Note: Descriptions are shown in the official language in which they were submitted.
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TITLE OF THE INVENTION
AGENT FOR REMOVING CALCIUM COMPOUNDS AND THE LIKE
FIELD OF THE INVENTION
The present invention relates to agents capable of
removing deposits or accumulations mainly containing
calcium compounds and associated other mineralized
compounds by dissolving.
BACKGROUND ART
Dental caries is thought attributable to
Streptococcus mutans growing on food particles remaining in
the oral cavity after meals and consequently producing
acids, which dissolve the enamel surface of teeth. On the
other hand, the remaining food particles decomposed by oral
microorganisms which predominantly include Streptococcus
mutans form dental plaque , which adheres to the surfaces of
teeth and is converted into dental calculus with time.
Dental calculus consists mainly of inorganic
mineralized salts contained in saliva and deposited on the
surfaces of teeth, and of organic substances derived from
saliva, bacteria and food particles. Dental calculus
contains 82 . 9~ ( by weight , the same as hereinafter ) of
inorganic substances including 30.72 of calcium, 16.85 of
phosphorus , 1 . 044 of magnesium, 0 . 0196 of iron and 1 . 393
of carbonic acid. The calculus contains 8.34 of proteins
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( including keratins , mucins and nucleoproteins ) and 2 . 7~ of
fats . The calculus also contains trace amounts of metals
such as; copper, silver, sodium, tin, zinc, aluminum,
barium, strontium and chromium, according to Encyclopaedia
Chimica (Kyoritsu Shuppan Co., Ltd., Japan). The main
component of the dental calculus is calcium phosphate of
apatite-type structure as is found in those of teeth and
bones.
The mechanism of dental calculus formation is 1 ) the
remaining food particles involved by oral microorganisms and
2)consequently deposited calcified mineral compoundsfrom
saliva. Dental calculus also contains magnesium compounds
in amounts considerably smaller than those of calcium
compounds.
"Dental spittoon" and a drainpipe connected thereto
in the dental unit are used for a long period. Deposits of
calcium and magnesium compounds and accumulation of
non-calcified organic materials , which are generally
referred to "scale" , are adhered on surfaces of the
drainpipe. It needs common practice to periodically clean
the pipe with chemical agents; hydrochloric acid, sulfuric
acid or strong acids , or caustic soda or like strong alkali or
with a chlorine compounds, to flow into the pipe and to
exclude the deposit or accumulation for decomposition.
For removing the scales with such chemicals , it not
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only deteriorates the drainpipe but also entails the problem
that the waste water resulting from cleaning gives rise to
environmental pollution. Furthermore, some chemicals used
in combination are likely to evolve noxious chlorine gas .
Dental calculus is formed also on dentures surface
through the same mechanism as described above. Removing
calculus from the denture is the same manner as tooth
brushing, using an abrasive material in the past as
mechanically scrubbing off the calculus compounds . It is
recently used in general practice the immersed denture in a
cleaning solution, then thoroughly wash the denture with
water and set the denture in the oral cavity. However, the
denture cleaning agent could exclude lipids and proteins and
has no or little effect to remove calcium compounds .
The conventional denture cleaning agent is adapted
to exhibit cleaning ability by the combination of the
bleaching effect of oxidizer, cleaning effect of surfactant,
substrate decomposing effect of enzyme, cleaning and
decomposing effect of alkali , cleaning assisting effect of
chelating agent , stirring effect due to bubbling, etc . The
oxidizer having a bleaching effect or the alkali serving as a
cleaning agent , if used for long times , showed the occurrence
of discoloring and deteriorating the polymethyl
methacrylate resin and ceramic materials which are usually
used as dental materials .
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Since urine contains high amounts of calculus
consisting mainly of inorganic compounds , such as calcium
oxalate, the toilet bowl for use in daily and the drainpipe or
the like connected thereto have the problem of calcium
deposition on the inner wall of the pipe during a long period
of use as seen the same in the drainpipe of the dental
equipment.
An object of the present invention is to provide an
agent for effectively removing deposits comprising
substances discharged from the living body, especially
deposits containing calcium and magnesium compounds.
The removing agent of the present invention is
useful for cleaning dentures and also suitable for use in
dental spittoon and drainpipes connected thereto, toilet
devices and drainpipes connected thereto, and various
drainpipes installed in the transportation means such as
trains , vessels and aircraft , i . a . , for uses involving the
necessity of removing scale containing calcium compounds or
magnesium compounds and deposited on inside of pipe walls .
