JP5653550B1 - Neutralization promoting ion sustained release dental film - Google Patents

Abstract

[PROBLEMS] To promote salivation or to gradually release calcium ions and phosphate ions into the oral cavity, which is useful for promoting remineralization of the tooth, but the recalcified tooth is the original hydroxyapatite. However, it is not desired to improve acid resistance. The present invention relates to a neutralization-promoting ion sustained-release dental film in which an ion sustained-release glass (a) contains an ion sustained-release glass that releases fluoride ions, strontium ions, and borate ions. The problem can be solved by sticking in the mouth. [Selection figure] None

Description

The present invention relates to a neutralization-promoting ion sustained release dental film containing an ion sustained release glass that continuously and slowly releases ions. The oral environment can be sounded by applying or sticking the neutralization-promoting ion sustained-release dental film to oral tissues such as dentin, tongue, palate, or prosthetic devices such as dentures.

In the oral cavity, when "decalcification" in which calcium ions and phosphate ions are eluted from the tooth substance (hydroxyapatite) and "calcification" in which calcium ions and phosphate ions are taken into the tooth substance are in an equilibrium state, the tooth substance Is kept healthy. However, if the oral cavity inclines to acidity due to the attachment of food or drink or plaque (food residue, exfoliated mucous membrane, etc.), the equilibrium relationship between demineralization and calcification is lost, and demineralization becomes advantageous. Ions elute excessively and progress to caries. Saliva plays a very important role in this equilibrium reaction. Since saliva has calcium ions and phosphate ions, it works in the oral cavity so that calcification is dominant. Furthermore, saliva has the ability to buffer to neutrality when the oral cavity is inclined to acidity because its components bicarbonate, phosphate, and protein have acid neutralizing ability. That is, the saliva protects the tooth from demineralization by both the effects of calcium ion and phosphate ion supply and acid buffering ability. However, since the ion supply capacity and the acid buffer capacity are limited, a material having tooth denaturation or acid buffer capacity has been demanded.

In general, it is widely known that active application of fluoride to a tooth is effective in preventing dental caries. Fluoride ions are taken into the tooth to form fluoroapatite, which contributes to improving the acid resistance of the tooth and leads to prevention of dental caries. Therefore, materials such as dentifrices or fluorine coatings containing fluoride salts are widely used for the purpose of preventing dental caries.

On the other hand, it is also known that saliva has the ability to suppress bad breath. The root cause of unpleasant bad breath is due to methyl mercaptan, hydrogen sulfide, etc., which are generated when bacteria are decomposed by bacteria. Saliva contains antibacterial substances such as lysozyme, lactoperoxidase, lactoferrin, and secretory immunoglobulin A, and can suppress bacterial growth. If dry mouth persists due to xerostomia (dry mice), physiological factors (temporary decrease in salivary secretion during sleep, etc.), side effects of drugs, etc., the effect of inhibiting bacterial growth by saliva cannot be obtained. Therefore, the bacteria in the oral cavity grow and the bad breath becomes obvious. Saliva has the ability to suppress bacterial growth as well as the maintenance of dentine such as decalcification and calcification, and is essential for maintaining the oral environment in a healthy state.

Patent Document 1 describes an oral care composition expected to prevent bad breath. An oral fragrance composition having a masking effect against bad breath and excellent in refreshing feeling and refreshing feeling is disclosed. An oral fragrance composition containing one or more fragrances selected from the group consisting of a flavor having a mint note, a flavor having a film lath note and a flavor having a fruit note as an active ingredient has excellent palatability and bad breath It is excellent in masking and has an excellent effect that can give a comfortable feeling to the user. However, it only makes it difficult to detect bad breath by the flavor, and does not fundamentally solve the cause of bad breath.

In Patent Document 2, as an invention capable of fundamentally solving bad breath, two or more kinds of bad breath reducing active ingredients and flavors selected from oct-2-ynoic acid methyl ester, non-2-ynoic acid methyl ester and the like are disclosed. An oral care product containing ingredients to prevent bad breath is disclosed. By blending a bad breath reducing active ingredient and inhibiting the production of methyl mercaptan and hydrogen sulfide by bacteria, unpleasant bad breath can be prevented only with a flavor composition that does not have an intense flavor. However, although the possibility of suppressing bad breath is suggested, there is no description on improving acid resistance of the tooth.

Patent Document 3 discloses an oral care product containing methylglyoxal (hereinafter referred to as MGO) and cyclodextrin. The bactericidal effect of MGO can effectively exert an antibacterial action against periodontal disease-causing bacteria such as P. gingivalis and F. nucleatum. Furthermore, by using α-cyclodextrin in combination, the antibacterial effect of MGO is improved, and a bactericidal / sterilizing effect can be expected in the treatment of periodontitis. In addition, when a polysaccharide-degrading enzyme or a proteolytic enzyme is added at the same time, the antibacterial composition acts directly on the bacteria, and plaque and tongue coating can be removed, thereby suppressing bad breath. However, although the possibility of suppressing bad breath is suggested, there is no description on improving acid resistance of the tooth.

Patent Document 4 discloses an edible film for oral hygiene that suppresses bacterial growth by promoting saliva secretion. An edible film for oral hygiene in which an organic acid, particularly citric acid, tartaric acid, fumaric acid, malic acid, succinic acid, and lactic acid is blended as a base material for promoting saliva secretion is exemplified. When an edible film containing the organic acid is affixed to an elderly person who is deficient in saliva secretion or a patient suffering from dry mice, saliva secretion is promoted and an effect of inhibiting bacterial growth is expected. However, when saliva secretion is normal, a great effect cannot be expected.

Patent Document 5 discloses an oral care product that contributes to remineralization of teeth and improvement in acid resistance. Solid oral composition comprising calcium-containing component, fluorine-containing component and phosphate, calcium ion sustained release from calcium-containing component, fluoride ion sustained release from fluorine-containing component, phosphate It can be expected that dental minerals will be remineralized and acid resistance will be accelerated by phosphate ions released slowly from the surface.

