JPH0124187B2 - - Google Patents

Description

[Detailed description of the invention] The present invention relates to solid cleaner compositions.

Conventionally, in order to remove oil-based stains caused by marking pens using oil-based ink, crayon marks, handwriting, and other oil-based stains, organic solvents that can dissolve or swell the objects to be removed have been used. An impregnated body such as coarse hair is impregnated and stored in an appropriate container, and one end of a core made of felt or the like is brought into contact with the impregnated body and the other end is exposed outside the container so that the organic solvent reaches the exposed part by capillary action. There are commercially available cleaners that are used to remove exposed portions by wiping and dissolving or swelling the exposed portions by contacting the portions to be removed.

However, in such cleaners, since the organic solvent is directly impregnated into the impregnated body and the core body,
A portion always remains in the impregnated body due to capillary action, and the entire amount cannot be used. In addition, the dissolved dirt permeates or stains the core by capillary action, staining the exposed portion and re-contaminating the object when used next time.

The present invention solves this drawback, and is a solid that has thixotropy, which gels and becomes solid in its natural state, but when a moderate force is applied, the applied part turns into a sol and can be easily applied. A cleaner composition is provided.

That is, the present invention provides dibenzylidene sorbitol,
Gelling agents selected from tribenzylidene sorbitol and derivatives thereof; organic solvents selected from monohydric alcohols, polyhydric alcohols, derivatives of polyhydric alcohols, and esters; The present invention relates to a solid cleaner composition containing at least one surfactant selected from anionic surfactants and nonionic surfactants.

Dibenzylidene sorbitol and its derivatives, tribenzylidene sorbitol and its derivatives (hereinafter simply referred to as gelling agents) used in the present invention have the general formula It is a condensate with an aromatic aldehyde represented by [wherein R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms]. Not only aromatic aldehyde condensates of sorbitol, but all aromatic aldehyde condensates of polyhydric alcohols with five or more hydroxyl groups have the effect of solidifying organic solvents, but aromatic aldehyde condensates of sorbitol in particular have the effect of solidifying organic solvents. This effect is great and can be used to great advantage. Examples of dibenzylidene sorbitol derivatives include compounds in which the benzene nucleus of the benzylidene group of dibenzylidene sorbitol is substituted with an alkyl group having 1 to 3 carbon atoms, such as [di(P-methylbenzylidene)]-sorbitol, Examples include [di(m-ethylbenzylidene)]-sorbitol. At the same time, tribenzylidene sorbitol derivatives have 1 carbon atom at any position of the benzene nucleus of the benzylidene group of tribenzylidene sorbitol.
Examples include compounds substituted with ~3 alkyl groups, such as [tri(P-methylbenzylidene)]
Examples include sorbitol, [tri(m-ethylbenzylidene)]sorbitol, and the like. In the present invention, compounds selected from dibenzylidene sorbitol and its derivatives, and tribenzylidene sorbitol and its derivatives may be used alone or in combination.

These compounds vary depending on the resin and solvent used, but are usually 2 to 12 parts by weight per 100 parts by weight of the composition.
Preferably 5 to 10 parts by weight are used. (Hereinafter, parts by weight are simply referred to as parts.) If the amount of the gelling agent is too small, the composition will not solidify, or even if it solidifies, it will be too soft and difficult to use. or,
If the amount is too large, sufficient hardness can be obtained, but there is a disadvantage that the composition becomes brittle.

The organic solvent used in the present invention has a boiling point of 100 to 250℃
Monohydric alcohols, polyhydric alcohols, derivatives of polyhydric alcohols, esters, etc. can be advantageously used.

Monohydric alcohols include butyl alcohol, amyl alcohol, benzyl alcohol, etc. polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, etc., and polyhydric alcohol derivatives include ethylene glycol monomethyl ether. , ethylene glycol monoisopropyl ether, ethylene glycol isoamyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monobutyl ether Examples of the esters include methyl benzoate, ethyl benzoate, butyl benzoate, 3-methoxybutyl acetate, and butyl acetate. Among these, monohydric alcohols include benzyl alcohol, butyl alcohol, etc., polyhydric alcohols include ethylene glycol, propylene glycol, etc., and derivatives of polyhydric alcohols include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, 3-methoxybutanol, etc., and as the esters, methyl benzoate, ethyl benzoate, 3-methoxybutyl acetate, etc. are preferably used.

These organic solvents can be used alone or in combination of two or more, and are preferably 60 to 95 parts per 100 parts of the composition.
It is used in a proportion of 75 to 90 parts.

If the amount of organic solvent is too small, the composition will become hard and brittle, making it difficult to apply. Moreover, since the amount of adhesion inevitably decreases, it becomes difficult to remove the dirt. If the amount is too large, it will be difficult to solidify the composition, resulting in poor hardness.

