JPS62155208A - Wrapped dentifrice - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application: The present invention relates to toothpaste cream packaged in plastic laminated tubes, mechanical dispensers, flexible sachets, etc.

In particular, the present invention relates to toothpaste creams that have compatible contact properties with polyolefin surfaces of packaging such as plastic laminated toothpaste tubes, mechanical dispensers, or flexible sachets.

Conventional technology: Traditionally, toothpaste uses a lead tube coated with wax,
Traditionally packaged in flexible metal tubes such as unlined or epoxy resin lacquered aluminum tubes, the use of flexible shape-retaining plastic laminate tubes has increased in recent years.

Plastic laminate toothpaste tubes typically consist of an inner layer of polyolefin resin that is in direct contact with the toothpaste, and at least one intermediate layer that also includes an aluminum foil layer that prevents flavor from being lost from the toothpaste. It is also desirable to have an intermediate layer of paper present to provide stiffness to the tube. The outer layers are usually polyolefin resins, one of which is colored white. It also has printed markings that are protected by a clear polyolefin laminate overlay paper. Furthermore, an intermediate laminate layer or flexible plastic may be present.

Mechanical toothpaste dispensers may also have a polyolefin surface that contacts the toothpaste. In fact, the polyolefin itself may be the housing for the dispenser. Flexible sachet packets may also have a polyolefin surface that contacts toothpaste.

Toothpastes typically include a liquid vehicle of water and a humectant, a gelling agent solid vehicle, and a water-insoluble dentifrice. Toothpastes made of such materials, where the wetting agent is glycerin and sorbitol, and where the polishing agent is an alkaline earth metal salt such as dicalcium phosphate, may also include aluminum tubes with an inner coating of one layer of epoxy resin lacquer. Including, soft metal pastes have been packaged in toothpaste containers. However, when such toothpastes are packaged in containers with polyolefin inner surfaces, such as plastic laminated toothpaste tubes, mechanically actuated toothpaste dispensers, and flexible sachets, syneresis occurs and liquid drains from the toothpaste body. It has been found that separation occurs, thus making tooth brushing undesirable.

Alternative Measures to Solve the Problem: An advantage of the present invention is that phase separation of packaged toothpaste in contact with polyolefin materials is substantially prevented. Other advantages will become apparent from the disclosure below.

The present invention relates to a packaged toothpaste, the toothpaste being in direct contact with a polyolefin resin surface, the toothpaste comprising at least one of water, glycerin and sorbitol in combination with a preservative as a stabilizer against syneresis. About 20% by weight liquid vehicle (weight ratio of glycerin to sorbitol from about 25:1 to about 3:1)
a toothpaste solid vehicle consisting of about 1 to 5% by weight of an alkali metal carboxymethyl cellulose dentifrice gelling agent, about 20 to 75% by weight of a dentally acceptable water-insoluble alkaline earth metal salt polishing agent; The present invention relates to a packaged toothpaste comprising at least about 0.1% by weight of % C,-a alkyl parahydroxybenzoate ester as the preservative.

In toothpaste formulations, the liquids and solids must be combined in proportions to form a cream having the desired consistency that can be extruded from the package. The liquid in the toothpaste of the present invention mainly consists of water, glycerin, and sorbitol. The total liquid vehicle should be at least 2 oz.
It is usually contained in a range of about 20 to 75% by weight. Alkali metal carboxymethylcellulose is used as a toothpaste gelling agent or gum. Sodium carboxymethylcellulose is preferred. The content of gelling agent is about 0.1-5%, preferably about 0.5-2% by weight of the formulation.

Water is usually included in tooth brushing in an amount of about 10 to 50% by weight, preferably about 15 to 35% by weight. Glycerin and sorbitol are usually blended in a total amount of about 15 to 50% by weight, preferably about 20 to 75% by weight of the toothpaste, and the weight ratio of glycerin to sorbitol is 25:1 to about 3:1, usually about 0.25. =1 to about 0.8: 1, preferably about 0
．． 6:1 to about 0.8:1. The sorbitol used in the present invention is 6L of commercially available sorbitol syrup.
It is a mixture consisting of 7 Oit weight % sorbitol and 30 weight % water.

To prevent the toothpaste from undergoing syneresis when in direct contact with the polyolefin resin surface of the toothpaste package, one of the preservatives from the "paraben Cpa de αb #%)" family is added at a preferred minimum level of 0.25% by weight. May be added.