SUMMARY OF THE INVENTION
The present invention provides an agent for
removing calcium compounds and magnesium compounds, the
agent being a composition comprising at least a
hydroxycarboxylic acid and a sulfamic acid.
The agent of the invention for removing calcium
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compounds and magnesium compounds comprises a base
composition containing at least a hydroxycarboxylic acid and
a sulfamic acid and is prepared by mixing 5 to 100 parts by
weight of a binder with 100 parts by weight of the base
composition, and shaping the resulting mixture.
The hydroxycarboxylic acid to be used is , for
example, at least one acid selected from the group consisting
of glycolic acid, malic acid, lactic acid, tartaric acid,
citric acid, hydroacrylic acid, alpha-hydroxybutyric acid,
glyceric acid, tartronic acid, salicylic acid,
m-hydroxybenzoic acid, p-hydroxybenzoic acid, gallic acid,
mandelic acid and tropic acid.
The sulfamic acid to be used is , for example ,
amidosulfamic acid.
DETAILED DESCRIPTION OF THE INVENTION
A detailed description is stated below of the
removing agent of the invention containing at least a
hydroxycarboxylic acid and a sulfamic acid.
The term "hyroxycarboxylic acid" refers to acids
including an alcoholic hydroxyl group and a carboxyl group in
the molecule, such as aliphatic carboxylic acids including
glycolic acid, malic acid, lactic acid, tartaric acid,
citric acid, hydroacrylic acid, alpha-hydroxybutyric acid,
glyceric acid and tartronic acid; and aromatic carboxylic
acids including salicylic acid, m-hydroxybenzoic acid,
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p-hydroxybenzoic acid, gallic acid, mandelic acid and tropic
acid. The acid used is not limited to these examples.
These carboxylic acids can be used singly, or at
least two of them are usable when so desired.
Incidentally, the hydroxycarboxylic acid to be used
can be any of levorotatory, dextrorotatory and racemic
compounds with respect to the optical activity thereof .
Levorotatory hydroxycarboxylic acids are naturally
available and are therefore more preferable.
The sulfamic acid used is, for example,
amidosulfamic acid. The N-alkyl and N-aryl derivatives of
the amidosulfamic acid, which are highly soluble in water,
are desirable to use. Such sulfamic acids are usable also
singly, or at least two of them are usable when so desired.
The acids to be used in the present invention are
those safe to use for a long period of time, preferably those
which are solid at room temperature, and more preferably
those resembling naturally productive acids in chemical
structure and highly biodegradable.
The hydroxycarboxylic acid and the sulfamic acid
are used preferably in a ratio by weight of 1: 9 to 9 : 1, and
more preferably 1: 9 to 7: 3.
The removing agent of the present invention can be
used in the form of an aqueous solution or a powder, whereas
when shaped into suitable forms of various sizes , the agent
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is adjustable in the dissolving-out concentration of the
effective component and life.
The agent can be prepared in the shaped forms by
mixing a powder of hydroxycarboxylic acid with a powder of
sulfamic acid to obtain a basic composition, mixing 5 to 100
parts by weight of a binder powder with 100 parts by weight of
the basic composition substantially uniformly, and shapes
for the mixture as desired by a tableting machine .
Examples of binders usable are carboxymethyl-
cellulose (CMC), sodium carboxymethylcellulose (CMC-Na),
polyvinyl pyrrolidone (PVP), hydroxypropyl cellulose (HPC),
hydroxypropyl methylcellulose (HPMC), methylcellulose
(MC), hydroxypropyl starch (HPS), and similar carbohydrates
or organic polysaccharide, although not limitative. These
binders have activity to retard the dissolving of
hydroxycarboxylic acid and sulfamic acid in water, such that
the time taken for these acids to dissolve in water can be
controlled as desired by varying the amount of binder to be
used.
It is desirable to use the basic composition in the
form of a powder or aqueous solution without the binder when
it is required to produce an immediate effect on the
substances to be removed (calcium compounds and/or magnesium
compounds).
