JPS60188309A - Dentifrice composition - Google Patents

Abstract

PURPOSE:A dentifrice composition, containing nonhydrated calcium hydrogenphosphate having an average value of crystallite size within a specific range measured by X-ray diffractometry, as a polishing agent, and having excellent cleaning ability and mild polishing properties. CONSTITUTION:A dentifrice composition containing 5-50wt%, based on the total composition, nonhydrated calcium hydrogenphosphate having 300-3,500Angstrom , preferably 300-3,000Angstrom average value of crystallite size measured by the X-ray diffractometry, preferably 0.30-0.78g/cm<3> static bulk density, 0.40-0.95g/cm<3> dynamic bulk density, 0.60-1.40g/cm<3> tapping density, 1.0-5.0mu diameter measured by the Blaine method, 1.0-30mu, particularly 5-20mu average particle diameter and 2.0-30m<2>/g specific surface area measured by the BET method as a polishing agent. Preferably, the above-mentioned nonhydrated calcium hydrogenphosphate has 0.1-5mum average value of primary particle size and is a spherical adhered aggregate of plate crystals with 0.5-0.9 average roundness.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has a cleaning capacity of 1 (5-1 teeth).
I recommend 1 loss for namel quality.
Regarding toothpaste compositions having Ill in kll I, 111N polishing agent (111N), which is generally used for N++ polishing (:1, Yama's j61 Naefuzuki and 1), removes stains, plaque, and the like. It has a high ability to efficiently remove deposits that adhere to the teeth and damage the tooth's J-namel trade. In this case, it is desirable to have a mild abrasive property1) that prevents the deposition of dental plaque, m?'i. Efficiency of physical removal such as (A) can be increased by increasing the abrasive power of A grinding. 125 If brushing is not done properly, it increases the possibility of causing a wedge-shaped defect and damages the tooth surface, which may reduce the gloss of the southern surface.1For this reason, conventional J, There has been a demand for a toothpaste composition that has an appropriate abrasive power and has an excellent cleaning effect without causing damage.

The inventors have developed the above tft! As a result of intensive research in response to Cao Wang, we found calcium hydrogen phosphate anhydrate having crystallites with an average crystallite size in the range of 300 to 3500 as measured by X-ray diffraction. (dibasic calcium phosphate, anhydrate), among which the static bulk density is 0.
30 to 0.78 tusks/d, and the dynamic bulk turtle is 0.40 to 0.
．． At 95'iJ/cm, the tapping density 1α is 0, 60''-1, /IC'
) Zhong/'Cl11', B1Non's value is 1.0・j'i, OIt-(f is present, average particle (Y is 1.0).
(') ~ 30 ft, specific surface area is 81ETF person'c2, 0-30 m/'# CA; far t
)(f) is a material 11 suitable as an abrasive, and the top t1
When calcium hydrogen diphosphate anhydrate is used as an abrasive, l1lii II silk acid! It has been discovered that by increasing the II + +>i force to a higher value ν), the photographing power can be reduced in the direction of 1-1, and the present invention has been incorporated into the present invention. l + II 1 name agent (abrasive power and cleaning power [, f are in a proportional relationship, so to increase cleaning power li
till IF There is a road-cao that increases the power of the town, achieving (K and high Qing 1 mortar) power and low 1tll polishing power at the same time; L
I had to go to work C. On the other hand, the average f1ri of the two crystallites measured using the X-ray diffraction method decreased to 300 and 360.
When using calcium hydrogen phosphate anhydrate, which has 0 crystallites, the following experimental example (J shown, J, U (
：Despite its low abrasive power, it has high cleaning power, and this calcium hydrogen phosphate anhydrate is used in 11 countries.
It was discovered that the characteristics of 1, 15, and 6 cleaning (ω force and low polishing force) can be simultaneously satisfied by cleaning the tooth in 1 minute without causing any damage to the Tf metal trade of the tooth. ()It is b.

It is conventionally known that calcium hydrogen phosphate anhydrate (dibasic calcium hydrogen phosphate anhydrate) is used as a polishing agent for toothpaste +1'.

However, the average crystallite size of the conventionally used calcium hydrogen phosphate anhydrate measured by X-ray diffraction is about 3,800 to 4,300, and the specific surface area is 1 to 1.
2 I/'It (BEE Dingho) Hodomaro, Mitsu 1 Ken is 2.890
'il), /cm, and this is in the J: sea urchin normal particle size range (10-30μ
The abrasive power of m) is too high, and when used as an abrasive in 11, ΔDΔ(Δmerican
D ental A 5sociaNon) etc.
! RDA method (Radio), which is internationally limited.

Δactive Denn Abration method)
If the value of polishing exceeds 250 and the brushing method is inappropriate, long-term use may cause wedge-shaped defects (there was also wear).For this reason, conventionally For Of (). On the other hand, -6
- Calcium hydrogen phosphate anhydrate (secondary calcium phosphate anhydrate) according to the present invention has an average crystal -r size 11r1 of 300 to 3500 as measured by X-ray diffraction method.
Compared to the conventional -B, the crystal has fewer sharp edges and is more rounded, and its polishing power is significantly lower, making it the best in China and Germany.
It takes only 15 hours to use as a polishing agent, and has superior cleaning power (1'i stain removal power) compared to other polishing agents that have the same polishing power as hemp. Whitening, garlic U>
For the first time in 44 I, the 1st Song Dynasty was demonstrated.

The present invention will be explained in detail below.

Toothpaste composition according to the present invention, il 3! l'nee! l
-The experiments shown in the xIIA diffraction method until -C'J:
Calcium hydrogen phosphate anhydrate (dibasic calcium hydrogen phosphate - Contains anhydrous product), so it has moderate abrasive power and high cleaning power for teeth as described above.

Here, hydrogen phosphate car used in the present invention 7
= Lucium anhydrate has an average crystallite size of 300 to 3
Although it has a size of 500 people, a size of 300 to 3000 people is particularly suitable for use in terms of cleaning power and the like. On the other hand,
If the average crystallite size is less than 300 AJ, the cleaning power is too low, and if it is larger than 3500 AJ, the abrasive power is too high and cannot be used for the purpose of the present invention.