The addition of preservatives at these levels provides sufficient preservation of the toothpaste against bacterial contamination, without compromising the susceptibility of the basic formulation. The paraben material used is a C1-4 alkyl parahydroxybenzoate ester, usually a Cl+4 alkyl parahydroxybenzoate containing an alkyl group having 1 to 4 carbon atoms such as methyl-, ethyl-, propyl-1 or butyl parahydroxybenzoate. esters and mixtures thereof (eg, in a weight ratio of about 1:5 to 5:1). Methyl parahydroxybenzoate [Nipgin M
M) 1% and a weight ratio of methyl parahydroxybenzoate and butyl parahydroxybenzoate 1:1
mixture of (Nipa-stat)
) is preferred. Parabens are usually added in an amount of about 0.1 to 5% by weight, preferably about 20 to 7% by weight.

The dentally acceptable water-insoluble alkaline earth metal salt polish contains about 20 to 75%, preferably about 35% by weight of the toothpaste.
~60% by weight is blended. Typical salts include dicalcium phosphate dihydrate, anhydrous dicalcium phosphate, calcium carbonate, tricalcium phosphate, calcium pyrophosphate, trimagnesium phosphate trihydrate, magnesium carbonate, and mixtures thereof. be. Most preferred are calcium salts, especially dicalcium phosphate dihydrate, or a mixture of dicalcium phosphate dihydrate and anhydrous dicalcium phosphate.

In addition to the alkaline earth metal salt polish, additional polishes such as hydrated alumina or calcined alumina may be used, for example, at a weight ratio of alkaline earth metal salt to alumina material of about 2.5:1 to
The ratio may be about 4:1 and the total amount of polishing agent in the toothpaste may be about 25-75% by weight.

Organic surfactants can also be used in the toothbrushing process of the present invention to increase the prophylactic effect, to facilitate sufficient dispersion of the composition throughout the oral cavity, and to make the toothbrushing process more cosmetically acceptable. .

The organic surfactant may be an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, or a cationic surfactant, and as a surfactant it is a detergent substance that imparts detergent and foaming properties to the composition. It is preferable to use Preferred among these detergents are water-soluble salts of higher fatty acid monoglyceride monosulfates such as the sodium salt of monosulfate monoglycerides of hydrogenated coconut oil fatty acids, water-soluble salts of higher alkyl sulfates such as sodium lauryl sulfate, and dodecyl Water-soluble salts of alkylarylsulfonates such as sodium benzenesulfonate, water-soluble salts of olefinsulfonates such as sodium olefinsulfonate having an olefinic group having 12 to 22 carbon atoms, water-soluble salts of higher alkylsulfoacetate, 1 , water-soluble salts of higher fatty acid esters of 2-dihydroxypropanesulfonate, substantially saturated higher lower aliphatic aminocarboxylic acid compounds such as those having a fatty acid group, an alkyl group or an acyl group having 12 to 16 carbon atoms. These include water-soluble salts of aliphatic acylamides. An example of the last mentioned amide is N-
lauroylsarcosine, and the sodium, potassium, and ethanolamine salts of N-lauroyl, N-myristoyl, or N-balmitoylsarcosine, which significantly reduce the effectiveness of these compounds in the composition. It shall be substantially free of prone soaps or similar higher fatty acid substances.

Amides are particularly preferred because they not only have the effect of reducing the solubility of tooth enamel in acidic solutions, but also have an excellent long-term inhibitory effect on acid formation in the oral cavity due to the decomposition of carbohydrates. This is because it shows. Another desirable material is long chain fatty acid sodium monoglyceride sulfonate, used alone or in combination with sodium lauryl sulfate.

Other particularly suitable surface-active substances include nonionic surfactants, such as the condensate of sorbitan monostearate with about 20 moles of ethylene oxide or the condensate of ethylene oxide with propylene glycol ("Pluronic" products), and milanols. Examples include amphoteric surfactants such as long chain (alkyl)amino-alkylene alkylated amine derivatives sold under the trade name "Milanol" such as C2M. Diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride, benzyldimethylstearylammonium chloride, benzyldiethylstearylammonium chloride, tertiary amine, one of the three groups bonded to the desired element is a fatty alkyl group (12 to 18 carbon atoms) , two are (poly)oxyethylene groups (usually about 2 to 5 (1
7) tertiary amines containing an ethanoloxy group, salts of these tertiary amines with acids, and compounds having the structural formula (wherein R is a fatty alkyl group having 12 to 18 carbon atoms) base,!,'/s Z is a number that totals 3 or more)
, and salts of compounds of this structural formula with inorganic or organic acids, and the like may also be used. Approximately 0.0 during tooth brushing
Preference is given to using 5 to 5% by weight of said surfactant. Most preferably, the surfactant is an anionic surfactant, especially sodium lauryl sulfate.