JP 2004-018431 A Special table 2009-506082 JP2013-184971 JP2007-326808 JP 2002-167318 A

Although the conventional techniques for promoting salivary secretion or the sustained release of calcium ions and phosphate ions in the oral cavity are useful for promoting remineralization of the tooth, the recalcified tooth is not the original hydroxy. It is only reformed to apatite, and no improvement in acid resistance is desired. An oral care composition that gradually releases fluoride ions is excellent in that acid resistance is improved by forming fluoride apatite by taking in fluoride ions that are released slowly from the composition. However, since there is a calcium ion source and a fluoride ion source in the oral care composition, as a result of water being taken into the oral care composition, immediately after the calcium ions and fluoride ions are dissolved. Since a poorly soluble calcium fluoride salt is formed, it was a problem that the effect of improving acid resistance could not be sufficiently obtained.

As a result of intensive studies to overcome the above-mentioned problems, the present inventors have found that when the dental film of the present invention is applied to an oral tissue or a prosthetic device by including an ion sustained-release glass in the dental film. As a result, the present inventors have completed the present invention by finding the acid buffering ability and the acid resistance of the tooth. That is, the present inventors provide the following inventions.
Specifically, it is a neutralization-promoting ion sustained release dental film having a thickness of 15 μm to 500 μm, which includes an ion sustained release glass (a) and a non-polymerizable film forming material (b).
The ion sustained-release glass (a) is preferably an ion sustained-release glass that releases fluoride ions and further releases one or more kinds of ions among divalent to tetravalent ions.
It is preferable that the ion sustained-release glass is an ion sustained-release glass that releases fluoride ions and further releases one or more kinds of ions from strontium ions, aluminum ions, and borate ions. Furthermore, it is preferable to gradually release at least fluoride ions, strontium ions, and borate ions.

Improvement of acid resistance of teeth by divalent to tetravalent ions sustainedly released from ion sustained release glass used in the present invention, acid neutralization in the oral cavity, and acid resistance of teeth by sustained release of fluoride ions Improvement in sex is expected.
Fluoride ions that are slowly released from the ion-release glass are taken into the tooth and form fluoroapatite, thereby improving acid resistance. Strontium ions are also taken into the tooth and form strontium apatite. Since the acid resistance of strontium apatite is higher than that of hydroxyapatite, it is expected that the acid resistance of the tooth will be improved by the sustained release of strontium. In addition, strontium ions have an acid neutralizing ability to shift to neutrality when the surrounding oral environment is inclined to acidity. In other words, it was found that the improvement of the acid resistance of the tooth and the transition of the oral environment to neutrality can be achieved simultaneously by the synergistic effect of strontium ions and fluoride ions, and the present invention has been completed. Furthermore, unlike the elution of ions from the salt compound, since ions are sustainedly released from the glass skeleton, counter ions do not exist in the vicinity, and inhibition of the sustained ion release due to salt formation does not occur, so that stable ion sustained release can be achieved.

Another action of the present invention is to maintain the oral environment in a good state by the bacteriostatic action of borate ions that are released from the sustained-release glass. It is expected to suppress the growth of bacteria that produce methyl mercaptan and hydrogen sulfide, which are the cause of bad breath, by the bactericidal effect of borate ions that are gradually released from the sustained-release glass. That is, since the growth of bacteria in the oral cavity is suppressed, prevention of bad breath is expected.

The neutralization-promoting ion sustained-release dental film of the present invention contains an ion sustained-release glass, and ions based on the glass composition are sustainedly released from the glass.

The ion sustained-release glass used in the present invention can be used without any limitation as long as it contains one or more glass skeleton-forming elements that form a glass skeleton and one or more glass-modifying elements that modify the glass skeleton. . In the present invention, an element that can be a glass skeleton forming element or a glass modifying element depending on the glass composition, so-called glass amphoteric element, is included as a category of the glass skeleton forming element. Specific examples of the glass skeleton-forming elements contained in the sustained-release glass include silica, aluminum, boron, phosphorus and the like, but they can be used alone or in combination. Specific examples of glass modifying elements include halogen elements such as fluorine, bromine and iodine, alkali metal elements such as sodium and lithium, alkaline earth metal elements such as calcium and strontium, etc. In addition to the above, a plurality can be used in combination. Among these, it is preferable to include silica, aluminum, and boron as glass skeleton forming elements, and fluorine, sodium, and strontium as glass modifying elements. Specifically, silica glass including strontium and sodium, fluoroaluminosilicate glass, Examples thereof include fluoroborosilicate glass and fluoroaluminoborosilicate glass. Further, from the viewpoint of sustained release of fluoride ions, strontium ions, aluminum ions, and borate ions, more preferred is fluoroaluminoborosilicate glass containing sodium and strontium, and the glass composition range is SiO2 15-35 mass%. Al2O3 15-30% by mass, B2O3 5-20% by mass, SrO 20-45% by mass, F 5-15% by mass, Na2O 0-10% by mass. This glass composition can be confirmed by using instrumental analysis such as elemental analysis, Raman spectrum, and fluorescent X-ray analysis. However, if the measured values by any analytical method match these composition ranges, there is no problem. Absent.

There is no restriction | limiting in particular in the manufacturing method of these glass, It can manufacture by manufacturing methods, such as a melting method or a sol-gel method. Among these, a method of producing by a melting method using a melting furnace is preferable from the viewpoint of easiness of designing a glass composition including selection of raw materials.
Although the ion sustained-release glass used in the present invention has an amorphous structure, there is no problem even if it includes a part of a crystalline structure. Further, the glass having the amorphous structure and the glass having the crystalline structure are not problematic. There is no problem even if it is a mixture. Whether the glass structure is amorphous or not can be determined using an analytical instrument such as an X-ray diffraction analysis or a transmission electron microscope. Among them, the ion sustained-release glass used in the present invention preferably has an amorphous structure having a homogeneous structure because various ions are gradually released by an equilibrium relationship with the ion concentration in the external environment.

Since the sustained release of various ions from the ion sustained-release glass used in the present invention is affected by the particle size of the glass, it is necessary to control the particle size by methods such as wet or / and dry pulverization, classification, and sieving. . Therefore, the particle size (50%) of the ion sustained-release glass used in the present invention is not particularly limited as long as it is in the range of 0.01 to 100 μm, but is preferably in the range of 0.01 to 50 μm, more preferably 0.1. It is in the range of ˜5 μm. The shape of the glass may be any shape such as a spherical shape, a plate shape, a crushed shape, and a scale shape, and is not particularly limited, but is preferably a spherical shape or a crushed shape. The ion sustained-release glass is preferably an ion sustained-release filler obtained by pulverizing glass.