J3, Calcium hydrogen phosphate anhydrate used in the present invention has a static density of 0.30 to 0.787/cm according to the measurement method shown in the experimental example. The ilI high density is 0.40-0.95 teeth/d, the tapping density is 0.60-1.40')/c-if, the 71-noon diameter is 1.0-5.0μ, Average particle size is 1.0
~30 lt, and the specific surface area is 2.0~3 by BET method.
Preferably, it is 0 m/l. In particular, average particles (those with a diameter of 5 to 20 μm) are preferably used in terms of the use of 1i%, such as roughness.

In addition, the calcium hydrogen phosphate anhydrate used in the present invention has an average particle size of 0.1 to 5 fl.
The average size of the -8-order particles (hereinafter referred to as J3), in which plate-like crystals of IIl are fixed and aggregated, is 1°, which is the value measured from the electron micrograph. Calcium hydrogen phosphate anhydrate has a plate-like shape, with flaky crystals densely interlocking in a pinecone shape.
It is preferable that the crystalline structure is in an aggregated form, and in this case, the crystal structure is clearly defined as follows: -t) Difference λ, <r 5. ), or spherical calcium hydrogen phosphate anhydrate (this type of calcium hydrogen phosphate anhydrate 4J average roundness lfj
[Wadcll, J, Qeol, 40° 1932.4/13-451] was 0.45-0.
95, particularly 0.5 to 0.9, preferably 6. ) were used, and the former (-t) was particularly excellent in terms of di-stable effect, and the 19th spherical type (li) was used in terms of usability such as roughness and gloss imparting effect (corrosion). ing.

In addition, the above-mentioned calcium hydrogen phosphate anhydrate should be added in an amount of 1 to 60% (heavy %, hereinafter the same) of the entire composition, especially 5%.
It is preferable to set it to 50%.

Calcium hydrogen phosphate anhydrate of the present invention can be prepared by -9- conventional methods such as US Pat. No. 2,287,699 (19
42), No. 3012852 (1961), No. 3066056 @ (1962), No. 3169096 (1965), Japanese Patent Publication No. 39-3272.3273, etc. in the neutralization reaction between phosphoric acid and milk of lime. Control crystal growth or crystal properties and specific growth of individual crystal faces 3! It can be manufactured by adding a crystal modifier to give a certain effect. In this case, as the crystallizing agent, for example, a phosphoric acid condensate and its salt can be suitably used, and it is preferable that the addition of (a) is carried out during the neutralization reaction between phosphoric acid and milk of lime. In addition, addition of crystal modifier 1
1 is 0 of the produced calcilyl hydrogen phosphate anhydrate
．． It is preferably 1 to 30% by weight, particularly 0.5 to 20% by weight, and especially 1 to 10% by weight. The apparent density and true density marks also tend to decrease. On the other hand, if the amount added is less than 1% by weight, the average crystallite size becomes larger than that of 3500-10-wt., and the polishing force becomes high. ')'!
I'j! If the amount added is more than 30%, the average crystallite size will be 300%.
) may show low color and high purity properties.The anhydrous product of the present invention, calcilano hydrogen phosphate, is produced by A).
- Addition #ii of the above crystallizing agent in the culm, addition timing,
Addition amount 1, phosphoric acid degree, reaction temperature, reaction time, stirring speed]α, addition method of milk of lime, origin of b1 size, etc., as appropriate τ
Various grades of -B can be prepared. For example, if you mix the electrolyte: calcium compound and phosphate compound at 50-90%
When a phosphoric acid condensate is added to J (1'), the calcium hydrogen phosphate anhydrate of the present invention can be suitably obtained.

As other components of the dentifrice composition of the present invention, appropriate components can be used depending on the type thereof.

In this case, in the present invention, in addition to the above-mentioned calcium hydrogen phosphate anhydrate, other abrasives, such as calcium hydrogen phosphate dihydrate (dibasic calcium phosphate
dihydrate) and conventional ~11 uniform 11 - Calcium hydrogen phosphate anhydrate with crystallite size of about 3800 to 4300, calcium carbonate, calcium birophosphate, insoluble sodium f1-metaphosphate, amorphous Groups such as silica, crystalline silica, precipitated silica, aluminosilicate, aluminum oxide, aluminum hydroxide, microcrystalline cell [l-su, resin, tribasic magnesium phosphate, magnesium trichloride, tribasic calcium phosphate, titanium chloride, etc.] It is possible to use one type of abrasive or a mixture of two or more types of abrasives, but when using other abrasives in combination in the present invention,
It is preferable to use one or more of calcium hydrogen phosphate dihydrate, aluminum hydroxide, aluminum silica, aluminosilicate, calcium carbonate, insoluble sodium metaphosphate, and calcium birophosphate. here,
The mixing ratio (weight ratio) of the calcium hydrogen phosphate anhydrate of the present invention and the polishing agent is preferably 5:95 to 100:O, and within this range, the calcium hydrogen phosphate of the present invention The effect of anhydrous product is fully exhibited. In addition, in the present invention, it is preferable to incorporate tertiary magnesium phosphate, which can prevent the assimilation of the composition and increase the stability tt+ of the composition. Note that the rJI abrasive abrasive content is usually 1 to 99%, particularly preferably 10 to 9!]% of the total composition.

In the case of toothpaste, carrageenan and carboxyme J-4y-1? are used as binders. / 11-sodium, medylcel [1-s, human 11-sodium, le[1-s]
-S, CarboxymethylHl:IT :l::C-1-
Tirrelolose 1 helium and other rel[1-su derivatives, alginate notorium and other alkali metals] I) Reginate, alginic acid protein 1 pyrene glycol J stell, 1 nilintan gum, tragacan 1 hegum , Karaya gum, gums such as E7 Labia gum, polyvinyl alcohol, sodium polyacrylate, carboxyvinyl polymer gelling silica, gelling aluminum silica, one or more of inorganic binders such as Veegum and Laponite.
- may be blended (compounding amount usually 0.5 to 5%).

- 1 3 - In addition, sorbitol, glycerin, ethylene glycol, propylene glycol, and 1 part thickening agent.

3-buty-1 non-glycol, polypropylene glycol, polypropylene glycol, xylitol, malt
-., rough chit, etc., or two or more types 1- may be blended (Blending Mi usually 10 to 70%).

