JPS62287966A - Polishing base material - Google Patents

Abstract

PURPOSE:To obtain the low polishing-high cleaning effect of a polishing base material such as dentifrice and lapping agents by applying a baking process at 70-1,200 deg.C to calcium hydrogenphosphate anhydride containing crystallites of sizes within a predetermined value measured via an X-ray diffraction method. CONSTITUTION:Calcium hydrogenphosphate anhydride containing crystallites of such a mean size as 200-3,500 angstrom or preferably 300-3,000 angstrom measured via an X-ray diffraction method is baked at temperature of 700-1,200 deg.C, thereby forming a polishing base material. This base material is cracked into grains of suitable sizes so that a mean grain diameter measured via a laser beam scattering method will be 2-3mum or preferably 5-25mum. In this case, the material when used as a polishing agent of dentifrice composition, is baked at a temperature level of about 700 deg.C or below. For use as a lapping agent for an IC wafer and the like, the material is baked at a level over 700 deg.C. In this way, low polishing-high cleaning effect becomes available and the material so processed is stable and water suspension type, thereby enabling preventing the effluence of calcium ion as far as practicable.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention The present invention relates to an abrasive substrate that has low abrasion and high cleaning effects and is stable in a water suspension system. For this reason, the present invention relates to an abrasive base material that is suitably used as an abrasive for toothpaste and as a lapping agent for IC wafers, metals, etc.

[6] Hemolymphs - Conventionally, X
The average crystallite size measured by line diffraction is 30
Calcium hydrogen phosphate anhydrate consisting of 0 to 3,500 crystallites is known to be useful (Japanese Patent Application Laid-Open No. 188309/1983).

However, according to the studies of the present inventors, the average value of the crystallite size measured by X-ray diffraction method is 200 to 35.
Calcium hydrogen phosphate anhydrate, which consists of 0.00 crystallites, has a relatively high solubility in water, and has the problem of elution of calcium ions in an aqueous suspension system. If the value is less than 1000 Å, when added to toothpaste compositions, the surface of the particles will dissolve over time, and the cleaning power will decrease over time, resulting in low polishing.
In some cases, the high cleaning function was impaired.

The present invention was made in view of the above circumstances, and provides a polishing base material that has low polishing and high cleaning effects, is stable in an aqueous suspension system, and is prevented from elution of calcium ions by water as much as possible. The purpose is to

Means and Effect for Solving the Problem The inventors of the present invention have conducted extensive studies to achieve the above object, and have found that the average crystallite size measured by X-ray diffraction is 200 to 3SoO. A polishing base material obtained by firing calcium hydrogen phosphate anhydrate having crystallites at a temperature of 70'C to 1200°C has the properties of the original calcium hydrogen phosphate anhydrate impaired. without getting lost.

It has excellent low abrasiveness and high cleaning ability, has low solubility in water, and is stable for long periods even in aqueous suspension systems.
There is no inconvenience such as the particle surface dissolving over time and the cleaning power decreases, and even after long-term storage in an aqueous suspension system, it effectively exhibits low abrasive and high cleaning functions.Moreover, the calcium hydrogen phosphate anhydrous When the compound is fired at 350°C or higher, the resulting polishing base material has a very high pig-styling effect and imparts excellent gloss to the tooth enamel surface, and this polishing base material can be incorporated into toothpaste, etc. The inventors have found that the active ingredients can be stably blended, and the astringent taste and feeling of use can be improved.

Furthermore, when calcining calcium hydrogen phosphate anhydrate having crystallites with an average crystallite size of 200 to 3500 as measured by X-ray diffraction at a temperature of 70°C to 1200'c, The present invention was based on the discovery that the addition of a magnesium compound or an aluminum compound further improves the stability against water and more effectively achieves a stable combination of active ingredients.

The present invention will be explained in more detail below.

The polishing base material according to the present invention is made of calcium hydrogen phosphate anhydrate having an average crystallite size of 200 to 3,500 crystallites measured by X-ray diffraction at 70°C to
It is fired at a temperature of 1200°C.

Here, the calcium hydrogen phosphate anhydrate used in the present invention has an average crystallite size of 200 to 3,500 crystallites, but the cleaning power of the abrasive substrate of the present invention is particularly high when the average crystallite size is 300 to 3,000 crystallites. It is suitably used for the following reasons.

In addition, the calcium hydrogen phosphate anhydrate used in the present invention has a density of 2.500 to 2 at 20°C.
．． 885g/ad, and the specific surface area is 2.5 by BET method.
It is preferable that the average particle size is 2 to 30 particles, particularly 5 to 25 particles, as measured by a laser light scattering method.