Furthermore, in order to enhance the sustained release of ions from the sustained-release glass, it is preferable that the surface of the glass be functionalized to improve the sustained release of ions. Specific examples of the surface treatment material used for the surface treatment include surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling materials, silane compounds, metal alkoxide compounds and partial condensates thereof. Preferably, an acidic polymer and a silane compound are used as the surface treatment material.

Method for surface treatment of ion sustained release glass using this acidic polymer and silane compound as surface treatment material, specifically, method of surface treatment with acid polymer after coating ion sustained release glass surface with silane compound Is exemplified below.

In an aqueous dispersion containing an ion sustained-release glass finely pulverized to a desired average particle size by pulverization or the like, a general formula (I)

（式中、ＺはＲＯ-、Ｘはハロゲン、ＹはＯＨ-、Ｒは炭素数が８以下の有機基、ｎ、ｍ、Ｌは０から４の整数で、ｎ＋ｍ＋Ｌ＝４である）で表されるシラン化合物を混合し、これを系中で加水分解または部分加水分解してシラノール化合物を経て、次いでこれを縮合させて、イオン徐放性ガラス表面を被覆する。

(Wherein Z is RO-, X is halogen, Y is OH-, R is an organic group having 8 or less carbon atoms, n, m and L are integers from 0 to 4 and n + m + L = 4). The silane compound is mixed and hydrolyzed or partially hydrolyzed in the system to pass through the silanol compound, which is then condensed to coat the ion-release glass surface.

In the above polysiloxane treatment method, the hydrolysis and condensation of the silane compound and the polysiloxane treatment on the glass surface are simultaneously carried out in the same system, but the hydrolysis and condensation of the silane compound are carried out in a separate system to reduce the condensation. A surface treatment method in which a silane compound (oligomer) is generated and mixed with an aqueous dispersion containing an ion sustained-release glass can efficiently form a polysiloxane film on the surface of the ion sustained-release glass. More preferably, it is a polysiloxane treatment method in which a commercially available low-condensation silane compound (oligomer) is used and mixed without undergoing a low-condensation production process. The reason why this method is preferred is that when a silane compound monomer is used, a large amount of water is present in the polysiloxane treatment step, so condensation occurs three-dimensionally, self-condensation proceeds predominately, and uniform poly It is considered that a siloxane film cannot be formed on the glass surface.

On the other hand, when a low-condensation silane compound (oligomer) is used, it is considered possible to form a polysiloxane film uniformly on the glass surface with unit units having a polysiloxane main chain of a certain length. The shape of the low-condensation silane compound (oligomer) is not particularly limited, but it is preferably linear rather than three-dimensional, and the longer the degree of polymerization, the poorer the condensation reactivity, and the sustained release of ions. The degree of polymerization is preferably in the range of 2 to 20, more preferably 2 to 6, because the formation of the polysiloxane film on the surface of the porous glass becomes poor. The molecular weight at that time is in the range of 500 to 600.

The polysiloxane treatment in the aqueous dispersion is carried out under a relatively slow stirring condition, the temperature is in the range of 20 ° C. to 100 ° C., more preferably in the range of 20 ° C. to 50 ° C., and the stirring time is usually several times. It is carried out in the range of minutes to several tens of hours, more preferably 30 minutes to 4 hours. Stirring does not require a special method, and can be performed by using equipment normally used in the general industry. For example, stirring may be performed using a stirrer that can stir slurry like a universal mixing stirrer or a planetary mixer. There is no problem if the stirring temperature is a temperature at which the aqueous medium does not volatilize, that is, a temperature below the boiling point of the aqueous medium. The stirring time is formed by condensation depending on the type or addition amount of the silane compound or low-condensed silane compound, the type of glass, the particle size and the proportion of the aqueous dispersion, the type of aqueous medium, and the proportion of the aqueous dispersion. The gelation rate to be affected is affected and must be adjusted and must be done until a gel is formed. If the stirring speed is too high, the gel structure will collapse and a uniform film will not be formed.

The aqueous medium is composed of water and alcohol. Addition of alcohol has a great effect of reducing the cohesiveness of the ion sustained-release glass in the drying step and further improving the crushability. Preferred alcohols are alcohols having 2 to 10 carbon atoms, but the addition of alcohols having 10 or more carbon atoms has a high boiling point and requires a long time to dry and remove the solvent. Specific alcohols include ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, iso-butyl alcohol, n-pentyl alcohol, iso-amyl alcohol, n-hexyl alcohol n-heptyl. Alcohol, n-octyl alcohol, and n-dodecyl alcohol are mentioned, More preferably, C2-C4 alcohol, for example, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, is used suitably. The addition amount of the alcohol is 5 to 100 parts by weight, preferably 5 to 20 parts by weight with respect to water. When the added amount is 100 parts by weight or more, problems such as a complicated drying process occur. The glass content is in the range of 25 to 100 parts by weight, preferably 30 to 75 parts by weight, based on the aqueous medium. When the content exceeds 100 parts by weight, the gelation rate by condensation is fast and it is difficult to form a uniform polysiloxane coating layer. When the content is less than 25 parts by weight, the glass settles under stirring or in an aqueous medium. Phase separation may occur. The amount of the silane compound added depends on the particle size of the glass, but it is in the range of 0.1 to 10 parts by weight, preferably 0.1 to 4 parts by weight in terms of SiO2. When the addition amount is 0.1 parts by weight or less, there is no effect of forming a polysiloxane coating layer, and even primary particles cannot be crushed and agglomerated, and when 10 parts by weight or more, the solidified product after drying is too hard. It cannot be crushed.