In addition, sodium lauryl sulfate, myristyl sulfate 1~
Water-soluble salts of higher alkyl sulfates whose alkyl group has 8 to 18 carbon atoms such as hydrogenated A7 oil fatty acid monoglyceride monosulfate sodium 111t1m, sodium dodecylbenzenesulfonate Hide's alkylaryl sulfonate, higher alkyl sulfonic acid Jn, higher fatty acid ester of 1,2-dihyde 1koxypropane sulfonate,
N-lauroyl, N-myristoyl or N-balmi] ~
AniA activators such as substantially saturated higher aliphatic acylamides of lower aliphatic aminocarboxylic acid compounds such as the sodium, potassium or ethanolamine salts of ilsarcosine, fatty acid jetanolamides, cy-14-yosaccharide mono- and dilaures Sucrose fatty acid ester, lactose fatty acid J sprue, lactose fatty acid ester, lactose fatty acid J sprue, lactose fatty acid 3HL containing 12 to 18 carbon atoms, lactose fatty acid ester F! , 1 stell,
Maltitol fatty acid - [sprue, stearic acid monoglyceride, sorbitan fat l/J: s sprue, polyoxy J tyrensol gotan monolaure-1, polyA xy T 1 nonsorbitan t nostea 1 no 1, polyoxy- <10.20./io, 60°80.
100 mol) hydrogenated castor oil, intermediates of di[dylene A oxide and p[]pyrene A kylide, and polyoxyethylene polyA:1 dipropylene t-nolauryl ester and other poly-[ethylene 1st oxides and fatty acids, fatty alcohol,
Condensation with polyhydric alkyl and polyIFil pyrene oxide/I 1-1 surfactant (compounding amount usually 0~10%)
, preferably 0.5-5%), but in the present invention, as the W-surface activated bamboo agent, sucrose fatty acid ester, especially fatty acid), (has a carbon number of 12 or 171, and has an average Nisdellian degree of It is preferable to use one whose is -15-1.2 to 1.8,
To this: 11 dentifrice compositions with extremely excellent foaming properties.
1 can be done. Note that the amount of sucrose fatty acid ester blended is preferably 0.5 to 10% of the total amount.

In this case, it is preferable to use an acylated amino acid and/or its salt, such as N-lyloylsarurodine sodium, in combination with the sucrose fatty acid ester. can be given. Here, the blending amount of the acylated amino acid and/or its salt is preferably 0.1 to 0.5% and 1%.

The dentifrice composition of the present invention further contains saccharin sodium, stevi'A1Lide, neohesberidyl dihydrochalcone, glycyrrhizin, perillartin, thaumatin, asparatylphenylalanine methylnispur, p-meF.
4-cinnamic aldehyde, sucrose, lactose, 9-saccharide,
11 flavoring agents such as saccharin sodium (0-1%, preferably 1) (0.01-0.5%), wintergreen oil, spearmint oil, peppermint oil, saccharin oil, clove oil,
Flavoring ingredients such as eucalyptus oil, omenthol, carvone, eugenol, aneneol, gelatin, peptone,
Contains whitening agents such as arginine hydrochloride, albumin, and casein, preservatives, silicone, pigments, and other ingredients.
For example, in the case of toothpaste, the above-mentioned desired ingredients are kneaded in an appropriate amount of water to obtain the product. Najl
) 1 In the present invention, C may contain J-Men 1 Hel and Tf/or Ane 1 ~ - as fragrance ingredients! IY Maminoku has created a toothpaste composition with 9 flavors and excellent f1!
can do. Here, the amount of omenthol added is 0
．． 05-・1%, the blend m of Anne1~-le is 0.0O5-
Preferably it is 0.5%.

Furthermore, in the present invention, allantoins, epsilon aminocaproic acid, tonone, 71 reamic acid, de1:stranase, amylase, protea-1! Enzymes such as , mutanase, lysozyme, liquefaction enzyme, lithium fluoride, alkaline gold such as monofluorophosphate, sulfurium monofluorophosphate, potassium monofluorophosphate, thorium fluoride, etc. , ammonium fluoride, fluorides such as stannous fluoride, 1 to chloride
Cisine salts, dihydrocholesterol, glycyrrhetinic salts, glycyrrhevenic acid, glycerophosphate, chlorophyll, calopeptide, water-soluble inorganic phosphoric acid compounds,
Active ingredients such as vitamins such as vitamins A, B, and E, plant extracts, anti-tartar agents, antibacterial agents, anti-inflammatory agents, etc. can be blended at 11 iF or more than 2 seconds.

The dentifrice composition of the present invention contains vitamin E and its esters (for example, nicotinic acid ester, acetic acid ester, etc.).
, monofluoro[1] such as monofluorophosphate
Alkali metal phosphate salts, De': Stranase, mutanase, and extracts from plants such as Toki, Gajutsu, Sukishaho, Jiyu, Mugwort, and Ephedra are stably blended, so these active ingredients are effectively absorbed. Use, ^self combined. in this case,
As the vitamin E and Nistil, the vitamin Nisdel trinicotinate is effectively used. In addition, the amount of vitamin [III and A] esters is 0.01~0゜=
18-5%. Furthermore, −1-nonor A [l
The blending amount of helium phosphate is preferably 0.1 to 1%, particularly 0.1 to 0.76%.
Preferably, the amount of Lanase and Mutana-1f to be blended is 0.1...2%. Also, the previous ff11. !
The formulation h1 of the extract of 1/1 is 0.01-1% and J
However, in the case of ephedra, the first period of A (1,5
% is preferable.1)

