JPS62207370A - Color forming composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which is useful for tooth paste, shampoo, etc., and exhibits color change clearly in a predetermined time containing an immobilized dye obtd. by fixing a water-soluble anionic dye to a water-insoluble cationic polymer and an ionic surfactant in a specified form. CONSTITUTION:100pts.wt. water-insoluble cationic polymer (a) having a surface area of 0.1-500m<2>/g and a particle size of 0.1-50mu (e.g., a bisphenol/ epichlorohydrin type epoxy resin/piperazine polycondensate) as a dye-fixing substrate is added to 0.5-20pts.wt. water-soluble anionic dye (b) (e.g., Red No.2). A solvent such as water, methanol, etc., is added thereto and the mixture is mixed under acidic conditions to ionically bond them to each other and the product is dried and crushed to obtain an immobilized dye (A). The component A is blended with an ionic or semipolar nonionic surfactant (B) (e.g., sodium laurylsulfate) in a weight ratio of A to be of 0.1/10-10/1 in such a form that the components A and B undergo an exchange reaction by an external action, e.g., by encapsulating the component A and blending the same.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a coloring composition that can be used in various products such as toothpaste and shampoo, and in particular, a coloring composition that produces a vivid color when exposed to external effects. It is related to.

[Conventional technology]

In general, some consumer products, such as carbonless paper or color-changing gum, are created by taking advantage of changes in usage conditions and conditions during use to develop a color tone that is different from the color tone before use. There are products that have been given commercial value, and it is desired that other products be given such functions as well.

For example, when it comes to tooth brushing, there is a correlation between the cleanliness of the teeth and the number of times you brush, and the more times you brush, the better the cleaning effect will be. However, in general, each person's habits determine the number of times they brush, and how much Currently, there is no guideline as to whether it is sufficient.

Therefore, there is a need for a toothpaste that indicates the end point of brushing by, for example, a change in color.

Therefore, the following techniques have already been proposed to provide such functionality.

(1) Using a pigment coated with a white pigment, the coating layer is peeled off by mechanical force such as friction or shearing force when necessary to reveal the color of the core pigment (JP-A-60-16913, JP-A-55 -153709) Method.

(iii) A method in which activated clay, zeolite, etc. is mixed with a coating or microcapsule of a color-forming organic compound having a conjugated double bond that reacts with them, and the coating is destroyed by mechanical force to cause a chemical reaction to develop color ( JP-A-49-1737), or a method that applies chemical reactions such as redox reactions.

1iii1 A method that utilizes intraoral changes such as pl changes and reactions with saliva (amylase).

However, in these methods, the color-forming substances are limited to pigments and oil-soluble dyes, so when used in an aqueous system, the resulting color tone is not as vivid, and most of the color changes are due to dispersion alone, so color development is not continuous. In addition, there were also problems with the safety of the coloring agent, and the above method was insufficient to be used as a time indicator for meat. On the other hand, a water-soluble dye with a bright color is mixed with a carrier (kaolin),
There are examples of dyes being coated with hydrophobic membrane materials or gelatin and blended into water systems, but water molecules and organic solvent molecules (ethanol, etc.) may permeate through the membrane material and elute the dye, and elution cannot be suppressed. However, when the coating was broken, the dye was immediately eluted by water molecules, making it unsuitable as a time indicator.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to provide a color-forming composition that can be used in an aqueous solvent system and exhibits a clear and distinct color change over a predetermined period of time.

[Means to solve the problem]

The present invention uses a water-insoluble cationic polymer as a dye immobilization base material, and immobilizes a water-soluble anionic dye on the base material by adsorbing or ionically bonding it to the immobilized dye. When the surfactant acts, an exchange reaction occurs between the water-soluble anionic dye and the surfactant,
This was done based on the knowledge that the water-soluble anionic dye gradually diffuses into the aqueous medium, and the vivid color of the water-soluble anionic dye is developed, thereby effectively solving the above-mentioned problems.

That is, the present invention provides an immobilized dye in which a water-soluble anionic dye is immobilized on a water-insoluble cationic polymer, and fB.
A coloring agent containing an ionic or semipolar nonionic surfactant, and containing the water-soluble anionic dye and the surfactant in an exchange reaction by external action. A composition is provided.

The water-soluble anionic dye shown in the composition diagram used in the present invention is as follows:
Any substance with an anionic functional group such as a carboxyl group or a sulfonate group in its molecule can be used, but for household consumer goods, from the standpoint of safety, water-soluble Anionic dyes are preferred. Specifically, Red No. 2 (Afrance), Red No. 3 (Erythrosin), Red No. 102 (Eucoccin)
, Red No. 1.04 (1) (Phloxin B), Red 10
No. 5 (1) (Rose Bengal), Red No. 106 (Anrad Red), Yellow No. 4 (Tartrazine), Yellow No. 5 (
Sunset Yellow FCF), Green No. 3 (Fast Green FCF), Blue No. 1 (Brilliant Blue FCF)
, Blue No. 2 (indigo carmine), etc. These dyes can be used alone or in combination of two or more.