The system in the “gel” state is dried and solidified by removing the aqueous medium. Drying consists of two stages of aging and baking, the former aiming at growth of the gel structure and removal of the aqueous medium, and the latter aiming at strengthening the gel structure. The former does not distort the gel structure and removes the aqueous medium, so it is necessary to perform it stationary, and equipment such as a box-type hot air dryer is preferable. The aging temperature is in the range of 20 ° C to 100 ° C, more preferably in the range of 40 to 80 ° C. When the temperature is below this range, the aqueous medium is not sufficiently removed. When the temperature is above this range, it rapidly volatilizes, which may cause defects in the gel structure or peel off from the glass surface. The aging time depends on the ability of the drier and the like, so there is no problem as long as the aqueous medium can be sufficiently removed.

On the other hand, the firing process is divided into temperature rise and mooring, and the former is better to gradually raise the temperature to the target temperature over a long period of time, and the rapid temperature causes poor heat conduction of the gel dispersion, thus causing cracks in the gel structure there is a possibility. The latter is firing at a constant temperature. The firing temperature is in the range of 100 to 350 ° C, more preferably 100 to 200 ° C.

As described above, the aqueous medium is removed from the gel by drying, and a contracted solidified product is obtained. Although the solidified product is an agglomerated state of ion sustained-release glass, it is not simply an agglomerate of ion-sustained-release glass, and polysiloxane formed by condensation is present at the interface between the individual fine particles. Therefore, when this solidified product is crushed to the equivalent of ion-controlled release glass before the polysiloxane treatment as the next step, an ion-controlled release glass whose surface is coated with polysiloxane is obtained. Here, “crush to the equivalent of an ion sustained release glass before the polysiloxane treatment” means to break up into primary particles of the ion sustained release glass coated with polysiloxane, and the original ion sustained release. The difference from glass is that the individual particles are coated with polysiloxane. However, secondary agglomerates may be included as long as there is no problem. The solidified material can be easily crushed by applying a shearing force or an impact force. As a pulverizing method, for example, a Henschel mixer, a cross rotary mixer, a super mixer, or the like can be used.

Examples of the silane compound represented by the general formula (I) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraallyloxysilane, tetrabutoxysilane, tetrakis (2-ethylhexyloxy) silane, and trimethoxychlorosilane. , Triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxydichlorosilane, tetraphenoxysilane, tetrachlorosilane, silicon hydroxide (silicon oxide hydrate), etc., more preferably tetramethoxysilane and tetra Ethoxysilane. Moreover, it is more preferable that it is an aggregate shown with the silane compound represented by general formula (I).
Moreover, it is more preferable that it is a low condensate of the silane compound represented by general formula (I). For example, it is a low condensation silane compound obtained by condensing tetramethoxysilane and tetraethoxysilane by partial hydrolysis. These compounds can be used alone or in combination.

Moreover, an organosilane compound can also be added as a part of silane compound represented by general formula (I) at the time of polysiloxane treatment. Specific examples of organosiloxane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, methoxytripropylsilane, propyltriethoxysilane, hexyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy Ethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropylmethoxysilane, γmercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, methyltrichlorosilane, phenyl Examples include trichlorosilane and the like, and methyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, and phenyltrichlorosilane are particularly preferable. These compounds can be used alone or in combination. However, since these organic groups exist in the polysiloxane layer, they may be subjected to distortion during the formation of the polysiloxane layer, which may cause a problem in mechanical strength. For this reason, it is necessary to keep only a small amount. Further, alkoxide compounds, halides, hydrated oxides, nitrates, and carbonates of other metals can be added as part of the silane compound represented by the general formula (I) during the polysiloxane treatment.

The most preferable surface-treated ion sustained-release glass of the present invention can be obtained by subjecting the ion sustained-release glass coated with the polysiloxane obtained in the above step to an acidic polymer treatment to react with an acidic polymer. For the acidic polymer treatment, equipment generally used in the industry can be used as long as it is a dry flow type stirrer, and examples thereof include a Hensyl mixer, a super mixer, and a high speed mixer. The reaction of the acidic polymer with the ion sustained-release glass on which the polysiloxane film is formed can be carried out by contacting the acidic polymer solution by impregnation or spraying. For example, it is only necessary to dry-flow polysiloxane-coated ion sustained-release glass, disperse the acidic polymer solution from above in the flowed state, and sufficiently stir. At this time, the method for dispersing the acidic polymer solution is not particularly limited, but a dropping or spraying method capable of uniformly dispersing is more preferable. In addition, the reaction is preferably performed at around room temperature. When the temperature is increased, the reaction between the acid-reactive element and the acidic polymer is accelerated, and the formation of the acidic polymer phase becomes uneven.
After the heat treatment, the heat-treated product can be easily crushed by applying a shearing force or an impact force, and the crushing method can be performed with the equipment used for the above reaction.

The solvent used for the preparation of the acidic polymer solution used for the reaction is not a problem as long as the acidic polymer is soluble, and water, ethanol, ethanol, acetone, and the like can be mentioned. Among these, water is particularly preferable, and the acidic group of the acidic polymer is dissociated and can react uniformly with the surface of the ion sustained-release glass.
The weight molecular weight of the polymer dissolved in the acidic polymer solution is in the range of 2000-50000 and in the range of 5000-40000. Surface-treated ion sustained release glass treated with an acidic polymer having a weight average molecular weight of less than 2000 tends to have low ion sustained release. An acidic polymer having a weight average molecular weight exceeding 50,000 increases the viscosity of the acidic polymer solution, making it difficult to perform the acidic polymer treatment. The acidic polymer concentration in the acidic polymer solution is preferably in the range of 3 to 25% by weight, more preferably in the range of 8 to 20% by weight. When the acidic polymer concentration is less than 3% by weight, the acidic polymer phase described above becomes brittle. Further, when the acidic polymer concentration exceeds 25% by weight, it becomes difficult to diffuse the polysiloxane layer (porous). On the other hand, when it comes into contact with the ion-releasing glass, the acid-base reaction is fast, and during the reaction, curing starts and aggregation occurs. Problem arises. Moreover, the addition amount of the acidic polymer solution with respect to the ion sustained release glass coated with polysiloxane is preferably in the range of 6 to 40% by weight, more preferably 10 to 30% by weight. In terms of this addition amount, the optimal value is 1 to 7% by weight for the amount of acidic polymer and 10 to 25% by weight for the amount of water relative to the polysiloxane-coated ion sustained release glass.