Furthermore, the calcium hydrogen phosphate anhydrate used in the present invention has an average particle size of 0.03 to 5p.
Preferably, the plate-like crystals are fixedly aggregated. The average size of the secondary particles referred to herein is a value measured and calculated from an electron micrograph.

Among these, spherical calcium hydrogen phosphate anhydrate is particularly suitable.

Calcium hydrogen phosphate anhydrate having an average crystallite size of 200 to 3,500 people can be prepared using conventional methods, such as U.S. Pat. No. 2,287,699 (1942) and U.S. Pat.
No. 852 (1961), No. 3066056 (196
2), No. 3169096 (196'5), Special Publication Show 3
In the neutralization reaction between phosphoric acid and milk of lime described in 9-3272.3273, etc., a modifier is used to control the growth of crystals or to affect the crystal properties and the specific growth rate of individual crystal faces. It can be manufactured by adding. 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 is carried out during the neutralization reaction between phosphoric acid and milk of lime.

The amount of crystallizing agent added is 0.1 to 40% by weight of the produced calcium hydrogen phosphate anhydrate, especially 0.5 to 30% by weight.
It is preferable to express it in % by weight, and the larger the amount added, the more the growth of crystals is inhibited and the crystallites tend to become smaller. This calcium hydrogen phosphate anhydrate is manufactured by adjusting the amount, timing, speed, and concentration of the crystallizing agent added during the manufacturing process.

Various grades can be obtained by appropriately controlling the reaction temperature, reaction time, stirring speed, etc. For example, calcium hydrogen phosphate anhydrate used in the present invention can be suitably obtained by reacting a calcium compound mixed with an electrolyte and a phosphoric acid compound at a temperature of 50 to 90'C and adding a phosphoric acid condensate. be able to.

The polishing base material of the present invention has the above-mentioned average crystallite size of 2.
00-3500A calcium hydrogen phosphate anhydrate,
More preferably, a spherical shape is fired at a temperature of 70°C to 1200°C. The firing time is usually 1 minute to 2 minutes.
It is 4 hours.

Here, when the firing temperature is 70°C to 400°C and the firing time is 1 minute to 5 hours, the fired product is made of calcium hydrogen phosphate.
It is mainly composed of anhydrate.

Also, the firing temperature is 400℃~1200℃ and the firing time is 3 minutes~
In the case of 24 hours, the baked product will be mainly composed of calcium pyrophosphate. In this case, when using the abrasive base material of the present invention as an abrasive for toothpaste compositions, etc., it is preferable to use one that has been fired at 700'C or less (higher firing temperatures will increase the hardness of the fired product). On the other hand, when used for polishing and polishing the surfaces of IC wafers, metals, etc., it is preferable to use a material fired at 700° C. or higher.

Note that other firing conditions are not particularly limited, and for example, the firing atmosphere may be air or an inert atmosphere such as nitrogen or argon.

In addition, as mentioned above, the firing raw material is calcium hydrogen phosphate anhydrate with an average crystallite size of 200 to 3,500 people, and this can be obtained by the above-mentioned production method, but especially the above-mentioned production method. In this step, calcium compounds such as calcium oxide, calcium hydroxide, calcium carbonate, and calcium chloride and phosphoric acid compounds such as phosphoric acid, ammonium phosphate, and alkali metal phosphates are combined with pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, Polyphosphoric acids such as hexapolyphosphoric acid and decapolyphosphoric acid, these polyphosphoric acids and alkali metals and alkaline earth metals.

One or more types of crystallizing agents selected from phosphoric acid condensates such as salts with aluminum group and salts thereof are added in an amount of 0.1 to 50% by weight, more preferably 0.5 to 50% by weight in terms of CaO of the calcium compound. It is preferable to use calcium hydrogen phosphate anhydrate obtained by adding 40% by weight, more preferably 1 to 30% by weight and reacting at a temperature of 60° C. or higher as a firing raw material, and use such a firing raw material. By doing so, it is possible to reliably obtain a polished base material with a higher degree of roundness.

Furthermore, in the present invention, it is preferable to add a magnesium compound and/or an aluminum compound to the raw material calcium hydrogen phosphate anhydrate during firing, thereby obtaining a polishing base material that is more stable against water. It will be done. In this case, as the magnesium compound, one or more types of magnesium phosphate monobasic, magnesium phosphate dibasic, magnesium tertiary phosphate, magnesium chloride, magnesium sulfate, etc. can be used, but especially magnesium phosphate tribasic. As the aluminum compound, aluminum phosphate, aluminum silicate, etc. can be preferably used. The amount of these magnesium compounds and aluminum compounds used is 0 to 20% by weight, preferably 0.5 to 10% by weight, based on the raw material calcium hydrogen phosphate anhydrate.

