WO2014050028A1 - Curing agent paste and method for producing same, and alginate impression material kit for dental use - Google Patents

Description

Hardener paste, method for producing the same, and dental alginate impression material kit

The present invention relates to a curing agent paste, a method for producing the same, and a dental alginate impression material kit.

When a cast crown restoration process or a defect prosthesis process or the like is required to restore a tooth or the like, first, a mold such as an abutment tooth is obtained. Next, a model made of gypsum or the like is produced using the obtained mold. And a prosthesis is produced based on the model, and the produced prosthesis is attached to an abutment tooth or the like. This type of abutment tooth is referred to as an impression, and the curing agent for obtaining the impression is called an impression material. As this impression material, an alginate impression material, an agar impression material, a silicone rubber impression material, a polysulfide rubber impression material, a polyether rubber impression material, or the like is used. Among them, the alginate impression material is most widely used because it is inexpensive and easy to handle.

作業 The following procedure is used to obtain an impression using an alginate impression material. First, what knead | mixed each component which comprises an alginate impression material is put on the tray for impression imitating a dentition. Next, a tray with impression material is pressed against the teeth so as to wrap the teeth in the oral cavity. Then, after the alginate impression material is cured, the alginate impression material and the tray are integrally removed from the teeth and removed from the oral cavity.

This alginate impression material is used by kneading a gelling reagent such as alginate and calcium sulfate and a main component such as water. In the state before use, the alginate impression material is a powder type in which the solid content excluding water is powdered, or a paste (based on alginate and water) as a main component in order to ensure storage stability. There is a paste type using a combination of a material paste) and a paste (curing agent paste) whose main component is a gelling reagent. In use, in the powder type, powder and water are kneaded, and in the paste type, two types of paste are kneaded.

In powder type alginate impression materials, skilled techniques are required by hand for kneading. In contrast, the paste type alginate impression material can be easily automated and labor-saving in the kneading operation by using a dedicated kneading apparatus for kneading the base paste and the curing agent paste. For this reason, in recent years, paste-type alginate impression materials are becoming popular in the form of replacing powder-type alginate impression materials.

With respect to the conventional paste type alginate impression material curing agent, a paste-like composition comprising a divalent metal salt, a reaction retarding agent and a fluid plasticizer (Patent Document 1), a curing agent comprising gypsum and a nonionic surfactant. (Patent Document 2), gypsum and a hardly water-soluble liquid compound, a surfactant, a curing agent composed of an amino acid compound (Patent Document 3), a curing agent composed of gypsum, a slightly water-soluble liquid compound, and a moisturizer (Patent Document 4) , Calcium sulfate, surfactant, magnesium oxide, a hardener made of a poorly water-soluble liquid compound (Patent Document 5), and the like are known.

Such paste-type alginate impression materials are usually provided to users such as dentists and dental hygienists in a form where both the base paste and the hardener paste are hermetically stored in a packaging container such as an aluminum pack. Is done. Here, in the kneading operation, the opening of the packaging container for the base paste is connected to the base paste injection port of the kneading apparatus, and the opening of the packaging container for the curing agent paste is connected to the curing agent paste injection port of the kneading apparatus Connect to In this state, the two types of paste supplied from the respective packaging containers into the kneading apparatus are automatically kneaded in the kneading apparatus, and then the kneaded product is discharged out of the kneading apparatus. Thereby, the user can obtain a kneaded material. Therefore, when performing such a kneading process, the paste in the packaging container needs to have appropriate fluidity so that the paste in the packaging container can be smoothly supplied into the kneading apparatus. is there. For this reason, the viscosity of the paste hermetically stored in the packaging container is adjusted so as to have appropriate fluidity immediately after production.

However, in the hardener paste, the fluidity decreases with time and self-cures. And when hardening generate | occur | produces, since it becomes impossible to discharge a hardening | curing agent paste from the opening part of a packaging container, the hardening | curing agent paste for producing a kneaded material cannot be utilized. In other words, the expiration date of the curing agent paste that is hermetically stored in the packaging container depends on the progress of self-curing. The progress rate of self-curing determines the expiration date of the curing agent paste.

Here, it is considered that the reason why the curing agent paste is self-cured due to a decrease in fluidity with the passage of time is due to the reaction of moisture contained in the curing agent paste with calcium sulfate (gypsum) over time. It is done. In order to solve this problem, it is necessary to remove moisture in the hardener paste.
Patent Document 4 proposes to improve the expiration date of the curing agent paste by blending a drying agent such as calcium chloride or magnesium chloride as a moisturizing agent in the curing agent paste to remove moisture in the curing agent paste. However, the effect was not always sufficient. That is, as an indication of long-term storage, when the amount of water contained in the curing agent paste is 0.05% by mass or less, the amount of desiccant must be extremely increased, and the amount of desiccant increases. Immediately before taking an impression, when kneaded with a base paste mainly composed of alginate and water, the amount of water in the base paste changes or bubbles generated from the desiccant are mixed in the paste. As a result, the operability and impression performance of the paste are adversely affected.

JP 58-35105 A JP 59-101410 A JP-A-6-32709 International Publication No. 2012/063618 JP-A-9-315924

This invention makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention can suppress the self-curing of the curing agent paste in a state of being hermetically stored in the packaging container over a long period of time, a method for producing the same, and the self-curing during storage for a long period of time. At the same time, an object of the present invention is to provide a dental alginate impression material kit having good operability and impression performance during use.

