WO2014017360A1 - Hardening paste and kit for preparing alginate curable composition - Google Patents

Description

Hardener paste and alginate curable composition preparation kit

The present invention relates to a curing material paste and a kit for preparing an alginate curable composition, and more particularly, to prepare an alginate curable composition used for applications such as a dental alginate impression material and a domestic nipple pack. The present invention relates to a curing material paste used for the preparation, and an alginate curable composition preparation kit in which the curing material paste is used.

When a cast crown restoration process or a defect prosthesis process is required to restore a tooth or the like, first, a mold such as an abutment tooth is taken. 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.
A mold such as an abutment tooth is referred to as an impression, and a hardening material for obtaining an impression is referred to as 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, an impression material (that is, an alginate curable composition) in which each component constituting the alginate impression material is kneaded is placed on an impression tray simulating 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.

In use, the alginate impression material is used by kneading a gelling reagent such as alginate and calcium sulfate and water. Such alginate impression materials are classified into two types depending on the storage form.
One is a powder type in which the solid content excluding water is stored as a powder and kneaded with water at the time of use. The other is a paste (base paste) mainly composed of alginate and water and a paste (curing material paste) principally composed of a gelling agent. This is a paste type in which two types of paste are kneaded.

In the powder type alginate impression material, a skill of manual operation is required for the kneading operation.
In contrast, the paste type alginate impression material can be easily automated and labor-saving in the kneading operation by using a dedicated kneading device for kneading the base paste and the curing material paste. For this reason, in recent years, paste-type alginate impression materials are becoming popular in place of powder-type alginate impression materials.

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, during the kneading operation, the opening of the base paste packaging container is connected to the base paste inlet of the kneading apparatus, and the opening of the hardener paste packaging container is connected to the hardener paste inlet of the kneading apparatus. Connect to In this state, after the two types of paste supplied from the respective packaging containers into the kneading apparatus are automatically kneaded in the kneading apparatus, the kneaded product is discharged out of the kneading apparatus. Thereby, the user can obtain a kneaded material (curable composition) (for example, Patent Documents 1 to 3). Therefore, when performing such a kneading process, the paste in the packaging container is uniformly dispersed and has an appropriate fluidity so that the paste in the packaging container can be smoothly supplied into the kneading apparatus. It is necessary to have.

Especially, the hardener paste is a paste obtained by dispersing a large amount of powder components such as gypsum (calcium sulfate) in a solvent, and the dispersibility of the powder components is important. If the dispersibility is insufficient, the powder material and the liquid material are separated, which adversely affects the impression performance. Further, even if the powder component is sufficiently dispersed at the stage immediately after production, if the viscosity of the paste is low, the powder component will cause sedimentation during storage, resulting in a problem in storage stability. In order to suppress the sedimentation and separation of the powder component, it is conceivable to increase the viscosity of the paste. However, if the viscosity of the paste is increased, the paste cannot be discharged from the kneader. Thus, in the prior art, the storage stability of the paste (powder component sedimentation suppression) and the fluidity of the paste (dischargeability from the kneading apparatus) are not compatible, and even in a high viscosity state, There has been a strong demand for the development of a hardener paste that ensures fluidity.

A technique for blending a surfactant into a curing material paste is known. For example, in Patent Documents 4 and 5, from the viewpoint of improving miscibility with a base paste, a surfactant, specifically, a curing agent paste is used. Techniques for blending decaglycerin trioleate and the like are disclosed as examples. However, this document neither describes nor suggests the purpose of achieving both the above-described paste storage stability (inhibition of settling and separation of powder components) and paste fluidity, and in fact the interface specifically shown above. The activator had an HLB of 7.0, and the effect of improving the physical properties was not sufficient when these were used.

Moreover, the curable composition (alginate curable composition) like an alginate impression material is applied also to the use of a domestic nipple pack (refer patent document 6).
Such a nipple pack for livestock is used to prevent infection of livestock mastitis, and by applying a curable composition as described above to a nipple of livestock such as cattle, a cured film is formed. It protects the teats for a period of time during the dry period that is susceptible to mastitis. Thereby, invasion of the microbe from a teat can be prevented and the infection to a mastitis can be prevented.