Here, the extract of the patterned material (well, the previous jjll!
It is good to use one extract of 1Ffi in the middle seeds, and even if these 11 extracts are used under the circumstances, J, k,
Alternatively, a mixture of two or more of the above plants f'+t+ is extracted l)
It is also possible to use a mixture of these extracts. In addition, as the solvent extract of the plant, narcissus extract, organic solvent extract, etc. are preferably used.1. /
44/ru1゜In addition, the raw stones used to obtain the above extract include dried herbal medicines, dried shreds, dried powders, etc.: those obtained by extracting oil from these after subjecting them to steam thermal surface treatment, and the remains of their offspring. Pickling; or pre-T11 plants in 1 part water and 1 part ethyl
-chill, ethylene chloride, dioquinone, -19
- Acetone, 1 Lower alcohols such as tanol and methanol, acids 11! A obtained by extraction with a polar solvent such as -1-Puru, P1'' pyrene glycol, glyc[aniline]
Extraction residue of A resin and A: The above plants were treated with n-hexane, petroleum dichloromethane, ligroin, Schiff [1 hexane, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tolutin, benzene, etc.] When extracting with non-41 soluble W, one selected from the group consisting of oleo-1 nodine and its extraction residue is used. When obtaining an extract of the plant from these raw materials, one or more of these raw stones are mixed with a polar solvent and/or a non-polar solvent (
The above-mentioned solvents may be used for the extraction treatment, and the extract (i.e., the extract or the solvent removed from it) is collected. Note that a mixed solvent of a lower alcohol or the like and water is also suitably used as the solvent when obtaining a solvent extract of the nt1 patterned product. In this case, this extract can be used as is, but it must be treated with steam heat! I! This extract or the steam hot surface residue is activated (11 charcoal,
After treating the extract with an adsorbent such as 11 algae or acidic white paper, the residue obtained by steam thermal surface treatment is treated with the solvent extract fraction and 1. It is suitable for use in Extraction 1) Extraction method (A method known to the public can be used, such as adding 1 part dry powder of a plant to a solvent. For example, add 1 pot of dried material to the same tank. 1 stroke, preferably l) or 5 to 10 times the weight of the solvent.
) [1, Muro-brown under the war is under boiling 51) and 0.5-2
Extract for 4 hours, preferably in the 1st column J3, for 10 hours. A method is adopted, such as collecting the extract separately from the extraction residue.In this case, if necessary, the extraction residue is subjected to the same extraction process again to obtain an extract, and this is combined with the previous extraction solution. They can be used in combination. 1. It is preferable to use the extract obtained in this way by distilling off the solvent by a method such as vacuum streaking, freezing, drying, spray drying, etc.

-21- Next, an example of production of calcium hydrogen phosphate anhydrate of the present invention will be shown.

[$I Production Example 11 An aqueous solution 31 in which 4.02 g of magnesium chloride was dissolved was heated to 80°C, and 380 g of quicklime was added under stirring.
Continuing stirring for 30 minutes, change the quicklime to W4.
and prepare milk of lime. Coarse particles were removed using a sieve with a size of 100 mesh and 1.
i) Take 1 q of milk of lime with 1ill pox.

Next, 85% phosphoric acid aqueous solution 1. , f to 75° C. and adding said milk of lime at a rate of 600 sh/h under stirring;
When the pH value of the reaction solution reached 2.2, milk of lime was added (Jf row 1) and 80% of birophosphoric acid was removed by P2O5 exchange.
．． The addition is started at a rate of 39/min and the birophosphoric acid addition is stopped when the pH value is 2.8. However, the addition of milk of lime is continued until the 11 value of the reaction solution becomes 5.0. Thereafter, the reaction solution was filtered, the filter cake was washed with water, and then dried at 60° C. for 24 hours. In addition, we decided to change the cotton to which the phosphoric acid condensate or its salt such as birophosphoric acid or sodium birophosphate was added. By changing the speed, various crystallite sizes,
Static bulk density, dynamic bulk density, tapping density, plain diameter, average particle diameter 1, specific surface area - Calcium hydrogen phosphate anhydrate 1! It's possible to do that! Ru.

[Production Example 2] Heat 3 aqueous solutions containing 3.7 liters of magnesium chloride to 80°C, add 3,907 liters of quicklime, and continue stirring for 30 minutes. : Tsu C
Digest 1 liter of quicklime and prepare 4 liters of T1 ash milk. This milk of lime is passed through a 100 mesh sieve to remove coarse particles, and the milk of lime with a concentration of 128'7/1 is sieved with calcium oxide.

Next, add 75% phosphoric acid aqueous solution 11 to 78°0
l Heat and stir on 5' hourly. (Add the milk of lime at a rate of 1 cup. When 11 of the reaction solution reaches O, El, 5
Step C (Start addition of 1 phosphoric acid at line 111 after addition of 1 ash milk), when ptl reaches 1.2, start addition of phosphoric acid +111 +l-me-23- The addition of milk of lime is continued until F)11 of the reaction solution becomes 5. (The total amount of milk of lime added is 5.3
J, the amount of birophosphoric acid added is 13.51, and the amount of birophosphoric acid added per 100 parts of calcium oxide is 2.
After that, the reaction solution is filtered, the furnace block is washed with water, and then dried at 60° C. for 24 hours to obtain calcium hydrogen phosphate anhydrate of the present invention.

[Manufacturing Example 3] Heating an aqueous solution 31 in which 3.42 grams of magnesium chloride was dissolved in 807; and stirring, 393 grams of quicklime was added.
By continuing stirring for 30 minutes, the quicklime is digested and milk of lime is prepared. This milk of lime was passed through a 100 mesh sieve to remove coarse particles, and the milk of lime of 1291/J was filtered through calcium oxide exchange. Jru.

Next, 1 J of a 70% phosphoric acid aqueous solution was heated to 80° C. and stirred at a rate of 54011 I/hr for i[! Milk of lime was added, and when the pH of the reaction solution reached 0.4, the addition of birophosphoric acid was started, and l) I+ reached 1.0 -24
- Stop the addition of pyrophosphoric acid at the point ++ ('i Continue adding the milk of ash, and stop adding the milk of lime when the I)11 of the reaction solution reaches 5.0.

As a result, the total amount of milk of lime added was 5.2), the amount of birophosphoric acid added was 13.0 parts, and the amount of birophosphoric acid added was 1.2 parts per 100 parts by weight of calcium oxide. 9/l car m
Corresponds to the + part. This is dried according to a conventional method to obtain calcium hydrogen phosphate anhydrate of the present invention.

By adjusting the timing and rate of addition of birophosphoric acid, calcium hydrogen phosphate anhydrate having various hanging forces can be obtained.

Next, an experimental example will be shown to specifically explain the 91 Song Dynasty of the calcium hydrogen phosphate anhydrate of the present invention.