Preferably, the toothpaste also contains fluorine-containing compounds that have beneficial effects on the protection and hygiene of the oral cavity, such as reducing the solubility of enamel in acids and protecting teeth from erosion. Examples of these compounds include sodium fluoride, stannous fluoride, potassium fluoride, potassium tin fluoride (SnF2.KF), sodium hexafluorostannate, stannous fluoride chloride, and zirconium fluoride. Examples include sodium acid and sodium monofluorophosphate. These substances are substances that dissociate or release fluorine-containing ions into water, and the water-soluble fluorine content is usually within the range of about 0.01 to 1% by weight, which is an effective amount and does not show toxicity. It is preferable to mix it into toothpaste in such an amount that there is no need to worry about it.

A preferred fluorine-containing system is sodium monofluorophosphate, usually at a content of about 0.076 to 7.6% by weight, preferably 76%, or a mixture of sodium monofluorophosphate and sodium fluoride, for example about 2= They are blended at a weight ratio of 1. When sodium monofluorophosphate and sodium fluoride are used together, a 1:1 mixture is also desirable. The preferred total amount of soluble fluoride is about 1000-1500 ppm.

Suitable flavorants or sweeteners can be used to incorporate flavor into the compositions of the present invention. Suitable flavor components include flavor oils, such as trumpet oil,
Mentha oil, wintergreen oil, sweet safras oil, clove oil, sage oil, eucalyptus oil, marjoram, cinnamon,
These include lemon, orange, and methyl salicylate. Suitable sweeteners include sucrose, lactose, maltose, xylitol, sodium 6-methyl-3,
Examples include 4-dihydro-1,2,3-oxathiazin-4-one, sodium cyclohexylsulfamate, perillartintr, and sodium saccharin. Flavoring agents and sweetening agents are used in combination,
It is incorporated in the composition of the present invention in an amount of about 0.01 to 5% or more.

Various calcium and magnesium ion suppressants can also be used to adjust the physical properties of the composition. Suitable inhibitors are water-soluble inorganic polyphosphates, such as tetrasodium pyrophosphate or disodium pyrophosphate, which are partially neutralized or acidic.
IJ phosphate is preferred.

Other suitable inhibitors include alkali metal salts of citric acid, preferably sodium salts. Generally, such compounds affect the physical properties of the scrub and are therefore used in small amounts in the formulation, usually about 1-3% by weight.

Toothpaste must have an appropriate pH for use. A pH range of 5 to 10 is particularly desirable. This pH value is a value obtained by directly measuring the pH of toothpaste. If necessary, substances such as citric acid may be added to adjust the pH to, for example, 6-7.

Various other substances besides those mentioned above can be incorporated into tooth brushing. Examples include colorants or whitening agents or pigments, rust inhibitors, silicones, chlorophyll compounds, ammonium compounds such as urea or diammonium phosphate, and mixtures thereof, and other component materials. Whitening agents, such as titanium dioxide, typically present at about 0.5-2%, are effective in maintaining the appearance of toothpaste compositions, as some discoloration may occur over time. .

The compositions of the present invention may include adjuvants in amounts that do not substantially adversely affect the desired properties and properties, and appropriate amounts are selected and used depending on the particular type of composition desired.

The compositions of the present invention may include about 0.1 to 5% by weight of an antibacterial agent. Typical antibacterial agents include N'-(4-chlorobenzyl)-N5- (2,4-
dichlorobenzyl) biguanide; p-chlorophenyl biguanide; 4-chlorobenzhydryl biguanide; 4-chlorobenzhydrylguanylurea; N-3-lauroxypropyl-N5-chlorobenzyl biguanide; to 1,6-di-chlorophenyl biguanide Kisan;1
．． 6-bis-(2-ethylhequin rubiguanide)hexane; 1-(lauryldimethylammonium)-8-Cp-chlorobenzyldimethylammonium)octane dichloride; 5.6-dichloro-2-guanidinobenzimidazole; N1-p -Chlorophenyl-N5-lauryl biguanide; 5-amino-1,3-bis(2-ethylhexyl)-
Examples include 5-methylhexahydropyrimidine and nontoxic acid addition salts thereof.