In the paste type alginate curable composition used for such a nipple pack, the storage stability and fluidity of the curing material paste (miscibility between the curing material paste and the base paste) is the same as when used as an impression material. There is a need for improvement.

JP 2001-112785 A Japanese Patent Laid-Open No. 2001-200778 JP 2002-263119 A JP 2008-222672 A JP 2012-106937 A JP 2006-50911 A

The present invention aims to achieve both the storage stability (suppression of sedimentation of powder components) and the fluidity of the paste, both of which have been difficult in the past in the curing material paste used for the preparation of the alginate curable composition.

The present inventors have intensively studied to overcome the above problems. As a result, it discovered that the said subject could be solved by mix | blending a specific surfactant with a hardening material paste.

According to the present invention,
(A) calcium sulfate,
(B) a polyglycerol fatty acid ester having an HLB of 2.0 to 6.0,
(C) a hardly water-soluble dispersion medium,
There is provided a hardener paste characterized by comprising:

In the curing material paste of the present invention,
(1) The poorly water-soluble dispersion medium has a solubility in 100 g of water at 20 ° C. of 5 g or less,
(2) containing polyglycerol fatty acid ester (B) in an amount of 1 to 50 parts by mass per 100 parts by mass of calcium sulfate (A);
(3) containing the hardly water-soluble dispersion medium (C) in an amount of 10 to 200 parts by mass per 100 parts by mass of calcium sulfate (A);
(4) The polyglycerin fatty acid ester (B) is at least one selected from decaglycerin pentastearic acid ester, decaglycerin pentaisostearic acid ester, decaglycerin pentaoleic acid ester,
(5) The following formula (1);
TI = η _A / η _B (1)
In the formula, η _A is a shear rate of 0.1 / s using a cone plate viscometer.
Viscosity measured at (25 ° C.)
η _B is a shear rate of 1.0 / s using a cone plate viscometer.
Viscosity measured at (25 ° C.)
The thixotropy index TI defined by
Is preferred.

According to the present invention, there is also provided a kit for preparing an alginate curable composition comprising a base paste containing (D) alginate and (E) water and the above-mentioned curing material paste.
In such an alginate curable composition preparation kit, trehalose is preferably blended in at least one of the curing material paste and the base paste.

The alginate curable composition preparation kit is used for forming a dental alginate impression material or a domestic nipple pack.

The curing material paste of the present invention contains (B) a polyglycerin fatty acid ester having an HLB of 2.0 to 6.0 in addition to (A) calcium sulfate and (C) a poorly water-soluble dispersion medium. As a result, it has high thixotropy. For example, the thixotropy index TI defined by the formula (1) is 1.5 or more. Therefore, this hardening material paste has a high viscosity exceeding 1000 poise when left standing. For this reason, sedimentation separation of solid content (calcium sulfate) in the paste in a state of being sealed and stored in the packaging container can be suppressed over a long period of time. In addition, when a high load is applied to this curing material paste, the viscosity is greatly reduced, it exhibits high fluidity, and can be discharged smoothly and stably from a kneading device by extrusion or the like, and the miscibility with the base paste is also improved. It is good.

Therefore, the hardener paste of the present invention is prepared as an alginate curable composition comprising a container in which the hardener paste is packaged and a container in which a base paste containing (D) alginate and (E) water is packaged. Served as a kit for use.
That is, the curable composition prepared by using a kneading apparatus or the like with the curing material paste and the base paste contained in this kit is cured after a certain period of time. By making it caulk, the surface of a predetermined part can be reflected on the surface of the cured product. Therefore, such an alginate curable composition preparation kit is suitably used for an application as an impression material, and particularly suitable for use as a dental impression material.

Moreover, said alginate curable composition is applied suitably also for the use of a domestic nipple pack. That is, in the curable composition applied to the use of the domestic nipple pack,
(I) High film forming ability,
(Ii) great adhesion to the nipple surface;
(Iii) After the film is formed, it should not be overcured by calcium ions contained in the milk that exudes from the mouth of the nipple (if overcured, the film will be wrinkled and cracked, resulting in a protective effect on the nipple. Will be damaged)
(Iv) Easy to peel off after use,
However, the above-described alginate curable composition is also excellent in these characteristics.