[Example 11 Test Example 11 The polishing power and cleaning power of calcium hydrogen phosphate having various average crystallite sizes and average particle diameters shown in Table 1.2 were determined by the following method. It was investigated. In this case, the calcium hydrogen phosphate anhydrate used had a specific surface area (BET method) of 2.5-25 = -20 i/2 and a density of 2.650 to 2.885 teeth/d. The results are shown in Table 3.

The average crystallite size was measured by performing X-ray diffraction of the powder, and the crystallinity of the powder was determined from the broadening of the peak using the crystallite size as an index (). . Here, the X-ray source was measured using alpha rays for Cu-, and the X-ray diffraction data was analyzed for the main peaks without overlap using SchOrrer's equation D- and λ/βCOSθ. The size was determined. In this case, the main peaks are 2
θ-53, 1°, 49.3°, 47.3'.

36.1°, 32.9°, 32.6°.

31.1°, 30.25°, 2B, 656°13.15
Averaged over °. Note that D is the crystallite size [
], λ is the measured xriA wavelength [in], β is the broadening of the diffraction line [rad ] (a-
Ad203 powder calcined at 1100° C. for 24 hours was used as a reference), K was the shape factor (constant -0, 9), and 0 was the Bragg angle of the diffraction line. Further, β is the fraction obtained by subtracting the half-width given by λ given by a highly crystalline material under the same conditions from the experimentally determined half-width.

F J, dent, RO8, VOl, 55. N+1
, 4.

563-573 lay 1IcHerenk-described (in the method J:suR1) Δ(f(+1iI f 0
ilC eyes ve l')entinAbrasion)
Measure() the value.

Collect cigarette tar in the usual way, this is 'lt'l.
The liquid was applied uniformly to the tile, and after it had dried, it was placed in a polishing container, and the powder (each calcium hydrogen phosphate shown in the table) 52 was mixed with 0.3% carboxymethyl cellulose and 1 helium. 60% glycerin aqueous solution containing 1
Using a suspension consisting of 5 fangs, a load of 200
In No. 7, after 2000 brushings and polishing, the rate of removal of tar from the tiles was visually evaluated.

In addition, as brushing brushes, there are 44 seven bundles,
Hair thickness 8 mil (approximately 0.2IIIT11), hair length -2
7- Made of nine (62) material with a diameter of 12 mm, and the hardness of the material is M according to the Household Goods Quality Indication Law.

Evaluation criteria score 1: w8 grass tar removal rate 0-10% 2: 11-2
0% 3: 21-30% 4: 31-40% 5: 41-50% 6: 51-60% 7: 61-70% 8: 71-80% 9: 81-90% 10: 91-100% -28- Table 1 r) CP-D Calcium Hydrogen Diphosphate Dihydrate Table 2 DCP-A Calcium Hydrogen Diphosphate Anhydrate *: Average aggregate particle size is 1-ecd &N0rth
rllp particle size distribution measuring device Product name - 29 = Table 3 Various calcium hydrogen phosphate TiJ'l@force and cleaning car 30 - [Experimental Example 21 J Calcium hydrogen phosphate anhydrate shown in Table 4 The polishing power and cleaning power of J: was investigated using the same method as in Experimental Example 1, and the IIO personnel of both ministries were examined. The result ψ is shown in Table 4.

As a result of the above, it has been found that the calcium hydrogen phosphate anhydrate of the present invention has a high cleaning ability despite being low in polishing.

The present invention will be specifically described below with reference to Examples and Comparative Examples; however, the present invention is not limited to the Examples described below.

-33- In addition, in the following examples, the composition of T, 1jlffi is below 100%. Ni-Mori-a J-Menthol 40% Carvone 30 Anise oil 10 Fennel oil 1 La Methyl Salicile 10 Amyl Formate 2 Ethyl Bublé ~ -3- 100% = 34 - Kichi J31m! -Men I~--L 30% Vepamine 1-Oil 10 Calfone 20 )l Netol 15 Cassia Oil 5 Wintergreen Oil 10 To Methylilycyle-1 2 Acyl Formate 3 100% Vepermin 1-Hale 20% Peppermint Oil 30 Anethole 20 Wintergreen oil 15 Cinnamic aldehyde 10 -J Rubnare-1, 5 100% -35= Peppermint oil 50% Carvone 10 Anise oil 15 Cassia oil 10 Methyl salicylate 12 Ethylformate 2 - 36-[Example 1] Solhi 1--L 30.0% Polybibin Non-Glycol 3.0 Poly-J Lengellicol 400 5.0 Carboxymethylylrel[''-Sodium 1.01 Natsukarinna 1- Lium 0.2 Sucrose palmidine ℃) 1 stell 0.5 (Average king stellation + u1.3. Contains palmitic acid 1fi 95%) Sucrose lauric diester 0.5 (Average - "Stellated r+, s, Contains lauric acid n165 %
) No. A 1.0 Tertiary magnesium phosphate 2.0 Silicic anhydride 3.0 Calcium hydrogen phosphate (((hydrate 50.0 174 qualities of calcium hydrogen phosphate anhydrate: average crystal Child
283〇8 Static High Density 0.73 Toothpaste = 37 - Dynamic Bulk Density 0.89 Il Tapping Density 1.18 Il Brain Diameter 3.30tt Average Particle Size 13.717 Specific Surface Area 3.9 Before / Toothpaste showed good foaming power and excellent foaming properties.

[Example 2] Glycerin 15.0% Sorbi]Hale 10.0 Propylene glycol 2.0 Polyethylene glycol 4000 1.0 Carpoxymethyl 1! Le 11-sodium 0.5 carrageenan
0.5 Saccharinna]・Rium 0.1 Sucrose palmitin mono(Ster) 0.5 (average esterified hemp, 3. palmitic acid content) 95%) Sucrose laurine diester 1.0 (average degree of esterification 168 .Lauric acid content 65%) Tranexamic acid 0.05 - 38 - Chlorhexidine hydrochloride 0.01 Kori A1.0 Tertiary magnesium phosphate 1.0 Calcium hydrogen phosphate dihydrate 10.0 Calcium hydrogen phosphate・Anhydrate 40,0 Calcium Hydrogen Phosphate ・Properties of anhydrate: Average crystallite 2890 people static bulk density 0.50 teeth/d iIII bulk density 0.66z+ Tapping density 1゜00 〃 B1NON11 ¥; 1.80μ Average particle size 4.5 Specific surface area 3.0 buds/fangs This toothpaste had good foaming power and exhibited excellent foaming properties.