Means for solving the problems are as follows. That is,
<1> (A) Calcium sulfate containing calcium sulfate dihydrate, (B) a hardly water-soluble liquid compound, and (C) a surfactant as main components, and having a moisture content of 0.05% by mass or less There is a hardener paste.
<2> The curing agent paste according to <1>, wherein the calcium sulfate contains 5% by mass or more of calcium sulfate dihydrate.
<3> (A) Calcium sulfate containing calcium sulfate dihydrate, (B) a poorly water-soluble liquid compound, and (C) a surfactant,
A method for producing a curing agent paste, wherein the calcium sulfate, the poorly water-soluble liquid compound, and the surfactant are vacuum kneaded under a temperature condition not exceeding 60 ° C.
<4> (A) Calcium sulfate containing calcium sulfate dihydrate, (B) a hardly water-soluble liquid compound, and (C) a surfactant as main components, and having a water content of 0.05% by mass or less. A curing agent paste,
A dental alginate impression material kit comprising (D) an alginate and (E) a base paste containing water as a main component.
<5> The dental alginate impression material kit according to <4>, wherein the calcium sulfate contains 5% by mass or more of calcium sulfate dihydrate.

According to the present invention, the above-mentioned problems in the prior art can be solved, and the curing agent paste capable of suppressing the self-curing of the curing agent paste in a state of being hermetically sealed in the packaging container over a long period of time, and a method for producing the same In addition, it is possible to provide a dental alginate impression material kit that can suppress self-curing during storage for a long time and at the same time has good operability and impression performance during use.

According to the present invention, while maintaining the operability and impression performance of the impression material, the curing agent paste capable of suppressing the self-curing of the curing agent paste in a sealed state in the packaging container over a long period of time, and a method for producing the same As well as a dental alginate impression material kit. The hardener paste of the present invention can be suitably used not only for dental use but also as a pack material for protecting the teat as disclosed in, for example, JP-A-2006-50911.

The present inventors diligently studied to solve the above problems, and obtained the following knowledge.
As the curing agent paste, calcium sulfate dihydrate is preferably used from the viewpoint of gradually curing the impression material by reacting with the alginate in the base paste and imparting the operability and impression performance of the impression material ( For example, see Patent Document 4).
However, it is considered that the crystal lattice of calcium sulfate dihydrate is destroyed by heat, and crystal water derived from calcium sulfate dihydrate is liberated in the hardener paste. On the other hand, in other words, by radiating the frictional heat during vacuum kneading, where the heat is most applied to the kneaded product, and controlling it below a certain temperature, it is possible to suppress the destruction of the crystal lattice of calcium sulfate dihydrate, It is considered that crystallization water can be prevented from free diffusion into the curing agent paste.
From this point of view, the temperature conditions during vacuum kneading were controlled to produce a curing agent paste. When producing a curing agent paste by vacuum kneading each component, the temperature conditions for vacuum kneading were set to 60 ° C. The knowledge that the moisture content of the manufactured hardening agent paste can be suppressed to 0.05 mass% or less was obtained by controlling not to exceed.
In Patent Document 5, as a temperature condition in the production of the curing agent paste, from the viewpoint of eliminating the delay in curing time when the curing agent paste is used after long-term storage, a mixture of magnesium oxide and a surfactant is used at 40 ° C to Although it is supposed to be heated at a temperature of 150 ° C., in addition to the generation of crystal water derived from calcium sulfate dihydrate on the high temperature side, controlling the temperature condition of vacuum kneading not to exceed 60 ° C. Not considered. Based on the above knowledge, it is required to control the paste sample containing calcium sulfate dihydrate so as not to exceed 60 ° C. for processes other than vacuum kneading.

(Curing agent paste and manufacturing method thereof)
The curing agent paste of the present invention includes (A) calcium sulfate containing calcium sulfate dihydrate, (B) a hardly water-soluble liquid compound, and (C) a surfactant as main components, The water content of is 0.05% by mass or less.
Moreover, the manufacturing method of the said hardening | curing agent paste is the temperature conditions which do not exceed 60 degreeC at least said (A) calcium sulfate, said (B) poorly water-soluble liquid compound, and said (C) surfactant. It is characterized by vacuum kneading.

<Production method>
Hereinafter, the manufacturing method of the said hardening | curing agent paste is demonstrated more concretely.
If the curing agent paste has a function of cooling the kneaded product at the time of kneading, for example, a device capable of circulating cold water through a jacketed kneading container, a known stirring mixer can be used for paste production. Can be used.
Here, the stirring mixer is not particularly limited and may be appropriately selected depending on the purpose. For example, a rotating container type mixing kneader such as a ball mill, a ribbon mixer, a kneader, an internal mixer, a screw kneader. And a fixed container type mixing and kneading machine having a horizontal axis or a vertical axis such as a Henschel mixer, a universal mixer, a Laedige mixer, and a butterfly mixer. Among these, from the viewpoint of heat dissipation efficiency, it is preferable to use a kneader having a function of circulating cooling water inside the stirring blade.