The anionic and nonionic surfactants used in the present invention need to be dissolved in an organic solvent,
In order to facilitate the removal of dirt, it is preferable to use a material that has high detergency, penetrating power, or wetting power.

Examples of anionic surfactants include sodium dodecylbenzenesulfonate, sodium β-naphthalenesulfonate formalin condensate, sodium dialkylsulfosuccinate, and sodium polyoxyethylene alkyl phenyl ether sulfate; examples of nonionic surfactants include polyoxyethylene nonylphenyl ether sodium sulfate. enyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monostearate,
An example is polyoxyethylene octylphenyl ether.

One or more of these surfactants can be used in an amount of 0.5 to 10.0 parts, preferably 2.0 to 8.0 parts, per 100 parts of the composition.

If the amount of surfactant is too small, the cleaning power, penetrating power, or wetting power will be reduced, and depending on the composition of the stain, it may be difficult to remove it. On the other hand, if the amount is too large, gelation will be inhibited and the composition will not solidify, or even if it solidifies, it will be soft and difficult to use.

In the present invention, resins, perfumes, abrasives, etc. can be added to the above-mentioned essential components as necessary.

The use of resins is particularly desirable and can improve the hardness and brittleness of the composition. The resin used needs to be dissolved in an organic solvent.

These resins include cellulose resins such as nitrocellulose, ethylcellulose, hydroxycellulose, cellulose acetate butyrate, hydroxypropyl cellulose, polyvinyl butyral,
Examples include vinyl resins such as polyvinyl acetate, vinyl acetate-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, and amide resins obtained by condensation polymerization of dimer acid and di- or polyamine. One or more types are composition 100
0.1 to 30.0 parts, preferably 2.0 to 8.0 parts, are used.

When the proportion of the resin used in 100 parts of the composition is small, the composition tends to crumble when a strong application force is applied.

On the other hand, if the amount is too large, the composition becomes too hard, making it difficult to apply and removing the applied portion.

To produce the composition of the present invention, for example, first, a surfactant and, if necessary, a resin, fragrance, etc. are added to and dissolved in an organic solvent while heating and stirring.

Next, the organic solvent used is heated to a temperature close to its boiling point, and a gelling agent is gradually added thereto, and the gelling agent is completely dissolved while maintaining the above temperature. Then, the composition of the present invention is produced by pouring it into an appropriate mold and cooling and solidifying it by means such as allowing it to cool.

The solid cleaner composition of the present invention can be smoothly applied to oil-based ink, crayon, and other stains, as well as to any material surface to which they have adhered, such as glass plates, plastic plates, metal plates, etc., and after application, the solid cleaner composition can dissolve or remove stains. It can be easily and cleanly removed by swelling it and wiping it with a cloth.

Furthermore, since dirt adhering to the composition during application can be easily removed by wiping with a cloth, there is no risk of staining the object to be newly coated.

The present invention will be explained below with reference to Examples.

Example 1 87 parts of ethylene glycol monobutyl ether are mixed with 5 parts of polyoxyethylene nonyl phenyl ether (trade name: Score Roll 900, manufactured by Kao Atlas Co., Ltd.), and the mixture is heated and stirred to dissolve. then 120
After raising the temperature to 0.degree. C., 8 parts of dibenzylidene sorbitol (trade name: Gelol D, manufactured by Shinnihon Rika Co., Ltd.) was gradually added and completely dissolved.

Then, the obtained solution was poured into a predetermined mold, cooled and solidified, and then taken out.

The solid cleaner composition thus obtained can be easily applied onto stains adhered to a glass plate (a coating film of nitrocellulose lacquer containing nitrocellulose as the main film-forming element and blended with a non-oxidized alkyd resin). Swells and dissolves dirt. Then, it could be easily and cleanly removed by wiping the area with a cloth.

Although the composition obtained in this example had a suitable hardness, it was somewhat brittle and crumbled slightly when applied with a large application force.

Example 2 82 parts of ethylene glycol monobutyl ether, 5 parts of polyvinyl butyral [trade name: Denka Butyral #2000L manufactured by Denki Kagaku Kogyo Co., Ltd.] and 5 parts of polyoxyethylene nonyl phenyl ether were mixed and heated at 120°C. Stir to dissolve. then 140
The temperature is raised to 0.degree. C., and while keeping it warm, 8 parts of dibenzylidene sorbitol is gradually added and completely dissolved. Then, the obtained solution was poured into a predetermined mold, cooled and solidified, and then taken out.

The solid cleaner composition thus obtained could be easily applied onto stains similar to those used in Example 1, and swelled and dissolved the stains. Then, it could be easily and cleanly removed by wiping the area with a cloth.

The solid cleaner composition obtained in this example had appropriate hardness and did not crumble during application.

Solid cleaner compositions of Examples 3 to 15 were obtained in the same manner.

The obtained solid cleaner composition can be easily applied to stains such as ink, crayon, and other edible oils adhering to various materials as in Example 1 or 2, and can swell and dissolve the stains, and can be wiped off with a cloth. This made it possible to remove it easily and cleanly.