After firing, it is crushed to an appropriate particle size depending on the purpose, but the average particle size measured by laser light scattering method is 2 to 30.
p, especially 5 to 25 p, is preferred as the polishing base material.

In this case, the average crystallite size, density, specific surface area, roundness, etc. of the polishing base material according to the present invention depend on the properties of the raw material calcium hydrogen phosphate anhydrate to be fired as described above. In particular, as the polishing base material of the present invention, the liquid absorption amount is 0.2 to 2.
mQ/g and a specific surface area of 2.5 to 50rd/g are preferred.

The polishing base material according to the present invention is suitably used as a polishing agent for oral compositions such as toothpaste compositions, a lapping agent for IC wafers and metal surfaces, and furthermore, spherical ones are suitably used as a lubricant, a fluidity improver, etc. .

In this case, when the polishing base material of the present invention is used for these purposes, various commonly used components can be used depending on the purpose. For example, when the abrasive base material of the present invention is incorporated into a dentifrice composition, thickeners, binders, surfactants, fragrances, sweeteners, preservatives, various active ingredients, etc. may be used, and if necessary, In addition to the invention polishing base material, other polishing agents are blended,
A dentifrice composition may be prepared.

Effects of the Invention The polishing base material of the present invention has high stability against water, and has low elution of calcium ions even in a water turbid system. Therefore, even after long-term storage in a water suspension system, the polishing substrate has low polishing and high cleaning performance. Demonstrate stable performance.

EXAMPLES Hereinafter, the present invention will be specifically explained by showing examples and comparative examples, but the present invention is not limited to the following examples.

Before explaining the Examples and Comparative Examples, examples of producing the calcium hydrogen phosphate anhydrate used in producing the base material of the present invention and the base material of the present invention will be shown.

[Production Example 1] Milk of lime is sieved through a 100-mesh sieve to remove coarse particles to obtain milk of lime containing 128 g/Q in terms of calcium oxide. Then, the 75% aqueous phosphoric acid solution IQ is heated to 78° C. and the milk of lime is added at a rate of 570° per hour while stirring. 60 minutes after the start of the neutralization reaction, 135 g of pyrophosphoric acid was added, followed by the addition of milk of lime, and the pH after the reaction was 6.
．． Continue until it reaches 0 (the total amount of added 7JUJ of milk of lime is 5.3Q.

The amount of pyrophosphoric acid added to 100 parts by weight of Ca O is 2
(equivalent to 0.0 part by weight). After that, 1 reaction solution was filtered,
After washing with water, the P mass is dried and crushed to obtain calcium hydrogen phosphate anhydrate.

[Production Example 2] Calcium hydrogen phosphate anhydrate obtained in Production Example 1 was fired at 450°C for 2 hours to obtain a polishing base material of the present invention.

[Production Example 3] Calcium hydrogen phosphate anhydrate obtained in Production Example 1 was fired at 700° C. for 2 hours to obtain a polishing substrate of the present invention (spherical calcium pyrophosphate).

[Production Example 4] Calcium hydrogen phosphate anhydrate 1 obtained in Production Example 1
00 parts by weight and 1 part by weight of tertiary magnesium phosphate were added and mixed, and the mixture was fired at 180° C. for 2 hours to obtain a polishing base material of the present invention.

[Experimental example/Comparative example I]

The polishing power (RD A value) and cleaning power of the polishing base material having the properties shown below were investigated by the following method. The results are shown in Table 1 and the drawings.

Danwang Ki Sumire A Calcium hydrogen diphosphate dihydrate (DCP-D) Average aggregate particle size 14pm B Calcium hydrogen diphosphate anhydrate (D CP-A)
Average crystallite size: 4550 people Average agglomerated particle size: 16% Density: 2.89g/a+? Specific surface area
1.2rn'/gC calcium hydrogen diphosphate
Anhydrate (in the above Production Example 1, the amount of pyrophosphoric acid added was Ca01
Calcium hydrogen phosphate anhydrate obtained by adjusting 20 parts by weight to 00 parts by weight) Average crystallite size 450 people Average aggregate particle size 23/a Density 2.60 g/aj Specific surface area
25 points/g D Calcium hydrogen diphosphate anhydrate (in the above Production Example 1, the amount of pyrophosphoric acid added was changed to CaO1
Calcium hydrogen phosphate anhydrate obtained by adding 5 parts by weight to 00 parts by weight) Average crystallite size 700 people Average agglomerated particle size 21p Density 2.84g/c+7 Specific surface area
g, 2m/g E: Polished base material C baked at 150°C for 2 hours.