Specifically, in order to add necessary components to the kneading tank and dissipate the heat in the kneading tank, circulating cooling water (preferably water at 10 ° C to 25 ° C) is circulated through the jacket and kneading is started at normal pressure. Then, in a state where it is uniform to some extent, the inside of the kneading tank is decompressed and vacuum kneading is performed.
At this time, periodically check the paste temperature at the part where the most shear force is applied to the paste at the time of kneading, for example, below the place where the stirring blade or high-speed chopper is installed, so that the paste temperature does not exceed 60 ° C. There is a need.
As a method for checking the paste temperature, the kneading may be interrupted and a thermometer or the like may be used, but a thermocouple temperature sensor or the like is previously installed in the kneading tank so that the paste temperature can be constantly checked. It is preferable to keep.
If the paste temperature rises and may become 60 ° C. or higher, the kneading is interrupted until the paste temperature is lowered, or the cooling water temperature is lowered.
The rotational speeds of the stirring blade and the high-speed chopper may be appropriately determined so that a desired curing agent paste viscosity can be obtained. However, the rotation speed is usually set so that the vacuum kneading time is in the range of 30 minutes to 120 minutes. It is preferable to set the stirring blade rotation speed within the range of 20 to 500 rpm and the high speed chopper within the range of 1,000 to 5,000 rpm.

The temperature condition during vacuum kneading is not particularly limited as long as there is no temperature rise exceeding 60 ° C., but from the viewpoint of sufficiently suppressing the destruction of the crystal lattice of calcium sulfate dihydrate, the temperature rise exceeds 42 ° C. It is preferable not to have any. If the lower limit of the kneading temperature is too low, the viscosity of the (B) poorly water-soluble liquid compound is increased and the kneadability is lowered. Therefore, the temperature is 30 ° C. or higher after the stable operation is started 5 minutes after the start of vacuum kneading. Preferably there is.
In the present invention, the temperature condition does not exceed 60 ° C. at the time of vacuum kneading, from a sudden change in kneading control, etc., for a very short period that does not substantially affect the destruction of the crystal lattice of calcium sulfate dihydrate, It is permissible to exceed 60 ° C. Specifically, during kneading, even if it exceeds 60 ° C., the temperature does not exceed 60 ° C. if it continues for a short time that does not exceed 5 seconds, more preferably, it does not exceed 2 seconds. Conditions are acceptable as maintained.

The kneading of the curing agent paste is carried out by vacuum kneading in order to prevent bubbles from being mixed into the paste and to increase the dispersion efficiency of the powder component and the liquid component and to obtain a uniform paste. The pressure condition for the vacuum kneading is 3 Torr to 60 Torr (1 Torr is about 133.32 Pa). If the pressure condition is less than 3 Torr, the kneading efficiency may decrease. If the pressure condition exceeds 60 Torr, not only the kneading efficiency but also bubbles may be mixed in the paste. Moreover, if it is this pressure condition, the water content in the said hardening | curing agent paste can be suppressed to 0.05 mass% or less by making temperature conditions into the conditions which do not exceed 60 degreeC.

<Each component>
As described above, the curing agent paste contains calcium sulfate (A) containing the calcium sulfate dihydrate, the poorly water-soluble liquid compound (B), and the surfactant (C) as main components, An optional component may be included as necessary.

-(A) Calcium sulfate-
As a specific component of the calcium sulfate (A), calcium sulfate used for the gelation reaction of alginate can be efficiently eluted in the presence of water, so that calcium sulfate dihydrate is always used. Furthermore, it selects suitably according to the objective and contains calcium sulfate hemihydrate (hemihydrate gypsum), calcium sulfate anhydrous salt (anhydrous gypsum), etc. as said calcium sulfate (A) components other than the said calcium sulfate dihydrate. Can be made.
The amount of calcium sulfate (A) to be blended is not particularly limited and may be appropriately selected depending on the intended purpose. It is 10 to 2 parts by weight based on 100 parts by weight of alginate contained in the base paste. It is preferably in the range of 000 parts by mass, more preferably in the range of 100 parts by mass to 1,000 parts by mass. In general, the content of the calcium sulfate (A) in the curing agent paste is preferably 5% by mass to 80% by mass, and more preferably 20% by mass to 60% by mass.
There is no restriction | limiting in particular as content rate of the said calcium sulfate dihydrate in the said calcium sulfate (A), Although it can select suitably according to the objective, 5 mass% or more is preferable and 15 mass% or more is more. Preferably, it may be 100% by mass. When the content is less than 5% by mass, the gel strength of the alginate is insufficient, the curing strength of the impression material is lowered, and the operability and impression performance of the impression material may be lowered.

-(B) Slightly water-soluble liquid compounds-
The hardly water-soluble liquid compound (B) is used to paste the curing agent paste. “Slightly water-soluble” means that the solubility in 100 g of water at 20 ° C. is 5 g or less.
Such a poorly water-soluble liquid compound is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include hydrocarbon compounds, aliphatic alcohols, cyclic alcohols, fatty acids, fatty acid esters, these fatty acids, Examples thereof include salts of fatty acid esters and hydrophobic polymers. Hereinafter, suitable examples of these various poorly water-soluble liquid compounds (B) will be shown.