Example 3 Dibenzylidene sorbitol 8 parts 3-methoxybutyl acetate [trade name: Methoacetate manufactured by Daicel Corporation] 88 parts polyoxyethylene sorbitan monostearate [trade name: Emazol 3130 manufactured by Kao Atlas Corporation]
4 parts [Trade name: Orange Oil Takada Kogyo Co., Ltd.] 0.08 parts Example 4 Methyl benzoate 86 parts Dibenzylidene sorbitol 7 parts Polyoxyethylene oleyl ether [Trade name:
Score Roll 400 manufactured by Kao Atlas Co., Ltd.] 3 parts Polyvinyl butyral 4 parts Orange oil 0.1 part Example 5 Dibenzylidene sorbitol 6 parts 3 methoxybutanol [Trade name: Methobutanol Manufactured by Daicel Corporation] 85 parts Sodium dodecylbenzenesulfonate [Trade name: Neopex Kao Atlas Co., Ltd.] 4-part cellulose acetate butyrate [Trade name:
CAB-EAB-381-1/2 Manufactured by Eastman Chemicals] 5 parts Example 6 Tribenzylidene sorbitol [Trade name: GELOL T Manufactured by Shinnihon Chemical Co., Ltd.] 10 parts 3-methoxybutyl acetate 81 parts Hydroxypropyl cellulose [Trademark] Name: Nisso
HPC Nippon Soda Co., Ltd.] 5 parts β-naphthalene sulfonic acid sodium formalin condensate [Trade name: Demol N Kao Atlas Co., Ltd.] 4 parts Example 7 Dibenzylidene sorbitol 6 parts Diethylene glycol monomethyl ether 84 parts Sodium dialkyl sulfosuccinate [Trade name: Rapizol β-80 manufactured by NOF Corporation] 5 parts Cellulose acetate butyrate 5 parts Example 8 Dibenzylidene sorbitol 8 parts 3-methoxybutyl acetate 85 parts Polyoxyethylene sorbitan monostearate
4 parts Polyvinyl butyral 3 parts [Trade name: Rose Oil Takada Kogyo Co., Ltd.] 0.08 parts Example 9 Dibenzylidene sorbitol 6 parts Ethylene glycol monoethyl ether 60 parts Ethyl benzoate 25 parts Polyoxyethylene nonyl phenyl ether [Trademark] Name: Emulgen 910 manufactured by Kao Atlas Co., Ltd.] 4 parts Ethyl cellulose [Trade name: Ethocel 7 manufactured by Dow Chemical Company] 5 parts Example 10 Tribenzylidene sorbitol 9 parts Ethylene glycol monobutyl ether 83 parts Polyoxyethylene octyl phenol ether [Trade name : Emulgen 810 manufactured by Kao Atlas Co., Ltd.] 4 parts Amide resin [Trade name: Versamide 711 manufactured by Henkel Japan Co., Ltd.] 4 parts Example 11 Dibenzylidene sorbitol 7 parts 3 methoxybutanol 85 parts Polyoxyethylene alkyl phenyl ether sulfate Soda [Trade name: Emar NC Kao Atlas Co., Ltd.]
5 parts polyvinyl acetate [trade name: Gosenil A75-Z5 manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.] 3 parts Example 12 Tribenzylidene sorbitol 10 parts ethylene glycol monobutyl ether 81 parts polyethylene glycol monostearate [trade name: Polynon S44 Manufactured by Tetsuno Yuka Co., Ltd.] 6 parts [Trade name: Lemon Oil Royal, manufactured by Takada Fragrance Co., Ltd.]
0.05 parts Cellulose acetate butyrate 3 parts Example 13 Dibenzylidene sorbitol 6 parts 3 Methoxybutanol 40 parts 3 Methoxybutyl acetate 46 parts Polyoxyethylene nonyl phenyl ether 4 parts Hydroxypropyl cellulose 4 parts Example 14 Dibenzylidene sorbitol 7 parts 3 Methoxybutanol 84 parts Sodium dialkyl sulfosuccinate 2 parts Polyoxyethylene octyl phenol ether
3 parts Polyvinyl butyral 4 parts Example 15 Dibenzylidene sorbitol 2 parts Tribenzylidene sorbitol 6 parts Ethylene glycol monobutyl ether 84 parts Polyoxyethylene nonyl phenyl ether 5 parts Cellulose acetate butyrate 3 parts

Claims (1)

[Scope of Claims] 1. A few gelling agents selected from dibenzylidene sorbitol, tribenzylidene sorbitol, and derivatives thereof, monohydric alcohols, polyhydric alcohols, derivatives of polyhydric alcohols, and esters. A solid cleaner composition characterized in that it contains at least one kind of an organic solvent selected from the above, and at least one kind of a surfactant selected from an anionic surfactant and a nonionic surfactant.