the above c), the HLB value (X) of the solvent is X ≦ 9 and the value (Y) of the solubility parameter is Y ≦
What is necessary is just 9.5 or less. The lower limit of the HLB value (X) and the solubility parameter value (Y) are not limited.
It is preferable that ≧ 8 and Y ≧ 7.

Of these, the boiling point is particularly 100
C. to 250.degree. C. are preferred.

As the solvent having such properties, at least one selected from ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, dipropylene glycol monomethyl ether and propylene glycol monobutyl ether is preferably used. be able to.

The content of the solvent in the solid marker of the present invention can be appropriately determined in relation to other components, but is usually about 20 to 80% by weight, preferably 30 to 80% by weight.
What is necessary is just 65 weight%. If the solvent is excessive, gelation may be difficult. If the amount of the solvent is small, it may be difficult to dissolve other components, and a uniform gel may not be obtained.

In the solid marker of the present invention, known additives such as a filler, a leveling agent, a viscosity modifier, a structural viscosity-imparting agent, and a dryness-imparting agent can be appropriately compounded as other components as required. . Also, for example, diethyl phthalate, dibutyl phthalate, dioctyl phthalate,
Plasticizers such as 2-ethylhexyl epoxyhexahydrophthalate, 2-ethylhexyl sebacate, and tricresyl phosphate can also be appropriately blended.

The gel hardness of the solid marker of the present invention may be appropriately set according to the use of the final product, etc.
About 30 kg / cm ² , preferably 8 to 22 kg / cm
^Let it be ² . In addition, the gel hardness can be changed depending on the type and the amount of the organic solvent and the gelling agent.

The method for producing the solid marker of the present invention is basically not limited as long as the above components can be uniformly mixed. For example, first, a resin for film formation is added and dissolved in a solvent (including a mixed solvent), and then a resin for improving adhesion is added with heating and stirring to completely dissolve the resin. Thereafter, a colorant is added, and the mixture is sufficiently dispersed by a mill or the like, and then a gelling agent is added to completely dissolve the colorant. The solution obtained at last may be poured into a container having a desired shape, and cooled and solidified. In the above method, heating may be performed as necessary to completely dissolve each component.

[0043]

The solid marker of the present invention is characterized in that a soluble fluorescent pigment using a polyamide resin as a carrier is used as a colorant.

[0044] Therefore, the ink is characterized in that the fluidity of the ink is not excessively reduced in the production process and that the aroma of formaldehyde is substantially not produced during the production and writing.

The solid marker has a writable property,
It can be applied to various materials such as paper, metal, ceramics, plastics, and glass.

Moreover, it is possible to write on a wet surface of these materials. That is, it has excellent wet surface writing properties and is useful as a solid marker for wet surface writing.

Further, the adhesiveness is excellent, and the coated film after being cured is hardened and does not transfer color. In particular, the leveling is better than the conventional product, and the shorthand writing can be easily performed. Furthermore, it has excellent cap-off performance.

The solid marker of the present invention having such characteristics can be suitably used as a solid marker applicable to any material, such as a drawing material and a paint, for a wide range of uses.

[0049]

EXAMPLES Examples and comparative examples are shown below to explain the characteristics of the solid marker of the present invention more specifically.

Example 1 15.0 parts by weight of cellulose acetate butyrate was added to 35.5 parts by weight of dipropylene glycol monomethyl ether and dissolved. The solution was heated and stirred at about 100 ° C., and further mixed with a xylene resin (“Nicanol HP-12”).
0 "(manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 20.0 parts by weight were completely dissolved. To the obtained solution, 10.0 parts by weight of titanium oxide as a colorant and 14.0 parts by weight of a fluorescent pigment (“NKS1004” manufactured by Nippon Fluorescent Co., Ltd.) using a polyamide resin as a carrier were added, and sufficiently dissolved and dispersed in a mill. Next, 5.5 parts by weight of a gelling agent (“Gel-all T” sorbitol-based gelling agent, manufactured by Nippon Rika Co., Ltd.) was added, and the mixture was completely dissolved while maintaining the above temperature. And solidified after cooling and solidification.