As the water-insoluble polymer used as a carrier for the dye, any water-insoluble polymer having a cationic functional group in its molecule can be used.

Specifically, examples include bisphenol/epichlorohydrin type epoxy resin piperazine polycondensate [trade name: Trevar (Toshi)], copolymer of acrylic acid ester and methacroyloxyethylene trimethyl halide, chitosan, etc. be done.

The form of the water-insoluble cationic polymer is arbitrary, but
Fine particles are preferred, and those with a large surface area are preferred in order to sorb or ionically bond water-soluble anionic dyes at a high rate per unit mold. Therefore, the surface area is 1 to 500 m'/gr, preferably 100 to 500 m'/gr.
'/gr, particle size is 0.1 to 500μ, preferably 1 to 2
It is desirable to use one with a diameter of 0μ.

The immobilized dye shown in the composition diagram can be prepared by any method, but for example, by adding water, a solvent such as ethanol to a water-soluble anionic dye and water-insoluble cationic polymer particles, and mixing them under acidic conditions, the two are mainly ionic. It can be easily prepared by combining, drying, and pulverizing. The amount of water-soluble anionic dye immobilized on the water-insoluble cationic polymer particles is approximately the same as that of an ion, but even an amount exceeding the ion equivalent can be stably immobilized by sorption to the particles.

As a guideline, it is preferable to use 0.5 to 20 parts by weight of the water-soluble anionic dye per 10011 parts of the cationic polymer.

The surfactant used as the component in the present invention is an ionic or semipolar nonionic surfactant, and the following are exemplified.

Anionic surfactant Alkylbenzene sulfonate with 8 to 16 carbon atoms (abbreviated as C8 to C+c, the same applies hereinafter), α of 08 to C2G
-Olefin sulfonate, C8-C+ 6 alkyl (alkenyl) sulfate salt, polyoxyethylene alkyl (alkenyl) sulfate salt with Cs-C+ s and 1-100 moles of ethylene oxide added, C8-C
I8 fatty acid salt, C8-C2° acyl sarcosinate, C8-C2□ fatty acid acyl-glutamate,
C8-C+ a alkylnaphthalene sulfonate, C
a-C20 fatty acid monoglysulfate ester salt, rosin acid salt, α- consisting of a 08-C20 alkyl (alkenyl) group in the main chain and a C1-C3 alkyl group or alkaline earth metal that further forms an ester bond with the main chain sulfo fatty acid salts,
C6~C2G dialkyl sulfosuccinate, Co~
C2G alkanesulfonate, 08-C2G alkyl phosphate, cholate, all-C,.

Examples include phosphoric acid monoester salts and diester salts having an alkyl group or an alkylphenyl group and an ethylene oxide addition mole number of 2 to 50. The counter ion of these anionic surfactants is Na.

KSMg, Ca or triethanolamine are used. The above surfactants can be used alone or in combination of two or more.

Cationic surfactant CIo -C24 mono long chain alkyl quaternary ammonium salt, C+ a-C24 mono long chain alkyl benzyl quaternary ammonium salt, Clo -C24 mono long chain alkyl ethoxy quaternary ammonium salt, chloride Examples include benzalkonium and benzethonium chloride.

These can also be used alone or as a mixture of two or more.

The amphoteric surfactants 08 to C22 include alkyl betaine type and alkylimidazolinium betaine type amphoteric surfactants.

Semipolar nonionic surfactant C6-C20 amine oxide and 06-C2G sulfoxide, C8-C2□ fatty acid dialkylolamide and its ethylene oxide adduct (number of moles of ethylene oxide added: 2-20 moles) is exemplified. These surfactants can be used alone or in combination.

Among the above surfactants, sodium lauryl sulfate is particularly preferably used in the present invention.

In addition, in the present invention, the composition diagram and the old) can be used in any amount, but the composition diagram/(B) can be used in an amount of 0.1/10 to 1.
It is preferable to use it in a ratio of 0/1 (weight ratio), preferably 1/10 to 5/1.

In the present invention, the above component diagram and IBI are contained in a form in which the water-soluble anion dye in the component diagram and the surfactant of component IBI undergo an exchange reaction due to an external action. Specifically, when the surface of the composition diagram is coated with a colorless, white, or light-colored material, such as when the composition diagram is encapsulated, the coating is destroyed by mechanical action or heating. There are cases. Furthermore, when component B] is encapsulated in a capsule or the like, both the component diagram and the IBI are encapsulated in the capsule or the like, and the coating may be destroyed by the above action. In this way, all that is required is an exchange reaction between the water-soluble cationic dye of the ingredient and the surfactant due to an external action, and as long as this state can be clearly established, the form of the ingredient and the old) can be It may be something.