-39- [Example 31 Glycerin 5.0% Sorbyol 35.0 Propylene glycol 2.0 Sodium carboxymethyl cellulose 0. 2. Xanthan gum 1.0 Satucalin sodium 0. 1 Potassium glycyrrhizinate: li O,01 lauryl'
6A acid moon ~ lium 1.0 lauroyl diethanolamide 0.3 monoflu JC
I Sothorium Phosphate 0.76 Fragrance A1. 〇Titanium dioxide 1.0 Aluminum hydroxide 20. (') Calcium hydrogen phosphate, anhydrate 30.0 Properties of calcium hydrogen phosphate, anhydrate: Average crystallite 19108-40- Static bulk density 0.70'i') 10f v1 Bulk density 0. 91 〃 Cod Pink Density 1.21 〃 B1Non Diameter 3.45/l Average Particle Size 13.4I! Specific surface area: 5.0 ze/) This toothpaste showed good fluorine stability.

[Example-1] Glycerin 25.0% Polyethylene glycol 4.00 1.0 Poly]nibrene gelicol 4000 1.0 Sodium carboxymethyl cellulose 1.0 Hea gum 0.2 Sodium saccharin 0.2 Subi primary noid 0.01 Sodium lauryl SVm 1. O N-lauroyl sarcosinate 0.1 Sodium monofluorophosphate 0.761 ~ Ranexamic acid 0.1 - 41 - Chlorhexidine salt 1.11 ('1.01 Kaori A
1.0 Tertiary magnesium phosphate 1.0 Calcium hydrogen phosphate, di-aqueous phase 20.0 Calcium hydrogen phosphate, anhydrate 25.0 11 qualities of calcium hydrogen phosphate, anhydrate: Average crystallite 1540 Human static high density 0.72S+/c I dynamic bulk density 0.92 Il Tapping tomato 1.21 rl Brain diameter 3.75μ Average particle size 16.3 n Specific surface area 4.1 I/Fang This toothpaste is good It showed fluorine stability.

[Example 5] Sorbitol 20.0% 42- Polyethylene glycol 4000 5.0 Veegum 1
．． 0 Carboxyvinyl polymer lytucarin sodium 0. 2 LaurylEhWisu1~Rium 1.0Dex] ~Lanage 1.0 Fragrance 11A 1.0 Calcium hydrogen phosphate anhydrate 50.0 Properties of calcium hydrogen phosphate anhydrate: Average crystallite 680 people Static density 0.387/c-if Dynamic bulk density turtle 0.49! ! Tapping fine polishing 0.78/l Bluminon diameter 1.75/l Average particle size 16.21? Specific surface area: 9.2 teeth/toothpaste This toothpaste showed good dextrapase stability.

- 43 - [Example 6] Glycerin 20.0% Sorbitol 20.0 Polyethylene glycol 400 2.0 Xanthan gum 1.0 Saccharin 1-lium 0.05 Stevioside 0.01 Potassium glycyrrhizinate 0.01 Sodium lauryl sulfate 1 .0 Lauroyl diethanolamide 0. 2 Dextranase 1.0 Mutanase 1.0 Kaori A 1.0 Calcium hydrogen phosphate dihydrate 10.0 Silicic anhydride 2.0 Calcium hydrogen phosphate anhydrate 30.0-44
- Properties of calcium hydrogen phosphate anhydrate: average crystallite
1750 people Static high density 0.51/cm' Dynamic bulk density 0.71'lI Tapping smallpox 1.09 l? Bluminon diameter 2.20. Z average particle diameter 9.31! 1 table FniR3,! M/g This dentifrice showed good DexF-lanase and mutanase stability.

[Example 7] Glycerin 10.0% Sorbitol 25.0 Carpoximebrucell [l-sodium 0.5 Veegum 0.2 Carbo-1 divinyl polymer 0.2 Satucarinna[-lium] 0.2 Lauryl sulfate [-lium] 1. O N-lauroyl monkey] Cine-1-0,3 sucrose laurindi J stell 0.5 - 45 - (average ■ sprue [1,8, laurin pregold tk! 65%
) Monoflu A℃ Putrium Phosphate 0.76 Chlorhexidine J1 λ Acid 1p O,01 Vitamin F Acetic Acid 1i 0
．． 1 Fragrance A 1.0 7gnesium tertiary phosphate 1. 〇Titanium dioxide 1.0 Calcium hydrogen phosphate, anhydrate / 1.0.0 Properties of calcium hydrogen phosphate, anhydrate: Average crystallite 137
0 static high density 0.49 tusk/C Gocho high density 0.64z+ Tapping density 0.94 1! Brane diameter 2.207. z Average particle size: 15,7 // Specific surface area: 8.4/9 This toothpaste exhibits good fluorine stability and vitamin F stability.

-46- [Example 8] Glycerin 15.0% Sorbitol 15.0 Propylene glycol 1.0 Polyethylene glycol 400 5.0 Carboxymethylcellulose Sodium-Rium 1.2 Carrageenan 0.
3. Xantanga 1. 0.2 1 Naccarin sodium 0.1 Lauryl sulfate 1.0 IT-stel in sucrose balmidine 1.0 (average esterification rα 1.3, palmitic acid content 95%) f kiss 1
Heranase 1.0 Vitamin F nicotinic acid ester 0.2 Kaori A 1.0 Aluminum hydroxide 5.0 Calcium hydrogen phosphate anhydrate 30.0-Heather - Total 100.0% -47- Calcium hydrogen phosphate・Properties of anhydrate: average crystallite
2520 density high density lx o, 6Fl/cm' Dynamic bulk density 0.86 II Tapping density 1.29 Blaine diameter 3,05μ Average particle diameter 13,6! I specific surface area 2.3 p/) This toothpaste had good foaming properties, as well as good Dextraner 1 stability and vitamin F stability.