As the hydrocarbon compound, any of a chain compound and a cyclic compound can be used. For example, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, kerosene, 2,7-dimethyloctane. And aliphatic chain hydrocarbon compounds such as 1-octene, alicyclic hydrocarbon compounds such as cycloheptane and cyclononane, and liquid paraffin which is a mixture of liquid saturated hydrocarbons.

Examples of the aliphatic alcohol include saturated aliphatic alcohols such as 1-hexanol and 1-octanol, and unsaturated aliphatic alcohols such as citronellol and oleyl alcohol. Examples of the cyclic alcohol include benzyl alcohol and meta-cresol.

Examples of the fatty acid include saturated fatty acids such as hexanoic acid and octanoic acid, and unsaturated fatty acids such as oleic acid and linoleic acid. Examples of the fatty acid esters include vegetable oils such as ethyl octoate, butyl phthalate, oleic acid glycerides, olive oil and sesame oil, and animal fats such as liver oil and whale oil.

Examples of the hydrophobic polymer include polysiloxane (so-called silicone oil), and more specifically, polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, polyphenylhydrogensiloxane, and the like. Can be mentioned.

In consideration of production cost, harmfulness to living body, influence on taste when taking impression of teeth, among the poorly water-soluble liquid compounds (B) listed above, the hydrocarbon compound, the hydrophobic heavy The coalescence is preferred, and liquid paraffin and silicone oil are particularly preferred. In addition, as the said slightly water-soluble liquid compound (B), it may be used individually by 1 type and may use 2 or more types together.

The blending amount of the hardly water-soluble liquid compound (B) is not particularly limited and may be appropriately selected depending on the intended purpose. It is 10 to 200 parts by mass with respect to 100 parts by mass of the calcium sulfate (A). It is preferably in the range of parts by mass, more preferably in the range of 20 parts by mass to 100 parts by mass.

-(C) Surfactant-
The surfactant (C) is used to paste the curing agent paste.
Such surfactant (C) is not particularly limited and may be appropriately selected depending on the intended purpose. Anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic interfaces Any of the active agents can be used. Hereinafter, suitable examples of these various surfactants (C) will be shown.

Examples of the anionic surfactant include alkyl sulfonates, alkyl benzene sulfonates, and alkyl ether carboxylates.
Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts.
Examples of amphoteric surfactants include aminocarboxylates.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene-polyoxypropylene block polymer, polyoxyethylene glycerin fatty acid ester, polyoxyglycerin fatty acid ester, sorbitan fatty acid. Examples include esters, sucrose esters, polyoxydiethylene alkylamines, block polymers of polysiloxanes and polyoxyethylenes, and the like.
In addition, as said surfactant (C), it may be used individually by 1 type and may use 2 or more types together.
The amount of the surfactant (C) blended is not particularly limited and may be appropriately selected depending on the intended purpose. It is in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the calcium sulfate (A). Is preferably within the range of 5 to 20 parts by mass.

-Optional component-
The optional component is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose. For example, the gelation regulator, filler, inorganic fluorine compound, metal oxide, amino acid Examples thereof include compounds, unsaturated carboxylic acid polymers, humectants, fragrances, colorants, antibacterial agents, preservatives, pH adjusters and the like.
In addition, as these additives, it can add suitably to any one or both of the said hardening | curing agent paste and the base material paste mentioned later. However, the filler is preferably added to both the base paste and the curing agent paste, and the gelling modifier is preferably added to the curing agent paste.

When the gelation modifier is used, the reaction rate between the alginate and the gelation reagent (calcium sulfate (A)) can be adjusted (delayed). For this reason, it becomes easy to adjust the curing time in accordance with the work time required from mixing and kneading each component constituting the impression material to taking an impression in the oral cavity.
The gelling modifier is not particularly limited and may be appropriately selected depending on the intended purpose. For example, i) an alkali metal such as trisodium phosphate, tripotassium phosphate, sodium pyrophosphate, sodium tripolyphosphate, etc. And phosphate containing ii) oxalate containing an alkali metal such as sodium oxalate and potassium oxalate, and iii) carbonate containing an alkali metal such as sodium carbonate and potassium carbonate. In addition, as said gelatinization regulator, it may be used individually by 1 type and may use 2 or more types together.
The blending amount of the gelling modifier can be appropriately selected according to other components and required curing time, but is preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the alginate. A range of 3 parts by mass to 15 parts by mass is more preferable. With such a blending amount, it is easy to adjust the curing time substantially corresponding to the working time, and in addition, the cured product can be sufficiently cured.

The filler is used to adjust the physical properties of the impression material cured body.
There is no restriction | limiting in particular as such a filler, Although it can select suitably according to the objective, Viscosity minerals, such as a diatomaceous earth and a talc, are preferable, and oxides of metals or metalloids, such as a silica and an alumina, are also used. Can do.
The blending amount of the filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably in the range of 50 parts by mass to 2,000 parts by mass with respect to 100 parts by mass of the alginate, A range of 100 parts by weight to 1,000 parts by weight is more preferable.

The inorganic fluorine compound, the metal oxide, and the amino acid compound are used from the viewpoint of adjusting the strength of the cured impression material, and preventing the surface of the gypsum model from being rough during impression collection and gypsum model manufacture.
Examples of the inorganic fluorine compound include potassium titanium fluoride and potassium silicofluoride. Examples of the metal oxide include magnesium oxide and zinc oxide. Examples of the amino acid compound include amino acid / formaldehyde condensates.