In addition, as the above-mentioned surface coating member, nitrocellulose,
Polymers such as ethyl cellulose, chitosan, sodium polyacrylate, polyvinyl alcohol, and white pigments such as titanium oxide, silicon oxide, calcium phosphate,
Calcium carbonate, aluminum hydroxide, magnesium phosphate, magnesium carbonate, talc, acid clay, etc. can be used. At this time, it is also possible to adjust the mechanical strength of the membrane material to control the rate of breakage due to mechanical destructive force and to adjust the color development start time.

Coloring with the coloring composition of the present invention is carried out in an aqueous medium. Here, "in an aqueous medium" includes not only water but also cases where an organic solvent such as ethyl alcohol, propylene glycol, or glycerin is added to water.

Although the coloring composition of the present invention has the above-mentioned structure as its basic structure, for example, fragrances, organic acid salts, water-soluble polymers, oils, etc. can be added thereto.

〔Effect of the invention〕

By using the color forming composition of the present invention, it is possible to obtain clear color development in an aqueous medium at a low concentration range unique to water-soluble dyes, unlike color development by pigments or by solubilization of oil-soluble dyes. .

In addition, when a polymer other than a cationic polymer is used as a carrier, the dye is eluted before use, but according to the method of the present invention, the water-soluble dye is stably immobilized on the cationic polymer and is free from external interference. By allowing an ionic surfactant or a semipolar nonionic surfactant to act on the immobilized pigment, the color density changes over time, so it can be widely applied as a time indicator for toothpastes, shampoos, etc.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

〔Example〕

Example 1 Immobilized pigment as a component in which a water-soluble anionic dye, Blue No. 1, was immobilized on a bisphenol epichlorohydrin type epoxy resin piperazine polycondensate [average particle size 5 μm, trade name: Torepal (Toshi)] was used. Next, 50 g of a 10% nitrocellulose ethyl acetate solution was added to 25 g of the fixed dye as a polymer for covering the fixed dye, and thoroughly kneaded in a mortar to obtain a dye mass. Next, this lump was placed in a small 300-sized crusher, and while being crushed, 70 g of titanium oxide was added and mixed to form a coating layer of titanium oxide on the surface of the pigment lump coated with nitrocellulose. When dried, the particle size is 1 to 10.

Surface-coated pigment particles of μ size were exposed.

The particle composition is shown below. Here, the dye fixation rate refers to the dye content in the fixed dye.

Surface-coated pigment particle composition: Fixed pigment (dye fixation rate 6%) 25 weight M% (hereinafter %
) Nitrocellulose 5% titanium oxide (
Anacuse type > 70% Next, 2% of the above surface-coated pigment particles were added to the following toothpaste containing sodium lauryl sulfate as component tB] to prepare a toothpaste containing the coloring composition of the present invention.

Meat layer composition Prescription 1 Prescription 2 Dibasic calcium phosphate 5Q, 0 wt% 50.0 wt% Sorbitol 20.0 20.0 Carboxymethyl cellulose 1.0 1.0 Saccharin
0.1 0.1 fragrance
1.0 1.0 surface coated pigment particles
2.0 2.0 Sodium lauryl sulfate 2.00 Purified water Balance Balance Next,
Add 1 g of physiological saline to 1 g of the above meat layer composition, and add 3XIQ
Using a toothbrush (Ristolion, normal hardness) on a Teflon plate with a brushing pressure of 400 gr/cat,
Brushing was carried out at a stroke rate of 120 times/min, and the blueness of the resulting foam was determined over time as the b value using a colorimeter, and the system was evaluated to determine whether or not it contained an anionic surfactant (formulation 1) that caused the exchange reaction. Difference Δb(
Δb-prescription 1-b prescription 2) are collectively shown in Table-1.

Table-1 Brushing time (minutes) Difference in foam coloration (△b value) 0.
50 1, 0 -2 1, 5 -3 2, 0 -10 3, 0 -15 4, 0 -24 5, 0 -35 In the above experiments, both systems of formulations 1 and 2 had surface-coated polymer particles by lashing. Exposure and dispersion of the immobilized dye occurs due to the destruction of It can be seen that between 1) and a system that does not contain an ionic surfactant and is only colored with a fixed dye that is exposed and dispersed by brushing (formulation 2), there is a large difference in the degree of foam coloration depending on the b value over time.