Examples 2 to 6 Solids were prepared in the same manner as in Example 1 except that the raw materials shown in Table 1 were used. The numerical values in Table 1 are "parts by weight".

[0052]

[Table 1]

The details of the gelling agent and resin products shown in Table 1 are shown below. -"Gelol D": Product name "Gelol D", sorbitol-based gelling agent, manufactured by Nippon Rika Co., Ltd.-"Gelol T": Product name "Gelol T", sorbitol-based gelling agent, manufactured by Nippon Rika Co., Ltd.-" PVB2000L "... Product name" Denka Butyral 2
000L ", polyvinyl butyral, manufactured by Denki Kagaku Kogyo Co., Ltd." Hi-Rack 111 "... Product name" Hi-Rack 11 "
"1", ketone resin, manufactured by Hitachi Chemical Co., Ltd. "Persamide 335" ... Product name "Persamide 33"
5 ", amide resin, manufactured by Henkel Hakusui Co., Ltd." Nicanol "... Product name" Dianal BR-10 "
"0", acrylic resin, manufactured by Mitsubishi Rayon Co., Ltd. "Eslec BL-SH": Butyral resin, manufactured by Sekisui Chemical Co., Ltd. Comparative Example 1 A solid material was prepared in the same manner as in Example 1 except that the raw materials shown in Table 2 were used. It was created. The numerical values in Table 2 indicate "parts by weight".

[0054]

[Table 2]

Comparative Example 2 A solid was prepared in the same manner as in Example 1 except that the raw materials shown in Table 2 were used.

Comparative Example 3 A solid was prepared in the same manner as in Example 1 except that the raw materials shown in Table 2 were used.

Comparative Example 4 A solid was prepared in the same manner as in Example 1 except that the raw materials shown in Table 2 were used.

Comparative Example 5 A solid was prepared in the same manner as in Example 1 except that the raw materials shown in Table 2 were used.

Comparative Example 6 A solid was prepared in the same manner as in Example 1 except that the raw materials shown in Table 2 were used.

Test Example 1 Solids (solid markers) obtained in Examples and Comparative Examples
Was examined for the aroma of formaldehyde (in the production process and during writing) and the fluidity of the ink during the production. The results are shown in Tables 1 and 2 below. In addition, each evaluation was performed as follows. (1) Solvent aromaticity (both during production and at the time of writing) At the time of the production process and at the time of writing, whether or not the solid marker raw material and the obtained solid marker actually had an aroma of formaldehyde was examined by using an odor. (2) Ink fluidity at the time of production The fluidity of the ink during the production process was visually confirmed, and comprehensive judgment was made in consideration of the ease of work. Specifically, the judgment was made mainly on whether or not the ink was in a paste form.

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Claims (4)

[Claims] 1. A solid marker comprising a colorant, a gelling agent, a resin component and a solvent, wherein the colorant is a soluble fluorescent pigment using a polyamide resin as a carrier. 2. The solvent has the following properties a) to c): a) the HLB value (X) of the solvent is X ≦ 6.5; b) the HLB value (X) of the solvent is X ≦ 8, and the solubility parameter value (Y) is Y ≦ 10, or c) the HLB value (X) of the solvent is X ≦ 9, and the solubility parameter value (Y) is Y ≦ 9.5. The solid marker according to claim 1, comprising: 3. A resin component comprising butyral resin, vinyl acetate resin, vinyl acetate-vinyl chloride copolymer resin, and vinyl acetate resin.
The method according to claim 1, comprising at least one selected from ethylene copolymer resin, cellulose acetate butyrate, ethyl cellulose and acetyl cellulose, and at least one selected from ketone resin, xylene resin, polyamide resin and acrylic resin. Solid marker. 4. A solid marker for writing on a wet surface according to claim 1.