[Example 91 Glycerin 25.0% Propylene glycol 2.0 Quinanthan gum 1.0 Satucalin sodium 0.2 Glycyllivonic acid potassium salt 0.01N-Lauroylsarcosine-1-0,3 lauroyldi]-tanolamide 0 .5- 48 - dinonyl sugar palmidine mono J stell 0.5 (average Nisderized J * 1.3. 95% palmitic acid silk) sucrose laurin di J stell 0.5 (average degree of esterification 1.8. lauric acid (Content: 65%) Monofluor An phosphate 0.76 Ranechirimic acid 0. 1 ri [1 Ruhexidine salt 1 ii 0.01 vitamin [resistant Fl! 2 Salt 0.1 Vitamin F Nicotinic acid Nissil 0.1 Flavor A
1.0 Silicic anhydride 2.5 Calcium hydrogen phosphate, anhydrate 40.0 Properties of calcium hydrogen phosphate, anhydrate: Average crystallite 2090 Static density 0.77 teeth/d Bulk density 0. 931! Tatuping V91! + mark 1.30 〃-49- Blaine diameter 3.95tt Average particle diameter 18.2! j Specific surface area 3.0 Go/9 This toothpaste had good foaming power and exhibited a stable foamed bamboo with a mild 41m feel. In addition, fluorine stability and vitamin F stability (t/Ib) are good.

[Example 10] Solubi 1--ol 35.0% Propylene glycol 2.0 Xanthan gum 1.0 Satucharin sodium 0.2 Lauryl sulfate, 1. O Gajutsu extract 0.01 Flavor A1.0 Tertiary phosphorus-based magnesium 1.0 Aqueous calcium phosphate, dihydrate 10.0 Calcium hydrogen phosphate, anhydrate 35.0- 50 - Calcium hydrogen phosphate, dihydrate Anhydrous properties: average crystallite
1640 Human static bulk density WIf 0.70i/am Dynamic bulk density 0.87 〃 Tapping density rci 1.20 〃 Blaine diameter 3.60μ Average particle diameter 12.9Il Specific surface + 1114. ．． 1, /7 This toothpaste 1 showed no discoloration even when gajutsu extract was blended, and showed a good stable blend. 1 "Example 111 Glycerin 10.0% Sorbitol 10.0 Propylene glycol 2.0 Carboxymethyl carrageenan 0.5 Natsukalinna 1 to Ryuhachi 0.1 Steviolide 0.01 Sodium lauryl sulfate 1.0 - 51 - Lauroirge Tanolamide 0.5 Dextraner L' 0.5 Mutanase 0.5 Citrus extract 0.01 Fragrance A 1.0 Silicic anhydride 2.0 Calcium hydrogen phosphate, anhydrous /15.0 Calcium hydrogen phosphate, anhydrous Properties of hydrate: average crystallite 2830
Human static bulk density 0.7. :l/cm" High density 0.89 Tapping density 1.18 Blaine diameter 3.30μ Average particle size 13.7!L Specific surface area 3.9I/cm This toothpaste contains gajutsu extract. There was no discoloration, and the enzyme stability was also good.

- 52 - [Example 121 Glycerin 30.0% Propylene glycol 2.0 Carpoxymable l? Ru 1-1-su sodium 1.3
11-Tucarinbotrium 0. 2 Lithium lauryl sulfate 1.5 L nofluorophosphate 1 Helium 0.76 Fragrance A 1
．． 0 Calcium hydrogen phosphate, anhydrate 50.0 Preservative Trace amount of calcium hydrogen phosphate, anhydrate Properties: Average crystallite
1650 Human Static Bulk Density 0.71 Fang/7 Dynamic Bulk Density 0.87〃 Tapping Density 1.20〃 Blaine Diameter 3.70μm 53 - Average Particle Size 12.7/I Specific Surface Area 2.7m/CI [Example 13] Glycerin 10.0% Sorbitol 10.0 Propylene glycol 2.0 Carpoxymethylcellulose sodium 0.7 Carrageenan 0.3 1 Natucarin sodium 0.1 Sodium lauryl sulfate 1.5 Monofluoroline i? I Butrium 0.76 Fragrance B
O.8 Magnesium hydrogen phosphate 2.0 Hydrogen phosphate 11, dihydrate 20.0 Calcium hydrogen phosphate anhydrate 25.0 Preservative Mildew-5/I - Calcium hydrogen phosphate Anhydrous properties: average crystallite
2510 Hasei bulk density 0.697/cn? Dynamic bulk density 0.90 〃 Tapping density 1.31 〃 Bu1nongko 3.30μ Average particle size 14. ．． 81f Specific surface area 2.7 m/1 [Example 14] Sorbitol 25.0% Propylene glycol 2.0 Sodium carboxymethyl cellulose Sodium saccharin 0.1 Sodium lauryl sulfate 1.5 Monoflu 71-ITI sodium phosphate 0.76 Flavor C1 .0 Tertiary magnesium phosphate 1.0 Calcium hydrogen phosphate, dihydrate 10.0 Calcium hydrogen phosphate, anhydrate 40.0- 55 - Preservative Properties of calcium hydrogen phosphate, anhydrate VI: Average crystallite 2 0 2 0 density high density a 0.76"i/c++ shear dynamic bulk density 0.89 Il Tapping tw degree 1.21 〃 Brain diameter 3.45f.z Average particle diameter 15.01f Specific surface V4 3.CW, 7g Example 15] Sorbitol 25.0% Propylene glycol 2.0 Carpoxymetallic acid sodium 1.1 Sodium saccharin 0.1 Notorium lauryl III!i acid 1.5 Monofluoroline Sodium acid 0.76- 56 - Kaori D 1, O Tertiary magnesium phosphate 2.0 Calcium hydrogen phosphate, anhydrate 45.0 Preservative Trace amount of calcium hydrogen phosphate, anhydrate 1 Quality: Average Crystallite 1240 static bulk density 0.52'iJ/am dynamic bulk density 0.651! Tapping animal Ira 0.94 Il Brain diameter 2.0011 Average particle (￥ 16.O1! 1 surface area 7.6'iJ/am) The toothpastes of Examples 12 to 1b all showed good fluorine stability.