Example 2 Surface-coated particles were collected in the same manner as in Example 1, except that the various dyes shown in Table 2 were used.Next, the particles were used to brush a toothbrush (wrist) on a 3 x 10 cm Teflon plate. The surface coated pigment particles were destroyed and the immobilized pigment was exposed by brushing for 2 minutes at a brushing pressure of 400 g/ctl and a stroke rate of 120 times/min. % sodium lauryl sulfate aqueous solution and dispersed at 35°C.
After shaking for minutes (number of strokes 120 times/m1n), 0.4
It was filtered through a 5μ membrane filter, the absorbance of the filtrate was determined at the maximum absorption wavelength of the dye, and the amount of free dye was determined from a calibration curve prepared in advance.

The results are summarized in Table 2 together with the dyes used.

Table 2 As is clear from Table 2, in the water-soluble anionic dye immobilization system, a large amount of dye was liberated from the exposed immobilized dye due to the exchange reaction, and the filtrate was noticeably colored, but the oil-soluble dye immobilization system In the chemical system, almost no coloring of the filtrate was observed.

Example 3 Using the same surface-coated pigment particles as in Example 1, powder was pulverized by the same brushing method as in Example 2 (brushing pressure 400 g/cm, number of strokes 120 times/min, brushing time 2 minutes). % surfactant and an inorganic electrolyte aqueous solution, and the amount of free dye was determined in the same manner as in Example 2, and the contribution of the surfactant to the release of the dye was investigated.

The results are summarized in Table 3 along with the surfactants and inorganic electrolytes used.

Table 3 As is clear from Table 3, when ionic and semipolar nonionic surfactants are used, coloring occurs due to free dyes based on exchange reactions, whereas when using simple inorganic ions and nonionic surfactants without polarity, It can be seen that dye release does not occur with surfactants.

Example 4 The same surface-coated pigment particles as used in Example 1 were used, and the amount of free dye was determined in the same manner as in Example 3, except that the amount of sodium lauryl sulfate added was changed, and the concentration of surfactant was determined. We investigated the effects of The results are shown in Table 4.

From Table 4, it can be seen that the amount of free dye is highest in the micelle forming region (at liquid crystal forming concentration, it decreases somewhat due to the decrease in the mobility of surfactant molecules. Below the critical micelle concentration, the amount of free dye I is It is clearly less than the concentration.

Example 5 Yellow particles prepared in the same manner as in Example 1 using the same surface-coated pigment particles as used in Example 1 or as a comparison example using yellow iron oxide with an average particle size of 0.5μ instead of the immobilized pigment. The following writing composition was prepared using surface-coated pigment particles containing iron oxide. Next, the degree of coloration when brushed in the oral cavity for a predetermined period of time was visually evaluated using the following evaluation criteria.

Tooth composition'=”lS Calcium diphosphate 50
,0% sorbitol 20.0
Carboxymethylcellulose 1.0 Saccharin 0.1 Fragrance

1.0 Fragrance active agent 2.0 Surface coated pigment particles 2.0 Purified water
Balance coloration evaluation standard 0 points No coloration (0-2ppm) *3
1 point Slightly colored (3-19ppm) 2 points Slightly colored (20-29ppm) 3 points Quite colored (30-49ppm) 4 points Vividly colored (5
0ppm<>” () indicates the amount equivalent to Blue No. 1 in the color sample using the above 1-bunch formulation, containing sodium lauryl sulfate as a surfactant, and free Blue No. 1 instead of surface-coated pigment particles. The panel consisted of 5 people, and the results were shown as the average score of the 5 people.The results are summarized in Table 6.

From Table 6, it can be seen that the teeth containing the coloring composition of the present invention are 2 to 3.
The color changes after 2.5 minutes, and the end point of brushing can be clearly sensed, and the degree of coloring increases over time and becomes more and more vivid, so it can be seen that the brushing time is very good because it can be controlled correctly.

Procedural Amendment Commissioner of the Patent Office Mr. Michibe Uga Tehe 1
, Incident Display 1986 Patent Application No. 50066 2
, Title of the invention Color-forming composition 3, Relationship with the person making the amendment Name of applicant (676) Lion Co., Ltd. 4, Agent ↓) Maro, Subject of amendment Detailed description of the invention in the specification column 1, “Surface area is 1 to 5” on page 7, line 1 to 2 of the specification
00 m"/gr, preferably 100-500m'/g
r," is corrected to "Surface area is 0.1 to 500 m'/g, preferably 1 to 500 m'/g, J.

2. On page 16 of the same book, in the third line from the bottom, "lashing" is corrected to "brushing."

Claims (1)

[Claims] (A) an immobilized dye in which a water-soluble anionic dye is immobilized on a water-insoluble cationic polymer; and (B) an ionic or semipolar nonionic surfactant, and the water-soluble anion can be formed by an external action. 1. A coloring composition comprising a dye and the surfactant in a form that undergoes an exchange reaction.