The unsaturated carboxylic acid polymer is used for facilitating control of the rate of change in viscosity when the components constituting the impression material are mixed and kneaded.

The humectant is used to improve the impression accuracy at the time of taking an impression and the drying resistance of the cured product after taking the impression.
Such a moisturizing agent is not particularly limited and may be appropriately selected depending on the intended purpose.However, it may be appropriately selected depending on the purpose, and non-saccharides such as disaccharides such as trehalose and sucrose, oligosaccharides such as raffinose, melezitose, stachyose, and cyclodextrins. Reducing sugar is preferred.
The blending amount of the humectant is not particularly limited and may be appropriately selected depending on the intended purpose, but is within the range of 100 parts by mass to 2,000 parts by mass with respect to 100 parts by mass of the alginate. It is preferably in the range of 400 to 1,200 parts by mass.

The curing agent paste does not exclude addition of a desiccant used for various purposes. However, when using the desiccant to control the moisture in the curing agent paste, it is necessary to add 50 parts by mass or more per 100 parts by mass of calcium sulfate, and when adding a large amount of the desiccant, When kneading with the base paste, the amount of moisture in the base paste changes and air bubbles generated from the desiccant are mixed into the kneaded product, thereby adversely affecting the operability and impression performance of the impression material. Therefore, the aspect of adding the desiccant in a large amount for the purpose of moisture control is excluded from the curing agent paste.
In addition, the desiccant said here means what adsorb | sucks water | moisture content itself, and the adsorbed water | moisture content is completely removed from a system, and the function as free water is lost. Specific examples of such a desiccant include substances having deliquescent properties such as urea, magnesium chloride and calcium chloride, polymers of polyhydric alcohols such as polyethylene glycol, and cellulose polymers such as methylcellulose.

<Physical properties>
The moisture content in the curing agent paste is 0.05% by mass or less, preferably 0.01% by mass or less, and ideally 0% by mass.
When the moisture content exceeds 0.05% by mass, the fluidity of the curing agent paste decreases with the passage of time, self-curing, and the curing agent paste can be discharged from the opening of the packaging container. Therefore, the curing agent paste cannot be used for producing the impression material.
Examples of the method for measuring the moisture content in the curing agent paste include a method using a Karl Fischer moisture meter.

As an evaluation of operability and impression performance of the impression material based on the curing agent paste, the elastic strain in the cured material of the impression material obtained by kneading the curing agent paste and the base material paste is particularly limited. However, it is preferably 20% or less, and more preferably 17% or less.
The permanent set in the cured material of the impression material is not particularly limited, but is preferably less than 5% and more preferably 4% or less.
These elastic strains and permanent strains are used immediately after (initially) the production of the cured paste, and when used after 1 year from the production of the cured paste, the increase is 40%. Is preferably within.
In addition, the elastic strain and permanent strain can be measured according to JIS T6513.

(Dental alginate impression material kit)
The dental alginate impression material kit of this invention has the said hardening | curing agent paste of this invention, and a base material paste.

<Curing agent paste>
Since the said hardening agent paste is common in the matter demonstrated with the said hardening agent paste of this invention, description is abbreviate | omitted.

<Base material paste>
The base paste includes (D) an alginate and (E) a base paste containing water as a main component, and may contain an optional component as necessary.

-(D) Alginate-
The alginate (D) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, i) alkali metal alginate such as sodium alginate and potassium alginate, ii) ammonium alginate, triethanolamine alginate And ammonium alginate. Among these alginates, it is preferable to use an alkali metal alginate from the viewpoints of availability, ease of handling, physical properties of the cured product, and the like. Moreover, as said alginate, 1 type may be used individually and 2 or more types may be used together.

The content of the alginate is usually preferably within the range of 2% by mass to 10% by mass in the kneaded product of the cured product paste and the base paste. Therefore, the amount of the alginate contained in the base paste is adjusted so that the content of the alginate is within the range in the kneaded product when viewed in the entire dental alginate impression material kit. To do.
The molecular weight of the alginate is not particularly limited and may be appropriately selected depending on the intended purpose. The viscosity of an aqueous solution containing 1% by mass of the alginate is 50 cps to 100 cps (1 cps is 0.001 Pa · The molecular weight is preferably within the range of s).

(E) Water As said water (E), tap water, ion-exchange water, distilled water, etc. can be utilized. The amount of the water is preferably used in the range of 100 parts by mass to 4,000 parts by mass with respect to 100 parts by mass of the alginate in the kneaded product when the kneaded product is prepared. More preferably, it is used in the range of 500 to 2,000 parts by mass.

-Optional component-
Since the optional component is the same as that described for the cured paste of the present invention, the description thereof is omitted.