On the other hand, it is desired to shape the agent
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in the form of blocks and masses if these substances are to be
dissolved slowly over a considerable period of time or to
permit the agent as shaped to retain its efficacy for a
predetermined period of time . For example , in the case where
the agent is shaped into pills , use of a larger number of
smaller pills results in a larger area of contact with water,
produces a greater efficacy but entails a shorter service
life than the use of a smaller number of larger pills if the
same amount of the agent is used. Thus, the form of the agent
and the size of the agent as shaped are determined suitably in
accordance with the purpose of use .
The removing agent of the present invention can be
used in combination with the components of conventional
cleaning agents, such as oxidizer, surfactant, enzyme,
chelating agent , etc . when so required.
The present invention is described below with
reference to specific examples .
Preparation of Samples
[Invention Example 1]
A 10 g of L-malic acid and 10 g of citric acid as
hydroxycarboxylic acids and 5 g of amidosulfamic acid as a
sulfamic acid were dissolved in 500 ml of distilled water to
obtain a sample of the invention .
[Invention Example 2]
A 100 g of L-malic acid and 50 g of citric acid as
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hydroxycarboxylic acids , 10 g of amidosulfamic acid as a
sulfamic acid and 18 g of carboxymethylcellulose as a binder
were thoroughly mixed together and made into tablets with a
diameter of 5 mm to obtain a sample of the invention .
[Comparative Example 1]
A commercially available cleaning agent for
dentures was prepared as the sample of Comparative Example 1,
the agent comprising 20 wt. $ of potassiummonosulfate, 40
wt . ~ of sodium perborate , 10 wt . ~ of sodium pyrophosphate , 3
wt . ~ of a protease , 5 wt . ~ of sodium dodecylbenzene-
sulfonate , 10 wt . ~ of sodium hydrogencarbonate and 12 wt . ~
of sodium sulfate .
[Comparative Example 2]
A commercially available cleaning agent for dental
spittoon and drainpipes was prepared as the sample of
Comparative Example 2. The sample solution contained a
lipase, sodium hydrogencarbonate, tartaric acid, sodium
hydrogentartrate, sodium carbonate and N-acylamino acid as
main components.
Experiments
[Experiment 1]
Calcium phosphate tablets were made, 5 mm in
diameter, using a tableting machine.
The 10 tablets of calcium phosphate were placed into
3 of 500 ml beakers , and the experimental solutions of
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Invention Example 1 and Comparative Examples 1 and 2 were
employed, each of 100 ml , into the beakers . Calcium
phosphate tablets for alterations in those solution were
examined at the room temperature .
[Experiment 2]
Calcium carbonate tablets were made, 5 mm in
diameter, using a tableting machine.
Ecperimenal design was the same as Experiment 1 to
check the calcium carbonate.
[Experiment 3]
Calcium oxalate tablets were made, 5 mm in diameter,
using a tableting machine.
Calcium sulfate tablets were evaluated in the same
manner as Experiment 1 .
[Experiment 4]
Calcium sulfate tablets were made, 5 mm in diameter,
using a tableting machine.
Changing patterns of the calcium sulfate tablets
were observed in the same manner as Experiment 1.
Incidentally, with reference to the experiments 1
to 4, calcium phosphate, calcium carbonate, calcium oxalate
and calcium sulfate were purchased from Wako Junyaku Co. ,
Ltd. in Japan.
[Experiment 5]
About 100 g of solid plaster of Paris were kept to
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remain in a drain trap , and 180 ml of the sample solution of
Invention Example 1 was passed through the trap. Changes of
plaster of Paris were observed. Experiments were conducted
also in the samples of Comparative Examples 1 and 2 as the
same manner of Invention Example 1 for changes of plaster of
Paris.
[Experiment 6]
Three test pieces (approximately 1 x 1 x 0.2 cm) of a
metal alloy (cobalt, nickel, gold, silver, platinum ) ,
widely used for dentures were prepared, exposed to flames for
a color change to black, oxidation of metal surface. The
test pieces were placed into three 100-ml beakers,
respectively, and they were checked for color changes in
oxidized film in the sample solutions of Invention Example 1,
and Comparative Examples 1 and 2 ( each 50 ml ) .
[Experiment 7]
Dentures with dental plaque and calculus deposited
on the surface of dentures were immersed in the sample
solutions of Invention Example 1 and Comparative Examples 1,
and checked for changes in the deposits . The plaque contains
organic substances including fats and proteins, while the
calculus contains magnesium compounds in addition to calcium
compounds.
[Experiment 8]
About 100 g of human discharges deposited on toilet
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bowls were given, then immersed in 180 ml of the sample
solution of Invention Example 1 and tested for changes .