The acidic polymer that can be used to form an acidic polymer reaction phase on the surface of an ion sustained-release glass coated with polysiloxane by the above-described method includes phosphoric acid residues, pyrophosphoric acid residues, thiophosphorus as acidic groups. It is a copolymer or a homopolymer of a polymerizable monomer having an acid group such as an acid residue, a carboxylic acid residue, or a sulfonic acid group. Examples of such polymerizable monomers include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, and citraconic acid. 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic anhydride, 5- (meth) acryloylaminopentylcarboxylic acid, 11- (meth) acryloyloxy-1,1- Undecane dicarboxylic acid, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate, 1,3-di ( (Meth) acryloyloxypropyl-2-dihydrogen Sulfate, 2- (meth) acryloyloxyethylphenyl phosphate, 2- (meth) acryloyloxyethyl 2′-bromoethyl phosphate, (meth) acryloyloxyethyl phenylphosphonate, di (2- (meth) acryloyloxy pyrophosphate) Ethyl), 2- (meth) acryloyloxyethyl dihydrogen dithiophosphophosphate, 10- (meth) acryloyloxydecyl dihydrogenthiophosphate, and the like. Among these polymers, homopolymers or copolymers of α-β unsaturated carboxylic acids, which have a relatively slow acid-base reaction with acid-reactive elements, are preferred. More preferred are acrylic acid polymers, acrylic acid-maleic acid copolymers, and acrylic acid-itaconic acid copolymers.

The ion sustained-release glass used in the present invention is characterized by the sustained release of ionic species based on the glass composition, and it releases a large amount temporarily by dissolution of metal fluoride or the like in water. Is different.
It can be determined whether or not the ion sustained-release glass or other filler has ion sustained-release properties by the following method.
Addition of 0.1 g of ion sustained-release glass or other filler to 100 g of distilled water, ion concentration (F1) sustained release in distilled water when stirred for 1 hour, or element concentration due to ion species (F1) In addition, when the concentration of ions (F1) that is slowly released in distilled water when stirred for 2 hours or the element concentration (F2) due to the ion species satisfies the relationship of the following formula (1), it can be regarded as ion sustained release. it can.
F2> F1... Formula (1)

F1 or F2 used here may be the ion concentration analyzed by a fluorine electrode, ion chromatography, etc., but it originates from the ion species correlated with the ion concentration analyzed using an inductively coupled plasma emission spectrometer There is no problem if the element concentration is used instead of the ion concentration. In addition, when there are a plurality of ions that are slowly released from the ion sustained-release glass, it is not necessary that all ion concentrations or element concentrations satisfy the formula (1), and at least one ion concentration or element concentration is the formula (1). Can be considered as sustained release of ions.
The ion sustained-release glass used in the present invention preferably has an acid neutralization ability due to the effect of ion sustained release. Acid neutralizing ability can be confirmed by adding 0.1 g of ion sustained-release glass to 10 g of lactic acid aqueous solution whose pH is adjusted to 4.0 and measuring pH change when stirring for 5 minutes. When the pH at that time is 5.5 or more, more preferably 6.0 or more, and most preferably 6.5 or more, it can be considered that acid neutralization ability is expressed.

The content of the ion sustained-release glass is preferably 1 to 35% by weight, more preferably 5 to 30% by weight, based on the total amount of the neutralization-promoting ion sustained-release dental film. When the content of the sustained-release glass is less than 5% by weight, the sustained-release amount of ions is insufficient, and effects such as strengthening the tooth and suppressing secondary caries cannot be expected. On the other hand, if it exceeds 35% by weight, the neutralization-promoting ion sustained-release dental film becomes brittle, making handling difficult.

The film-forming material (b) used in the neutralization-promoting ion sustained-release dental film of the present invention includes, for example, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, sodium polyacrylate, carboxymethylcellulose, hydroxypropylcellulose, ethylcellulose, hydroxy Ethylcellulose, hydroxypropylmethylcellulose, hydroxypropylmethylcellulose phthalate (HPMCP), cellulose acetate phthalate (also known as cellulose acetate phthalate, CAP), carboxymethylethylcellulose (CMEC), carboxymethylcellulose potassium, carboxymethylcellulose sodium, carboxymethylcellulose calcium, starch, xanthan gum , Karaya gum, sodium alginate Methylcellulose, carboxyvinyl polymer, agar, amylose, pullulan, chitosan, starch, sodium carboxymethyl starch, plantago seed coat, galactomannan, Eudragit, casein, alginic acid alkyl ester, gelatin, hydroxyethyl methylcellulose, ethyl methacrylate, trimethylammonium methacrylate Examples thereof include an ethyl copolymer, a dimethylaminoethyl methacrylate / methyl methacrylate copolymer, pullulan, and an acrylic acid / methyl methacrylate copolymer. It is preferable to have a polar group such as a carbonyl group, a hydroxyl group, an amide group, an amino group or a carboxyl group from the viewpoint of being retained on the oral tissue or the prosthetic device, and starch, sodium alginate, and polyvinylpyrrolidone are preferable. . These film components can be used not only individually but also in combination. For example, it is possible to control the sustained release amount of ions by blending two or more kinds of film components having different dissolution rates in the oral cavity.
The blending amount of the film forming material (b) is preferably 60 to 90%. When the blending amount of the film-forming material (b) is lower than 60%, it is difficult to form a film.

The neutralization-promoting ion sustained-release dental film of the present invention can contain a fluoride ion supply material. Specific examples of the fluoride ion supply material include fluoride salts and plant-derived fluorine compounds. Examples of fluoride salts include lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, aluminum fluoride, Manganese fluoride (II), iron fluoride (II), iron fluoride (III), silver fluoride (I), silver diammine fluoride, sodium hydrogen fluoride, potassium hydrogen fluoride, sodium fluorophosphate, hexafluoro Examples include potassium titanate, sodium hexafluorosilicate, sodium hexafluorophosphate, sodium pentafluorodistinate (II), and potassium hexafluorozirconate. Among the above exemplified fluoride salts, lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, and calcium fluoride are preferable, and sodium fluoride is most preferable. On the other hand, the plant-derived fluorine compound includes tea-extracted fluorine extracted from tea leaves. Fluoride ion supply materials can be used not only individually but also in combination. The compounding amount of the fluoride ion supply material is preferably 0.1 to 10%. When the compounding amount of the fluoride ion supply material is lower than 0.1%, the increase in the sustained release amount of the fluoride ion is small, and when it exceeds 10%, the fluoride ion supply material elutes in the oral cavity and the film is fragile. become.