The package in which the toothpaste is packaged can be any polyolefin laminate toothpaste tube. for example,
The tube is disclosed in U.S. Pat. No. 3,260,4 by Plant et al.
The one described in No. 10 may be used. The content of the disclosure is quoted below. As described in the Examples,
An aluminum foil base with a thickness of about 0.0013
Heat the foil to a temperature of 7°C and place one side of the heated foil.
Random copolymer made from ethylene and acrylic 1λ (acid content 3 ± 0.5% and melt intex 8
±1) of the extrudable film and at the same time press the opposite surface against the low density polyethylene film.

Using driven rolls, a laminate paste is obtained in which the copolymer layer is about 6 mils thick and the polyethylene layer is about 5 mils thick. This paste is then shaped into a tube and sealed.

After forming the tube shape into the tube body, the tube is filled with the toothpaste of the present invention. In this case, tooth brushing does not undergo syneresis.

Polyolefin laminate toothpaste tubes containing more intermediate layers can also be used satisfactorily for the toothpaste of the present invention without syneresis occurring. for example,
Reference is made below to the multilayer flexible sheet structure for toothpaste tubes described in the "Prior Art" section of U.S. Pat. No. 4,418,841 to Extin. In fact, the toothpaste of the present invention packaged in tubes of sheet material identified as Prior Art A and A-1 in U.S. Pat. No. 4,418,841 is satisfactory and substantially free of syneresis. do not have.

Such tubes A and A-1 consist of layers as shown below, listed in order from outer layer to inner layer.

A-1 1.5°mil LDPE 1.5
Mill LDPE2.0mil Pigmented LDPE 2.
LDPRl with 0 mil pigment, 6 mil (-per
1.6 mil paper 0.7 mil LD PE
2.0mil LDPE3.3mil EAA
1.0mil 0PP0.7mil foil 1.0mil EAA2.0mil E
A A O, 7 mil foil 1.2 mil L
D P E 2.0 mil EAA1
3.0 mil total 1.2 mil LDP
Rl 3.0 mil Total A, the abbreviations in 2 in A-1 represent the following.

LDPE: Low density polyethylene EAA: Ethylene acrylic acid OPP: Oriented polypropylene Fono-Shackman U.S. Patent No. 4.437,5
Mechanically actuated dispensers, such as those described in US Pat. No. 9, in particular for pasty substances, the disclosure of which is incorporated hereinafter, may also be used in the practice of the present invention. The housing of such dispensers is typically made of a polyolefin resin such as polypropylene. Thus, the resin of the toothing is essentially two layers, the inner surface of which is in contact with the toothpaste. Even when the toothpaste of the present invention is packaged in such a polypropylene mechanical disinser shell, syneresis does not substantially occur.

The advantages of the present invention are also seen when packaging toothpaste in flexible sachets having a polyolefin surface (usually low or medium density polyethylene).

The essence of the present invention will be further clarified by the Examples described below, but it goes without saying that the present invention is not limited thereto. Unless otherwise specified, all amounts and proportions listed below are by weight.

The following toothpaste was made to have a creamy consistency sheen, and the laminate structures A8 and A-
1 into each tube.

Part by weight Glycerin 6000 6000
Sodium monofluorophosphate 0.760
0.760 Sodium fluoride 0.
100 0.100 carboxymethyl cellulose
0.900 0.900 Sodium Tetrasodium Pyrophosphate 0.250
0.250 Sodium Saccharin 0.
200 0.200 lubito-ru 70% solution
24,000 24,000 deionized water - irradiation
16,923 17.173 Dicalcium phosphate dihydrate 4&000 4&OOO flavoring agent
0.950 0.95(1
After aging at 49°C for at least 9 weeks, tooth brushing (1
) was maintained in a creamy consistency in each laminate tube of structures A and A-1, but
Toothpaste (2) was placed in both tubes of Structures A and A-1 and separated into a liquid phase and a solid phase within 3 to 6 weeks at 49°C.

Example 2 Toothbrushing (1) 3 and (2) were prepared using U.S. Patent No. 4,437.
, No. 59) into a mechanical dispenser made of polypropylene housing.

Toothpaste (1) retained a creamy consistency, while toothpaste (2) separated into a liquid phase and a solid phase.

Results similar to the above were obtained in the following cases.