[Experiment 9]
Four tablets of the sample of Invention Example 2
and four tablets of calcium phosphate prepared in Experiment
1 were placed in a dental spittoon, and water was passed
through the spittoon at a rate of 50 ml/min for 1 hour. The
tablets of the sample and the calcium phosphate were then
checked for the weight loss .
[Experiment 10]
Eight tablets of the sample of Invention Example 2
were placed into each of a vacuum strainer of a dental unit
and a spittoon, water was continuously passed through each
device at a rate of 50 ml/min, and drainpipes connected to the
strainer and the spittoon were checked for changes in the
scale (containing calcium compounds and magnesium
compounds ) deposited on the pipe inner wall .
Experimental Results
Table 1 shows the results of Experiments 1 to 10.
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The results of Experiments 1 to 5 reveal that the
sample solution of Invention Example 1 is effective for
removing various calcium compounds , but that the sample
solutions of Comparative Examples 1 and 2 are almost
ineffective for removing calcium compounds.
The result of Experiment 6 indicates that the sample
solution of Invention Example 1 has an effect to remove the
metal oxide film.
With reference to the result of Experiment 7 , the
sample solution of Invention Example 1 and Comparative
Example 1 are comparable in the effect of removing fats and
proteins in the dental plaque . Although Invention Example 1
shows an effect to remove calcium compounds as of calculus ,
Comparative Example 1 was found almost ineffective in this
respect . The effect of Invention Example 1 to remove dental
plaque is thought attributable to the destruction of various
bacteria present in the plaque . The removing agent of the
present invention inhibits the growth of plaque, when used
for cleaning dentures periodically. The agent of the
invention is expected to diminish the formation of dental
calculus.
The result of Experiment 8 indicates that Invention
Example 1 is effective for decomposing the urine discharges
deposited on the toilet bowl. The deposit consists
predominantly of organic substances resulting from
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decomposition with bacteria and calcium deposits. This
indicates that the sample solution of Invention Example 1 has
an effect to exclude such soiled materials .
Experiment 9 shows that the sample solution of
Invention Example 2 containing a binder dissolved in water as
delayed, indicating that only the dissolved portion
contributed to the removal of calcium phosphate .
The result of Experiment 10 reveals that the sample
solution of Invention Example 2 was gradually dissolved with
water, gradually removing the scale (containing calcium
compounds and magnesium compounds) deposited on the
drainpipe inner wall.
The removing agent of the present invention is
recognized to capable of dissolving calcium compounds almost
completely ( see Experiments 1 to 5 ) .
Thus , the removing agent of the present invention is
effective for dissolving not only calcium compounds but also
magnesium compounds ( see Experiments 7 and 10 ) because both
calcium and magnesium are elements included in alkaline
earth metals and similar in chemical properties .
The removing agent of the present invention
characteristically consists of compounds with highly
biodegradable and is excellent in amenability to
environments and therefore suitable for excluding solid
materials in the inner wall of the drainpipes including those
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for dental unit, toilet drainpipes, drainpipes in operating
rooms and supply rooms of hospitals , and drainpipes in
trains , vessels , aircraft and like transporation means , and
also for removing filthy adhesives in various apparatus in
the field of chemical industry power generator equipment ,
heat exchangers and so on, which are associated with calcium
and mineralized deposits.
The agent of the invention for removing calcium
compounds and the like also acts to destroy organic
substances produced by bacteria, is therefore capable of
effectively removing both plaque and calculus , and is more
advantageous to use as a denture cleaning agent than
conventional agents.
For removing dental calculus containing calcium
compounds firmly deposited on the walls of drainpipes , it was
conventionally used with a strong acid solution which is some
difficult to handle in the safety use or which possibly
occurs erosion or corrosion to metals of the drain pipes ,
whereas the removing agent of the present invention is
adequately usable with safety and without metal corrosion.
The agent of the present invention has also activity
to dissolve organic substances including fats and proteins
and is therefore suitable for use as an agent for removing
deposits or accumulations of such organic substances in
drain pipes.
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The removing agent of the invention also has an
effect to remove metal oxide films and is suitable for use as
a cleaning agent for various drainpipes .
The embodiment described above is intended to
illustrate the present invention and should not be construed
as limiting the invention set forth in the appended claims .
It should be understood that various modifications can be
made within the scope of the claims .
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