(This polishing base material E essentially consists of calcium hydrogen phosphate anhydrate.) F: Polishing base material baked at 150° C. for 2 hours.

(This polishing base material F essentially consists of luciram hydrogen phosphate anhydrate.) G: Polishing base material C baked at 500° C. for 2 hours.

(This polishing base material G substantially consists of calcium pyrophosphate.) H: A polishing base material obtained by firing at 500° C. for 2 hours.

(This polishing base material H essentially consists of calcium pyrophosphate.) (1) = 100 parts by weight of polishing base material C was mixed with 1 part by weight of tertiary magnesium phosphate, and the mixture was fired at 150° C. for 2 hours.

J: 100 parts by weight of polishing base material C was mixed with 1 part by weight of tertiary magnesium phosphate and fired at 500°C for 2 hours.

K: 100 parts by weight of polishing base material C was mixed with 1 part by weight of aluminum phosphate and fired at 150"C for 2 hours.

L: Polishing base material C: 100 parts by weight to 1 part aluminum phosphate
Parts by weight were added and mixed and baked at 500°C for 2 hours.

M: Calcium pyrophosphate (conventional product) Among the properties mentioned above, the average crystallite size is measured by performing X-ray diffraction of the powder, and from the brushing of the peak, the crystallinity of the powder is determined by the crystallite size. was quantitatively expressed as an index. Here, xi'g is measured using α rays on Cu-, and the X-ray diffraction data is calculated using Scherrer's formula D=
The main peaks with no overlap were unraveled using λ/β cos θ, and the average crystallite size was determined. in this case,
The main peaks are 2θ=53.1' and 36.1°.

The average was taken for 32.6°, 30.25'', and 13.15', where D is the crystallite size.

λ is the measured X-ray wavelength C], β is the spread of the diffraction line (rad) purely based on the size of the crystallites (α-AI220° powder calcined at 1100°C for 24 hours was used as a reference) , K is the shape factor (constant = 0.9), θ is the Bragg angle of the diffraction line, and β is the value obtained from the experimentally determined half-value width by a material with very good crystallinity under the same conditions. This is the value obtained by subtracting the given half width.

In addition, the average aggregate particle size is Leed & North
rup particle size distribution measuring device (product name: Microtra)
c) (laser method).

Sadahisa Toyosara J, Dent, Res, Vol, 55. No.4,
563-573 by Hefferen.
ntin Abrasion) values were measured.

2) Watasa Sara Jojuku Collect cigarette tar in the usual way, apply it evenly on the tiles as a solution, heat and dry it, then set it in a polishing container and apply 5 g of the polishing base material. Using a suspension suspended in 15 g of a 60% glycerin aqueous solution containing 0.3% sodium carboxymethylcellulose, the tiles were brushed 2000 times at a load of 200 g, and the removal rate of tobacco tar from the tiles after polishing was visually evaluated.

In addition, as a brushing brush, there are 44 hairs,
A nylon (62) material with a bristles thickness of 8 mils (approximately 0.2 mm) and a bristles length of 12 mm was used, and the hardness of the material was M according to the Household Goods Quality Indication Law.

Evaluation criteria score 1: Tobacco tar removal rate 0~10% 2:
11-20% 3: 21-3o% 4: 31-40% 5: 41-50% 6: 51-60% 7: n 61-70% 8:
71-80% 9: 81-90% 10: 91-100% 1st
From the results shown in Table 1 and the drawings, it is recognized that the polishing substrate according to the present invention has a low polishing and high cleaning effect.

[Example/Comparative Example■]

The tooth enamel gloss improvement effect of the above-mentioned polishing substrates B, C, G, M and the following N was evaluated by the following method. The results are shown in Table 2.

Master 4 [Σ Polished base material C was fired at 900°C for 2 hours.

(This polishing base material N substantially consists of β-calcium pyrophosphate.) Average aggregate particle size: 25M Density: 3.09g/aj Specific surface area
A raw tooth cut into a size of 20g/g or 5mm x 5mm is embedded in resin.
The tooth enamel surface was smoothed with a rotary polisher, and then N
Gloss meter (Nippon Denshoku Kogyo Co., Ltd. (GLossMETERVG-10)
) The enamel surface was treated to a gloss level of 80.0±2.0.