-Manufacturing method-
There is no restriction | limiting in particular as a manufacturing method of the said base paste, According to the objective, it can select suitably, For example, it can manufacture using the well-known stirring mixer which can be utilized for paste manufacture.
Examples of the stirring mixer include a horizontal container such as a rotating container type mixing kneader such as a ball mill, a ribbon mixer, a kneader, an internal mixer, a screw kneader, a Henschel mixer, a universal mixer, a Ladige mixer, a butterfly mixer, or the like. A fixed container type mixing kneader having a vertical axis can be used.
In addition, in the manufacture of the base paste, after performing the first step of dissolving a component having a relatively high solubility in water, subsequently, relative to water such as the alginate Stirrer that does not apply a strong shearing force to the component to be dissolved or the solution in which this component is dissolved in the first step when performing a post-process that dissolves low-solubility components sequentially or collectively Can also be used.
As such a stirrer, a portable stirrer having the various stirrer blades, the same stirrer, the same side stirrer, a pipe stirrer, or the like can be used. Furthermore, in the production of the base paste, the mixing and kneading machine may be used alone or in combination of two or more.

<Usage>
First, the dental alginate impression material kit is used after kneading the curing agent paste and the base material paste with an automatic kneader or the like immediately before taking the impression.
In the kneading operation, the mixing ratio Rm of the base paste to the hardener paste (the amount of the hardener paste used / the amount of the base paste used [parts by mass / part by mass]) is not particularly limited and depends on the purpose. However, it is preferably in the range of 0.25 to 1.
The mixing ratio Rm can be displayed on the mixing ratio information display medium. As the mixing ratio information display medium, i) a product package including a cardboard box or the like, ii) an instruction manual for a product provided in at least one of a paper medium and electronic data, and iii) sealing the base paste Storage member (container, packaging bag, etc.) to be stored in a state, iv) Storage member (container, packaging bag, etc.) to store the curing agent paste in a sealed state, v) At least one aspect of paper medium and electronic data Product catalog provided, vi) In addition to the product, a message sent to the product user by e-mail or mail can be used. In addition, the mixing ratio Rm may be provided to the product user in a mode that can be recognized by the product user according to modes other than those shown in the above i) to vi). Here, in the case of providing a product user with a storage member including the base material paste and a storage member including the curing agent paste, or a storage member including any one type of paste, for these members, Instructions according to at least one of the product package and the paper medium are added as necessary.

Next, after preparing a kneaded product using the dental alginate impression material kit, the kneaded product is placed on a dedicated tray. And the impression is extract | collected by pressing the kneaded material piled up to this tray with target objects, such as a tooth | gear. Thereafter, after the kneaded product from which the impression has been collected is cured to become a cured product, a post-process such as making a plaster model based on the cured product is further performed. Here, as the tray, a known tray can be used without limitation, but a metal tray or a resin tray is generally used. Examples of the material of the metal tray include stainless steel, tin alloy, aluminum, plating treatment, or resin-coated brass. In addition, when the said dental alginate impression material kit is used, the said kneaded material is hold | maintained well in any said metal tray. Moreover, polymethacrylic acid ester etc. are mentioned as a material of the said resin-made trays.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

<Abbreviations for raw materials>
Various raw materials used in the manufacture of dental alginate impression material kits according to Examples and Comparative Examples described below are as shown in Table 1 below.

<Evaluation method>
Measurement method of “moisture content in curing agent paste” for samples according to examples and comparative examples described later, evaluation method regarding “presence / absence of curing agent paste solidification at 25 ° C. storage”, and “elastic strain of impression material, Evaluation methods for “permanent strain” are as follows.

1. Method for measuring “moisture content in hardener paste”:
1 g of each adjusted curing agent paste was weighed into a sample bottle, 4 g of sufficiently dried anhydrous toluene was added, and the mixture was stirred for several hours. Next, the amount of water contained in the solution was quantified using the Karl Fischer coulometric titration method.

2. Evaluation method of “presence / absence of solidification of curing agent paste at 25 ° C.”
Each prepared curing agent paste was vacuum-filled into an aluminum paste pack and stored in an incubator set at 25 ° C. When a predetermined period (initial, half year, one year later) passed, the curing agent paste pack was taken out, and the presence or absence of solidification of the paste in the pack was evaluated according to the following evaluation criteria.
Evaluation criteria:
[1]: No change at all. It has fluidity.
[2]: Although it is a little hard, fluidity remains and discharge from the mixer is possible.
[3]: Solidified and cannot be discharged from the mixer.

3. Evaluation method of "elastic strain and permanent strain of impression material":
The adjusted curing agent paste for the impression material and the base material paste were each vacuum filled into an aluminum paste pack and set in an alginate impression material automatic kneader ("AP mixer II" manufactured by Tokuyama Dental Co., Ltd.). The pumping amount of the mixer was adjusted so that the desired mixing ratio (curing agent paste / base paste) was obtained, and the paste was discharged into a strain test mold to obtain a cured impression material. The obtained cured product was measured for elastic strain and permanent strain according to JIS T6513.
Also, store the curing agent paste pack in an incubator set at 25 ° C., and when the predetermined period (initial, half year, one year later) has passed, take out the curing agent paste pack and store it in the same way. Later elastic strain and permanent strain were measured and compared with initial values.

<Curing agent paste manufacturing method>
The manufacturing method of the hardening | curing agent paste which concerns on an Example and a comparative example is as follows.