The neutralization promoting ion sustained release dental film of the present invention may contain a salivary secretion promoting material. A saliva secretion promoting material is a component that promotes the secretion of saliva in the oral cavity. If saliva secretion increases, food residue and mild plaque collected in the oral cavity are washed away, which is effective in preventing dental caries. As the saliva secretion promoting material, an organic acid can be used, and specifically citric acid, tartaric acid, fumaric acid, malic acid, succinic acid, and lactic acid can be mentioned. Saliva secretion promoters can be used not only individually but also in combination. The compounding amount of the organic acid is preferably 0.05 to 1%. When the blending amount of the organic acid is lower than 0.05%, the promotion of salivation is insufficient, and when it exceeds 1%, the sourness becomes very strong, so that it is not suitable for eating.

The neutralization promoting ion sustained release dental film of the present invention may contain a saliva buffering capacity improver. A saliva buffering capacity improving agent is a substance having an action of rapidly shifting the oral cavity to neutrality when the oral pH is lowered. Specific examples of the saliva buffering capacity improver include basic amino acids such as sodium hydrogen carbonate, disodium hydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, sodium carbonate, arginine and the like. The saliva buffer capacity improving agents can be used not only individually but also in combination. Furthermore, the neutralization-promoting ion sustained-release dental film of the present invention can be expected to synergistically increase the saliva buffering ability because strontium ions are gradually released into the oral cavity due to the effect of the specific ion sustained-release glass contained therein. .
It is preferable to mix 5 to 20% of the saliva buffering capacity improver. When the amount of the saliva buffer capacity improver is lower than 5%, the acid buffer capacity is not expressed, and when it exceeds 20%, the neutralization-promoting ion sustained-release dental film becomes brittle and difficult to handle. .

The neutralization-promoting ion sustained-release dental film of the present invention may contain an antibacterial material. Specific examples of the antibacterial material include cationic antibacterial agents such as chlorhexidine, cetylpyridinium chloride, benzethonium chloride, benzalkonium chloride, and decalinium chloride, and nonionic antibacterial agents such as isopropylmethylphenol and halogenated diphenyl ether. Antibacterial materials can be used not only individually but also in combination.
The neutralization-promoting ion sustained-release dental film of the present invention has antibacterial or bacteriostatic properties because borate ions are gradually released into the oral cavity when the specific ion sustained-release glass contained therein contains boric acid. Can be expected to increase synergistically.

The neutralization promoting ion sustained release dental film of the present invention can also contain a sweetener. As the sweetener, an artificial sweetener which is a non-cariogenic sweetener is particularly preferable. Artificial sweeteners are not metabolized by bacteria in the oral cavity and produce almost no acid, so they do not cause a decrease in oral pH. Specific examples of artificial sweeteners include xylitol, maltitol, aspartame, sorbitol, sodium saccharin, sucralose, reduced palatinose, palatinose, mannitol, erythritol, cyclodextrin and the like. Sweeteners can be used not only individually but also in combination.

From the viewpoint of operability, the thickness of the neutralization promoting ion sustained release dental film formed from the neutralization promoting ion sustained release dental film of the present invention is preferably 15 μm to 500 μm, more preferably 20 to 200 μm, 25 Most preferred is ˜60 μm. When the thickness is less than 15 μm, the neutralization-promoting ion sustained-release dental film becomes fragile, making it difficult to handle. When the thickness is 500 μm or more, the flexibility is low and sticking to a complicated site becomes difficult.
The shape of the neutralization-promoting ion sustained-release dental film is not limited to circular, oval, rectangular, square, polygonal, etc., as long as it can be applied to oral tissues or prosthetic devices. The area of the film for use is preferably 0.5 cm2 to 25 cm2. When the area of the neutralization-promoting ion sustained-release dental film is less than 0.5 cm 2, the ion sustained-release amount is insufficient, and when the area is 25 cm 2 or more, handling becomes difficult.

The neutralization-promoting ion sustained-release dental film of the present invention can be applied to any part of the oral cavity and prosthetic device as long as it has a smooth surface. For example, it can be affixed to oral tissues such as dentin, tongue and palate, or a prosthetic device such as a denture.
The neutralization-promoting ion sustained release dental film of the present invention can have a multilayer structure in order to control the sustained release of ions. For example, it is possible to control the sustained release of ions by forming a film layer containing an ion sustained release glass in the inner layer and a film having a three-layer structure consisting only of film components in both outer layers. Alternatively, in a two-layer neutralization-promoting ion sustained release dental film comprising a layer composed of an ion sustained release glass and a water-soluble film component and a layer composed of a poorly water-soluble film component, only from the water-soluble film layer It is possible to effectively release ions slowly. In the method for producing a film having a multilayer structure, for example, after each of a plurality of films is produced, the film having a multilayer structure can be obtained by pressure bonding, welding, or the like.

Although the film manufacturing method of this invention does not specifically limit, the following methods are illustrated. A film forming material or the like is dissolved or swollen in a volatile organic solvent having a boiling point of 100 ° C. or lower, such as water or ethanol or acetone. A method of obtaining a film by dispersing ionic sustained-release glass in a dissolved or swollen liquid and then drying by heating at 100 ° C. or higher to remove a volatile organic solvent is preferable.

  The test methods for evaluating the performance of the neutralization-promoting ion sustained release dental films prepared in the examples and comparative examples that specifically describe the examples and comparative examples of the present invention are as follows.