[Example 161 Glycerin 15.0% Sorbitol 10.0 = 57- Propylene glycol 2.0 Carrageenan 1.0 Glycyrrhizin 0. 1 Sodium lauryl 5A acid 1.5 Sucrose palmitine mono-ster 1.0 Dextranase 2.0 Kori E1.0 Tertiary magnesium phosphate 1.0 Calcium hydrogen phosphate anhydrate 50.0 Preservative Trace amount 14 substances of calcium hydrogen phosphate anhydrate: Average crystallite 1510 Human static bulk density 0.50'i+/cn? Dynamic bulk density 0.62! ! Tapping secret i revenge 1.04! I brane diameter 1.65/l average particle diameter 3.91! -58- Specific surface area 5.1-+Tl'/9 This toothpaste showed good digitistranose stability.

[Example 171 Sorbi 1 Hele 20.0% Propylene Glycol 2.0 Carboxymethyl Celsus Deviolioid 0. 1 Glypuritin 0. 1 lauryl sulfate fat helium 1.5 t-nofluorophosphate 1 helium 0.76 fragrance ￥31
1yo 0. 8 Tokisenjumono 0. 1 Tertiary Magnesium Phosphate 1.0 Aqueous Calcium Phosphate Dihydrate 25.0 Calcium Hydrogen Phosphate Anhydrate 25.0 Preservative Trace amount 59- Properties of Calcium Hydrogen Phosphate Anhydrate: Average crystalline Child
2 0 8 0△ Static high density O. ; U2 'J/m dynamic bulk density tη 0. fi5 ++ Tapping density 1, 07Il Brane diameter 2. fiOμ Average particle size 8,51! Specific surface area 1.5m. , Q [Example 181 Glycerin 15.0% Sorbitol 10.0 Carbobol polyvinylpyrrolidone 0. 1 Glycyrrhibun 0.2 Sodium lauryl sulfate 0. 7 N-Lauroyl Dircosine t- 0.3 Toraneki 1J
Ill 0. 1 Fragrance E o. 8 Elm extract 0.05 - 60 - Ephedra extract 0.05 Grind supplement extract 0.05 Magnesium triphosphate 1.0 Calcium hydrogen phosphate dihydrate 10.0 Calcium hydrogen phosphate Anhydrate 40.0 Preservative Trace amount of calcium hydrogen phosphate/Anhydrate properties: Average crystallite
2350 people ML high density 0.4OL'cm dynamic volume density 0.50 〃 Tatsuhinku density 1! J O,82I! Blaine diameter 1.4μ Average particle diameter 11.1jj Specific surface area 5.1 residues/min [Example 19] Glycerin 20.0% 61- Sorbi 1--L 10.0 Ki) J-Ntan gum 1.0 Satsukarinna 1~Riu 80, 1 Glypuritin 0.1 Sodium lauryl sulfate 1.2 Lauricidin 0.1 Dextrana-121.0 Koban [g O,8 J: Mogi extract 0.1 Magnesium tertiary phosphate 1.0 Phosphorus Hydrogen Oxygen) J Lucium Dihydrate 40.0 Calcium Hydrogen Phosphate Anhydrate 10.0 Preservative Trace Properties of Calcium Hydrogen Phosphate Anhydrate: Average Crystallite
3110 Human static high density 0.78 cyf Dynamic bulk density 0.92 〃 -(i2 - Cod pink density 1.38 〃 Bu1none diameter 4.0μ Average particle size 10.3J Specific surface area 2.5　/fan [Example 201 Glycerin 25.0% Xanthan gum 1.0 Satucarinna 1-lium 0.2 Sodium lauryl sulfate 1.O N-rau [l yl sarcosinate 0.5 Sucrose monopalmitate 0.5 Monoflu A lophosphate Sodium 0.76 aroma E O,
8 Calcium hydrogen phosphate, anhydrous 50.0 Preservatives Trace amount of water removal 100.0% -63- Calcium hydrogen phosphate, anhydrate 1111jj: Average crystallite: 450. Bulk density: 0.32S? /ciff Dynamic bulk density 0.42 ll Tapping density tα 0.6/l I! Blaine diameter 1.00μ Average particle size 18.2jj Specific surface area 2B, 81d/teeth All toothpastes of Examples 17 to 20 contain plant extracts 1
) It shows good formulation stability with no discoloration (/1).

In addition, the toothpastes of Examples 1 to 20 all had: (b) good taste (11), and exhibited low abrasiveness and high purity.

-64-

Claims (1)

[Claims] 1. Contains calcium hydrogen phosphate anhydrate having crystallites with an average crystallite size of 300 to 3500 as measured by Xl11 diffraction measurement. toothpaste composition. 2. Calcium hydrogen phosphate anhydrate has a static bulk density of 0.
30 to 0.78 tusk/d, and 01 Takanashimaro is 0.40 to 0.78 tusk/d.
0.95'j/cnr, and the tapping density is 0.95'j/cnr.
60-1. /10 teeth/d, and the brane diameter is 1.0-
5.07, the average particle diameter is 1.0 to 30 μ, and the specific surface of Yuzu is 2.0 to 30 I/? by the BET method. The special feature is
F 3. Sucrose fat #hi1 as a surfactant! The dentifrice composition according to claim 1 or 2, which contains an ester. -1-4. The m-stone group acid according to claim 3, wherein the fatty acid group of the sucrose fatty acid ester has 12 or 14 carbon atoms and has an average degree of ethralization of 1.2 to 1.8. 5. The amount of sucrose fatty acid ester in the entire composition is 0.
Claim 3 or 4 which is 5 to 10%]m
The dentifrice composition described. 6. Add acylated amino acids or their salts using surfactants (
) (Dentifrice composition according to any one of claims 3 to 5). 7. Claims 1 to 6 containing vitamin E and/or stellate as an active ingredient. The dentifrice composition according to claim 7. 8. The dentifrice composition according to claim 7, which contains vitamin E nisder nicotinate as the ester of vitamin [9]. 10. A dentifrice composition according to any one of claims 1 to 6, which contains dextranase and/-2- or mutanase as an active ingredient.Fill 1
The dentifrice composition according to any one of items 6 to 6. 11. Claims 1+, ti 8 to 61) containing an active ingredient and an extract of a plant selected from 1 no. Claims 1 to 1 contain 1 of the dentifrice composition according to any one of J, 1 of sharari ingredients, 1 of f-men, 1 of f-men, and/or 1 to 1 of anene.
Toothbrushing composition 3゜ according to any one of item 11