Next, 5g of the polishing base material was mixed with 15i1 of a 60% glycerin aqueous solution.
1 was injected into a polishing container set with the above-mentioned natural tooth test piece, and brushed using a horizontal polishing tester under the conditions of a load of 200 g and 7000 strokes/40 minutes. The same brush as in Example I was used for brushing. After 7,000 strokes of brushing, the increase or decrease in gloss was measured using the gloss meter, and the difference from the initial gloss was defined as the degree of improvement in gloss, which was evaluated based on the following evaluation criteria.

O: Gloss improvement degree +20 or more 0: II +15 or more + less than +20 X:
# Less than +15 In this case, the level that is visually recognized as sufficiently glossy is +20 or higher, and the level that is recognized as glossy is +15.
That's all.

Table 2 From the results shown in Table 2, it is recognized that the polishing substrate according to the present invention has an excellent gloss improvement effect.

[Example, comparative example ■]

After suspending 5 g of the polishing base material shown in Table 3 in 50 - of water and leaving it in a constant temperature bath at 20°C for 3 days,
The amount of calcium ions eluted from each polishing substrate was evaluated by passing it through paper and measuring the amount of calcium ions in the P solution by atomic absorption spectrometry.

The results are shown in Table 3.

Table 3 From the results shown in Table 3, the polishing base material according to the present invention has a water content of 1! i:
It is observed that the elution amount of Ca'' is small in the IIA system.

[Examples, comparative examples ~]

A toothpaste with the following formulation using the abrasive base material shown below was prepared, and after storing it at 40° C. for a predetermined period, the cleaning power was examined by the following method to evaluate the stability of the cleaning effect over time.

The results are shown in Table 4.

Higashi-Nori i-yu polishing base material 3o, 0%
Amorphous research silica 5.0 Sodium carboxymethyl cellulose 1.0 Colloidal silica 1.5 Propylene glycol 2.0 Glycerin 18.0 Sodium lauryl sulfate 1.5 Sodium saccharin 0.1 Fragrance
1.0 Preservative Trace amount of sodium monofluorophosphate o, 7410
0.0% The 111 BeniO Calcium Hydrogen Diphosphate Anhydrate (In the above Production Example 1, the amount of pyrophosphoric acid added was changed to CaO1
Calcium hydrogen phosphate anhydrate obtained by adding 10 parts by weight to 00 parts by weight) Average crystallite size 540 people Average agglomerated particle diameter 25% Density 2.70 g/aJ Specific surface area 18rrr/gP= Polishing base material 0 to 1
Baked at 50℃ for 2 hours.

(This polishing base material 0 essentially consists of calcium hydrogen phosphate anhydrate.) Q: Polishing base material O is baked at 500° C. for 2 hours.

(This polishing base material Q essentially consists of calcium pyrophosphate.) R: 1 part by weight of tertiary magnesium phosphate was added to and mixed with the 0100-weight part of the polishing base material, and the mixture was fired at 500°C for 2 hours.

S: 1 part by weight of aluminum phosphate was added to 100 parts by weight of the polishing base material, and the mixture was baked at 500°C for 2 hours.

The procedure was the same as in Example I except that 10 g of toothpaste was suspended and dispersed in a 60% glycerin aqueous solution as the suspension.

Table 4 From the results shown in Table 4, it is recognized that the polishing substrate according to the present invention has good stability over time in an aqueous suspension system.

Examples of use of the polishing base material of the present invention will be shown below.

[Use Example 131C Polishing composition for sea urchins, polishing substrate of the present invention, 2o% polyvinyl alcohol
4 〃Propylene glycol 10 /I ethylene glycol 10 〃Water
Remaining 100.0% by weight [Usage Example 2] Polishing composition for metals Polishing base material of the present invention 10% by weight Nonionic activator 5 Sodium polyacrylate
3n water
Residue

[Brief explanation of drawings]

The drawing is a graph showing the relationship between the polishing power and cleaning power of various polishing substrates.

Claims (1)

[Claims] 1. Calcium hydrogen phosphate anhydrate having crystallites with an average crystallite size of 200 to 3500 Å measured by X-ray diffraction at a temperature of 70°C to 1200°C. An abrasive base material characterized by being made by firing. 2. Density of calcium hydrogen phosphate anhydrate is 2.50
0 to 2.885g/cm^3, and the specific surface area is BET
2. The polishing substrate according to claim 1, which has an average particle size of 2.5 to 50 m^2/g and an average particle size of 2 to 30 μm. 3. The polishing base material according to claim 1 or 2, which is obtained by adding a magnesium compound and/or an aluminum compound to calcium hydrogen phosphate anhydrate and firing the mixture.