-Manufacturing method a-
A predetermined amount of each component shown in Table 1 above is weighed and charged into a kneading tank of an “Ico mixer” manufactured by Aiko Co., Ltd., in which a temperature sensor is attached in the vicinity of the stirring blade in the kneading tank, and the temperature of the paste in the kneading tank is adjusted. Therefore, 20 ° C. water was circulated through the kneading tank jacket. Pre-kneading was performed for 30 minutes, and when the respective components were mixed to some extent, kneading was interrupted once, and the paste adhering to the upper part of the kneading tank was scraped off using a rubber spatula.
Next, the inside of the kneading tank was decompressed (50 torr) and vacuum kneaded for 90 minutes to produce a curing agent paste. At this time, the temperature of the paste in the kneading tank was 30 ° C. or more after starting stable operation 5 minutes after the start of kneading, and was at most the temperature shown in Table 3. After completion of the kneading, the produced curing agent paste was collected, and vacuum-filled into an aluminum paste pack, and the curing agent paste was subdivided into each paste pack.

-Manufacturing method b-
A predetermined amount of each component shown in Table 1 above is weighed and charged into a kneading tank of an “Ico mixer” manufactured by Aiko Co., Ltd., in which a temperature sensor is attached in the vicinity of the stirring blade in the kneading tank, and the temperature of the paste in the kneading tank is adjusted. Therefore, 20 ° C. water was circulated through the kneading tank jacket. Pre-kneading was performed for 30 minutes, and when the respective components were mixed to some extent, kneading was interrupted once, and the paste adhering to the upper part of the kneading tank was scraped off using a rubber spatula.
Next, the inside of the kneading tank was decompressed (50 torr) and vacuum kneaded for 90 minutes to produce a curing agent paste. At this time, the temperature of the circulating water was adjusted as needed so that the temperature of the paste in the kneading tank was always 42 ° C. after the stable operation started 5 minutes after the start of kneading. After completion of the kneading, the produced curing agent paste was collected, and vacuum-filled into an aluminum paste pack, and the curing agent paste was subdivided into each paste pack.

-Manufacturing method c-
A predetermined amount of each component shown in Table 1 above is weighed and charged into a kneading tank of an “Ico mixer” manufactured by Aiko Co., Ltd., in which a temperature sensor is attached in the vicinity of the stirring blade in the kneading tank, and the temperature of the paste in the kneading tank is adjusted. Therefore, 20 ° C. water was circulated through the kneading tank jacket. Pre-kneading was performed for 30 minutes, and when the respective components were mixed to some extent, kneading was interrupted once, and the paste adhering to the upper part of the kneading tank was scraped off using a rubber spatula.
Next, the inside of the kneading tank was decompressed (50 torr) and vacuum kneaded for 90 minutes to produce a curing agent paste. At this time, the temperature of the circulating water was adjusted as needed so that the temperature of the paste in the kneading tank was always 58 ° C. after the start of stable operation 5 minutes after the start of kneading. After completion of the kneading, the produced curing agent paste was collected, and vacuum-filled into an aluminum paste pack, and the curing agent paste was subdivided into each paste pack.

-Manufacturing method d-
A predetermined amount of each of the components listed in Table 1 above was weighed and charged into a kneading tank of “Aiko mixer” manufactured by Aiko Co., Ltd., which was equipped with a temperature sensor in the vicinity of the stirring blade in the kneading tank. Once mixed to some extent, kneading was interrupted once, and the paste adhering to the upper part of the kneading tank was scraped off using a rubber spatula.
Next, the inside of the kneading tank was decompressed (50 torr) and vacuum kneaded for 90 minutes to produce a curing agent paste. At this time, the temperature control of the paste in the kneading tank was not performed, and the temperature of the paste in the kneading tank was simply recorded. After completion of the kneading, the produced curing agent paste was collected, and vacuum-filled into an aluminum paste pack, and the curing agent paste was subdivided into each paste pack.

-Manufacturing method e-
A predetermined amount of each component shown in Table 1 above is weighed and charged into a kneading tank of an “Ico mixer” manufactured by Aiko Co., Ltd., in which a temperature sensor is attached in the vicinity of the stirring blade in the kneading tank, and the temperature of the paste in the kneading tank is adjusted. Therefore, 20 ° C. water was circulated through the kneading tank jacket. Pre-kneading for 30 minutes and once the components were mixed to some extent, kneading was interrupted once, and the paste adhering to the upper part of the kneading tank was scraped off using a rubber spatula.
Next, the inside of the kneading tank was decompressed (50 torr) and vacuum kneaded for 90 minutes to produce a curing agent paste. At this time, the temperature of the circulating water was adjusted as needed so that the temperature of the paste in the kneading tank was always 65 ° C. after the start of stable operation 5 minutes after the start of kneading. After completion of the kneading, the produced curing agent paste was collected, and vacuum-filled into an aluminum paste pack, and the curing agent paste was subdivided into each paste pack.