[Measurement of amount of elements based on ions released from ion-release glass and various fillers]
0.1 g of ion-releasing glass or various fillers was added to 100 g of distilled water, stirred for 1 hour, and then gradually added to the solution filtered with a syringe filter for analysis (Chromatodisc 25A, pore size 0.2 μm: GL Sciences). The element concentration attributable to each released ion was defined as F1. Similarly, 0.1 g of ion-releasing glass or various fillers was added to 100 g of distilled water, stirred for 2 hours, and then subjected to the same operation, and the element concentration caused by each ion slowly released in the filtered solution was changed to F2. It was. Fluorine was measured for fluoride ions using a fluorine ion composite electrode (Model 9609: Orion Research) and an ion meter (Model 720A: Orion Research), and converted to fluorine element concentration using the value. At the time of measurement, 0.5 ml of TISABIII (manufactured by Orion Research) was added as an ionic strength adjusting agent. Calibration curves were prepared using standard solutions of 0.1, 1, 10, and 50 ppm. Other elements (Na, B, Al, Sr) were calculated by measurement using an inductively coupled plasma emission spectrometer (ICPS-8000: manufactured by Shimadzu Corporation). Calibration curves were prepared using standard solutions of 0.1, 1, 10, and 50 ppm. In addition, when the measurement element was out of the calibration curve range, the measurement was carried out with appropriate dilution.

[Evaluation of acid neutralization ability of ion sustained-release glass and various fillers]
The acid neutralization ability of the ion sustained-release glass used in the present invention was evaluated by the following method. 0.1 g of ion-releasing glass and various fillers were added to 10 g of lactic acid aqueous solution whose pH was adjusted to 4.0, and the pH after stirring for 5 minutes was measured using a pH meter (D-51: Horiba Seisakusho). It was evaluated by doing.

[Measurement of the amount of elements based on ions released from neutralization-promoting ion sustained-release dental film]
A neutralization-promoting ion sustained-release dental film cut into 18 mm × 18 mm is pasted on a glass plate (18 mm × 18 mm), and this glass plate specimen is immersed in 5 mL of distilled water, and the glass plate specimen is taken every hour. Was taken out and immersed again in 5 mL of fresh distilled water. This operation was performed three times in total, that is, three types of solutions containing ions released from distilled neutralized accelerated ion sustained release dental film in 0 to 1 hour, 1 to 2 hours, and 2 to 3 hours. Using these solutions, the amount of element based on each ion in the solution was measured in the same manner as in the above-described measurement method. In addition, when the measurement element was out of the calibration curve range, the measurement was carried out with appropriate dilution.

[Film thickness of neutralization promoting ion sustained release dental film]
The thickness of the neutralization-promoting ion sustained-release dental film was measured at 5 places using a micrometer (MDC25SB: Mitsumi), and the average value is shown in Tables 2 and 3 as the average film thickness.

[Evaluation of acid neutralization ability of neutralization promoting ion sustained release dental film]
A 15 mm × 15 mm neutralization-promoting ion sustained release dental film was attached to a glass plate (18 mm × 18 mm), and immersed in 5 mL of a lactic acid aqueous solution (adjusted to pH 4.0). Thereafter, the pH of the aqueous lactic acid solution after 6 hours and 24 hours was measured using a pH meter (D-51: Horiba Seisakusho).

[Evaluation of bad breath suppression effect]
In order to evaluate the bad breath suppression effect of the examples and comparative examples, the following tests were conducted on five persons. Evaluation was performed by applying a neutralization-promoting ion sustained-release dental film cut out to 18 mm × 18 mm on the tongue of each subject and comparing the bad breath after 30 minutes with the bad breath. For comparison of bad breath, we measured the concentration of sulfur compounds (VSC value) in the oral cavity derived from hydrogen sulfide, methyl mercaptan, dimethyl sulfide, etc. in the breath (XP-Breath-Tron: Shin Cosmos Electric Co., Ltd.) The VSC (1) value in the inside was compared with the VSC (2) value in the expiration after 30 minutes had passed since the pasting. As a result of the evaluation, the bad breath reduction rate (%) = (1−VSC (2) / VSC (1)) × 100 was calculated, and the average values of the five persons are shown in Tables 2 and 3.

The names of components used in Examples and Comparative Examples of the present invention and their abbreviations are shown below.
Film forming material Starch: Potato starch PVP: Polyvinylpyrrolidone (Molecular weight 630000, Tokyo Chemical Industry)
Fluoride ion supply material NaF: Sodium fluoride powder (Nacalai Tesque)
Sweetener Xylitol salivation promoter Citric acid

[Production of ion sustained-release glass 1]
Various raw materials of silicon dioxide, aluminum oxide, boron oxide, sodium fluoride, strontium carbonate (glass composition: SiO 2 23.8% by mass, Al 2 O 3 16.2% by mass, B 2 O 3 10.5% by mass, SrO 35.6% by mass, Na2O 2.3 mass%, F11.6 mass%) were uniformly mixed using a ball mill to prepare a raw material mixture, and the raw material mixture was melted at 1400 ° C. in a melting furnace. The melt was taken out of the melting furnace and cooled on a cold steel plate in a roll or water to produce glass. After 4 kg of alumina cobblestone with a diameter of 6 mmφ is put into an alumina pot (3.6 liters) of a 4-spindle vibration mill, 500 g of the glass obtained above is added and pulverized for 40 hours. Got. The 50% average particle size of the ion sustained-release glass 1 was measured by a laser diffraction particle size analyzer (Microtrac SPA: manufactured by Nikkiso Co., Ltd.) and found to be 1.2 μm. The amount of elements based on the ions released from the ion sustained-release glass 1 (the amount of ions of fluoride ions only) was measured, and the compatibility with the formula (1) was confirmed. The results are shown in Table 1.

[Production of ion sustained-release glass 2]
An ion sustained-release glass 2 subjected to the surface treatment by the following polysiloxane treatment and acidic polymer treatment was obtained.
500 g of the above-mentioned ion sustained-release glass 1 and a silane compound (a low condensate of a silane compound obtained by previously stirring 5 g of tetramethoxysilane, 1000 g of water and 100 g of ethanol for 2 hours at room temperature) were put into a universal mixing stirrer. Stir and mix for 90 minutes. Thereafter, heat treatment was performed at 140 ° C. for 30 hours to obtain a heat-treated product. This heat-treated product was pulverized using a Henschel mixer to obtain polysiloxane-coated ion sustained-release glass. While stirring 500 g of this ion-release glass coated with polysiloxane, an acidic polymer aqueous solution (polyacrylic acid aqueous solution: polymer concentration 13 wt%, weight average molecular weight 20000; manufactured by Nacalai Co., Ltd.) was sprayed using a Henschel mixer. . Thereafter, heat treatment (100 ° C. for 3 hours) was performed to produce a surface-treated ion sustained-release glass 2. The 50% average particle size of the ion sustained-release glass 2 was 1.3 μm as a result of measurement by a laser diffraction particle size measuring device (Microtrac SPA: manufactured by Nikkiso Co., Ltd.). The amount of elements based on the ions released from the surface-treated ion sustained release glass 2 (the amount of ions of fluoride ions only) was measured, and the suitability for the formula (1) was confirmed. The results are shown in Table 1.