+11! Use calcium carbonate instead of dicalcium phosphate hydrate: 1+0 Use dimagnesium phosphate trihydrate instead of dicalcium phosphate dihydrate; ■ Relative ratio of glycerin and sorbitol (70%) The amount is
10:15:0.25 vs. 10:15:0.3 and 6:2
4:1 to 6:24:O; (I■ methyl parahydroxybenzoate instead of methyl parahydroxybenzoate, respectively; furovir parahydroxybenzoate: butyl parahydroxybenzoate: 3 and methyl parahydroxybenzoate and butyl parahydroxybenzoate 5:1, l
: 1.1:5 mixture used; Case: υID Toothbrushing When packed in a flexible sachet made of layered rain (described in order from the outer layer to the inside) as shown below: 12.2μ Polyethylene terephthalate 21.3μ
White ethylene acrylic foil 9.0μ foil 3.3μ Ethylene acrylic acid 25.4μ Medium density polyethylene Toothpaste (1) 8 When changing the amount of methyl parahydroxy pen shade to 0.1 part, 49° Better results were obtained with toothpaste (2) after 0.016 weeks of aging. Separation then occurs in the toothpaste under accelerated aging conditions.

It is clear that the detailed description so far has been given by way of example only, and that various modifications are possible without departing from the spirit of the invention.

6 Contents of the amendment Procedures Amendment Document July Jθ, 1988 1, Indication of the case 1988 Patent Application No. 296493 2, Name of the invention Packaged toothpaste 3, Person making the amendment Relationship with the case Patent application Person Address Name Cordate Palmolive Company 4, d.
ri person t4Xnobmahmeq-7-W sea r154 niff leaf, -rne11 1hta correct.

rSuch compounds are used in small proportions in the formulation.

The exact amount will vary depending on the particular formulation, such as the physical characteristics of the toothpaste, and will typically be incorporated at about 1-3%. (2) The third line from the bottom of page 25 of the specification is amended as follows.

T (iii) Chrycerin and sorbitol (70%)
and methyl para above 1; roxybenzoate river versus j and above

Claims (19)

[Claims] (1) A packaged toothpaste, wherein the toothpaste is in direct contact with the surface of the polyolefin resin package, and the toothpaste is combined with a preservative as a stabilizer against syneresis using water, glycerin, and sorbitol (weight of glycerin to sorbitol). at least about 20% by weight of the liquid vehicle (with a ratio of about 0.25:1 to about 3:1);
1 to 5% by weight of an alkali metal carboxymethylcellulose toothpaste gelling agent, about 20 to 75% by weight of an acceptable water-insoluble alkaline earth metal salt polishing agent, and at least 0.1% by weight of C_1_-_4 as the preservative. A packaged toothpaste consisting of an alkyl parahydroxybenzoate ester. (2) The weight ratio of glycerin to sorbitol is approximately 0.25
The packaged toothpaste according to claim 1, wherein the ratio is 0.8:1 to about 0.8:1. (3) The weight ratio of glycerin to sorbitol is approximately 0.6:
3. The packaged toothpaste of claim 2, wherein the ratio is 1 to about 0.8:1. (4) The packaged toothpaste according to claim 1, which contains about 0.25 to 1% by weight of the preservative. (5) The packaged toothpaste according to claim 4, wherein the preservative is methyl parahydroxybenzoate. (6) The packaged toothpaste of claim 5, wherein said preservative is a mixture of two said alkyl parahydroxybenzoate esters in a weight ratio of about 1:5 and 5:1. (7) The packaged toothpaste according to claim 6, wherein the alkyl parahydroxybenzoate esters are methyl parahydroxybenzoate and butyl parahydroxybenzoate. (8) The packaged toothpaste according to claim 6, wherein the alkyl parahydroxybenzoate ester is contained in a weight ratio of about 1:1. (9) The packaged toothpaste according to claim 1, wherein the alkali metal carboxymethylcellulose is sodium carboxymethylcellulose. (10) The packaged toothpaste according to claim 9, which contains about 0.5 to 2% by weight of the carboxymethyl cellulose sodium. (11) The packaged toothpaste according to claim 1, wherein the water-insoluble alkaline earth metal salt is a calcium salt. (12) The toothpaste according to claim 11, wherein the calcium salt is dicalcium phosphate dihydrate. (13) The toothpaste according to claim 1, wherein the toothpaste is packed in a plastic laminate tube. (14) The toothpaste according to claim 13, wherein the inner polyolefin resin surface of the plastic laminate tube is polyethylene. (15) The toothpaste according to claim 14, wherein the polyethylene is low density polyethylene. (16) The toothpaste according to claim 1, wherein the toothpaste is packed in a mechanical dispenser having a housing made of polyolefin resin. (17) The toothpaste according to claim 16, wherein the polyolefin resin of the housing is polypropylene. (18) The toothpaste according to claim 1, wherein the toothpaste is packed in a flexible sash. (19) The toothpaste according to claim 18, wherein the inner polyolefin resin surface of the sash is made of low density polyethylene or medium density polyethylene.