(Example 1)
(A) 3.5 kg of dihydrate gypsum as calcium sulfate, (B) 2.0 kg of liquid paraffin as a poorly water-soluble organic solvent, (C) 350 g of Dec-3O as a surfactant, 100 g of P3Na, 440 g of FTK, 600 g of MgO, 400 g of ZnO, 2.92 kg of diatomaceous earth, and 300 g of amorphous silica were weighed, and a curing agent paste was produced by “Production method a”. The produced hardener paste was collected and vacuum packed into an aluminum paste pack, and the hardener paste was subdivided into each paste pack.
Next, 1 kg of potassium alginate as (D) alginate, 18 kg of distilled water as (E) water, and 580 g of diatomaceous earth as an optional component are weighed, and reduced in pressure using an “Aiko mixer” manufactured by Aiko. The substrate paste was adjusted by kneading. After completion of the kneading, the base paste was recovered, vacuum filled into an aluminum paste pack, and the base paste was subdivided into each paste pack.
The obtained curing agent paste was used to evaluate “1. Moisture content in curing agent paste” and “presence / absence of solidification of curing agent paste during storage at 2.25 ° C.”.
Each paste pack (dental alginate impression material kit) filled with the adjusted curing agent paste and base paste was set in an alginate impression material automatic kneader (“AP mixer II” manufactured by Tokuyama Dental Co., Ltd.). Delivery pump for hardener paste and base paste so that the mixing ratio (mixing ratio Rm) is 0.54 (hardener paste / base paste = 1,061 / 1,958 [parts by weight / parts by weight]) The cured product was obtained by adjusting the voltage and discharging both pastes. The obtained cured product was used to evaluate “3. Elastic strain and permanent set of impression material”.

(Examples 2 to 8, Comparative Examples 1 to 4, Reference Examples 1 and 2)
The curing agent paste and the base material paste were adjusted in the same manner as in Example 1 except that the composition and manufacturing method of the curing agent paste were changed to the contents shown in Tables 2 and 3 below. It was used to evaluate “1. Moisture content in hardener paste” and “presence / absence of solidification of hardener paste during storage at 2.25 ° C.”. Further, the evaluation of “3. Elastic strain and permanent strain of impression material” was performed in the same manner as in Example 1 except that the mixing ratio of the curing agent paste / base material paste was changed to the contents shown in Table 4 below. It was.

(Evaluation results)
Table 2 below shows the compositions of the curing agent pastes according to Examples 1 to 8, Comparative Examples 1 to 4, and Reference Examples 1 and 2. Further, “1. Moisture content in the curing agent paste” and “Curing at 2.25 ° C.” in the curing agent pastes according to Examples 1 to 8, Comparative Examples 1 to 4 and Reference Examples 1 and 2. Tables 3 and 4 below show the evaluation results of “presence / absence of solidifying agent paste” and “3. Elastic strain and permanent strain of impression material”.

※二水石膏含有率：Ａ成分全体１００％に対する二水石膏の含有比率

* Dihydrate gypsum content: Content ratio of dihydrate gypsum to 100% of total component A

The curing agent pastes according to Examples 1 to 7 are not cured even after being stored at 25 ° C. for one year, and maintain good strain physical properties (elastic strain, permanent strain).
On the other hand, the curing agent pastes according to Comparative Examples 1 to 3 were manufactured at a paste temperature exceeding 60 ° C. during vacuum kneading. The moisture content exceeded 0.05 mass%, and the curing agent paste solidified when stored at 25 ° C. for 1 year.
The curing agent paste according to Comparative Example 4 was a case where calcium sulfate dihydrate was not blended, but even when mixed with the base paste, the gel strength of the alginate was greatly reduced and did not cure.
The hardener paste according to Example 8 is a case where the blending amount of calcium sulfate dihydrate in calcium sulfate is reduced, but although it can be mixed with the base paste to obtain a cured body, the alginate gel Strength is insufficient and strain physical properties are reduced.
The curing agent paste according to Reference Example 1 and Reference Example 2 is a case where the moisture contained in the curing agent paste is to be removed using a desiccant, but the moisture content in the curing agent paste is 0.05 mass. It can be seen that, in order to reduce the content to 50% or less, it is necessary to add 50 parts by mass or more of a desiccant to 100 parts by mass of calcium sulfate. In the curing agent pastes according to Reference Example 1 and Reference Example 2 in which a large amount of desiccant is blended, the gel strength of the alginate is insufficient and the strain physical properties are greatly reduced.

As mentioned above, although embodiment of this invention was described, this invention is not limited only to the above-mentioned embodiment, Of course, in the range which does not deviate from the summary of this invention, a various change can be added.

Claims (5)

(A) Calcium sulfate containing calcium sulfate dihydrate, (B) a hardly water-soluble liquid compound, and (C) a surfactant as main components, and a moisture content of 0.05% by mass or less paste. The hardener paste according to claim 1, wherein the calcium sulfate contains 5 mass% or more of calcium sulfate dihydrate. (A) Calcium sulfate containing calcium sulfate dihydrate, (B) a hardly water-soluble liquid compound, and (C) a surfactant,
A method for producing a curing agent paste, wherein the calcium sulfate, the hardly water-soluble liquid compound, and the surfactant are vacuum kneaded under a temperature condition not exceeding 60 ° C. (A) a hardener paste containing calcium sulfate containing calcium sulfate dihydrate, (B) a poorly water-soluble liquid compound, and (C) a surfactant, and having a moisture content of 0.05% by mass or less,
(D) a base paste containing alginate and (E) water as main components;
A dental alginate impression material kit. The dental alginate impression material kit according to claim 4, wherein the calcium sulfate contains 5 mass% or more of calcium sulfate dihydrate.