[Production of ion sustained-release glass 3]
After mixing various raw materials of silicon dioxide, aluminum oxide, boron oxide, sodium fluoride and strontium carbonate, the mixture was melted at 1400 ° C. to make glass (glass composition: 19.8% by mass of SiO 2, 19.8% by mass of Al 2 O 3 B2O3 11.7% by mass, SrO 35.0% by mass, Na2O 2.3% by mass, F11.4% by mass). Next, the produced | generated glass was grind | pulverized for 10 hours using the vibration mill, and the glass 3 was obtained. 500 g of the glass 3 described above and a silane compound (a low condensate of a silane compound obtained by previously stirring 10 g of tetramethoxysilane, 1500 g of water, 100 g of ethanol, 70 g of methanol and 50 g of isopropanol at room temperature for 2 hours) are put into a universal mixing stirrer. And stirred for 90 minutes. Thereafter, heat treatment was performed at 140 ° C. for 30 hours to obtain a heat-treated product. This heat-treated product was crushed using a Henschel mixer to obtain an ion sustained-release glass coated with polysiloxane. While stirring 500 g of this glass coated with polysiloxane, an acidic polymer aqueous solution (polyacrylic acid aqueous solution: polymer concentration 13 wt%, weight average molecular weight 20000; manufactured by Nacalai Co., Ltd.) was sprayed using a Henschel mixer. Thereafter, heat treatment (100 ° C. for 3 hours) was performed to produce surface-treated ion sustained-release glass 3.
The surface-treated ion sustained-release glass 3 had a 50% average particle size of 3.1 μm as a result of measurement by a laser diffraction particle size measuring device (Microtrac SPA: manufactured by Nikkiso Co., Ltd.). The amount of elements based on the ions released from the surface-treated ion sustained-release glass 3 (the amount of ions of fluoride ions only) was measured, and the suitability for the formula (1) was confirmed. The results are shown in Table 1.

[Non-ion sustained release filler]
The following fillers were used as nonionic sustained release fillers.
FLX: Fuse Rex X (silica filler, particle size = 2.1 μm: Tatsumorisha)
SOC5: Admafine SO-C5 which is a silica filler (silica filler, average particle size = 1.6 μm: Admatechs)
The amount of elements based on the ions released from the filler (the amount of ions of fluoride ions only) was measured, and the suitability for the formula (1) was confirmed. The results are shown in Table 1.

As a result of adding 0.1 g of ion sustained-release glass and various fillers to 10 g of lactic acid aqueous solution whose pH was adjusted to 4.0 and stirring for 5 minutes, the pH of the ion sustained-release glass was 6.5 or more, and acid neutralization ability On the other hand, the nonionic sustained-release filler hardly changed its pH to 4.1, and it was confirmed that it has no acid neutralization ability. In addition, the amount of the element released from the ion sustained-release glass (the amount of ions of only fluoride ions) conforms to the formula (1), while the amount of the element released from the non-ionic sustained-release filler (fluoride ions) (Only ion amount) was confirmed not to conform to the formula (1).

The preparation method of the neutralization promotion ion sustained release dental film which mix | blended the said ion sustained release glass and the nonionic sustained release filler is as follows. To 4000 g of distilled water, the components constituting the neutralization-promoting ion sustained-release dental film shown in Tables 2 and 3 were added to a total of 100 g, and the mixture was heated and stirred at 80 ° C. for 1 hour. Then, it dried under reduced pressure at 90 degreeC for 20 hours, and obtained the neutralization promotion ion sustained release dental film. These compositions and evaluation results are shown in Table 2.

Examples 1 to 6, which are neutralization-promoting ion sustained-release dental films containing ion sustained-release glass, stably and slowly release ions of F, Na, B, Al, and Sr over a long period of time. It was confirmed that The sustained release of these ions in the oral cavity is expected to improve the acid resistance of the tooth, improve the acid buffer, and prevent bad breath. Further, from the evaluation of acid neutralization ability, the neutralization-promoting ion sustained release dental film neutralizes a lactic acid aqueous solution of pH 4.0 to around pH 6 after 6 hours and to near neutral after 24 hours. This suggests that the acid neutralizing ability is high. Regarding the evaluation of bad breath suppression, a decrease in the VSC value of 36 to 62% was confirmed, indicating that it is effective for bad breath suppression.

Comparative Examples 1 and 2, which are neutralization-promoting ion sustained-release dental films not containing ion sustained-release glass, do not release ions at all, suggesting that there is no effect of improving the acid resistance of the tooth. . Although Comparative Examples 3 and 4 which are neutralization-promoting ion sustained release dental films containing only sodium fluoride as a source of ions were confirmed to have sustained release of fluoride ions in the initial period of 0 to 1 hour, There is no subsequent sustained release of fluoride ions, and improvement in the acid resistance of the tooth can hardly be expected. Moreover, it was recognized from the evaluation of acid neutralization ability that it has no acid neutralization ability. Regarding the evaluation of bad breath suppression, there was almost no change in the VSC value, suggesting that it does not have a bad breath reduction effect.
 

Claims (1)

A neutralization-promoting ion sustained-release dental film comprising an ion sustained-release glass (a) and a film forming material (b) and having a thickness of 15 μm to 500 μm ,
The ion sustained-release glass (a) is fluoroaluminoborosilicate glass, and its glass composition range is
SiO2 15-35% by mass,
Al2O3 15-30% by mass,
B2O3 5-20% by mass,
20 to 45% by mass of SrO,
F 5-15% by mass,
Na2O 0-10% by mass,
A neutralization-promoting ion sustained-release dental film characterized in that the surface of an ion sustained-release glass surface is coated with a silane compound and then surface-treated with an acidic polymer .