In particular, in the nipple pack for livestock, the amount of the curable composition used for one film formation is significantly smaller than the amount used for one molding in the dental impression material described above. However, the curable paste of the present invention described above has high thixotropy, high fluidity at high loads, and extremely low fluidity at low loads. In either case, the amount can be adjusted easily and accurately. That is, the hardener paste of the present invention can be used for any application of a dental impression material and a domestic nipple pack, which is a great advantage of the present invention.

<Hardening material paste>
The curable material paste of the present invention is kneaded with a base paste containing alginic acid (D) and water, for example, an alginate curable composition applied to applications such as impression materials (especially for dental use) and livestock nipple packs. Is formed.
Such a hardening material paste contains calcium sulfate (A), polyglycerin fatty acid ester (B), and a hardly water-soluble dispersion medium (C) as essential components, and further contains other compounding agents that are blended as necessary. .
Hereinafter, each component mix | blended with a hardening material paste is demonstrated.

(A) calcium sulfate;
Calcium sulfate is a main component in the hardener paste, and is also a component called a gelling reagent. That is, this component reacts in the presence of water with an alginate in the base paste described later to form a cured product.
As calcium sulfate, dihydrate, hemihydrate, anhydrous salt, and the like are known. In the present invention, any of these can be used, and two or more can be used in combination.

The amount of calcium sulfate in the hardener paste is not particularly limited, but when kneaded with the base paste described later, for example, in terms of anhydrous salt per 100 parts by weight of alginate (A) in the base paste The hardener paste is used so that the amount of calcium sulfate is 10 to 2000 parts by mass, particularly 100 to 1000 parts by mass.

(B) polyglycerol fatty acid ester;
In the present invention, the polyglycerin fatty acid ester (B) is a nonionic surfactant for imparting thixotropy to this hardener paste, and particularly has an HLB (hydrophilic lipophilic balance) of 2.0 to 6.0. Those in range are selectively used. For example, when a nonionic surfactant whose anionic or cationic surfactant or HLB is outside the above range is used, the desired high thixotropic property is not exhibited.
Moreover, in the hardening material paste in which the polyglycerin fatty acid ester (B) having an HLB in the above range is used, it suppresses overcuring of the cured product obtained from the kneaded material with the base paste, and increases the film forming ability. It also has the advantage of being able to That is, since the flow of the poorly water-soluble dispersion medium (C) in the kneaded product of the hardener paste and the base material paste (aqueous alginate paste) described later becomes smooth, calcium sulfate (A) and alginate Since the curing with (D) proceeds uniformly over the entire kneaded product, local curing is prevented, and as a result, it is considered that overcuring is suppressed.

In the present invention, the HLB value is a value calculated by the Griffin method (WC Griffin, J. Soc. Cosmists., Chemists., 1, 311 (1949)) represented by the following mathematical formula.
HLB = 20 × (molecular weight of hydrophilic group part) / (molecular weight of surfactant)

Polyglycerin fatty acid ester is obtained by esterifying one or two or more hydroxyl groups of polyglycerol with fatty acid. The HLB of the polyglycerol fatty acid ester is comprehensively determined by the number of glycerin monomers, the number of esterified hydroxyl groups, and the type of constituent fatty acid. Generally, as the number of glycerin monomers increases, the HLB increases, and as the number of esterified hydroxyl groups increases, and as the number of carbon atoms of the constituent fatty acid increases, the HLB tends to decrease.

In the present invention, as long as the HLB is 2.0 to 6.0, the constituent fatty acid of the polyglycerol fatty acid ester is not particularly limited, and may be a saturated fatty acid or an unsaturated fatty acid. Generally, the constituent fatty acid has 15 to 22 carbon atoms, such as pentadecylic acid, palmitic acid, margaric acid, stearic acid, oleic acid, nonadecanoic acid, tuberculostearic acid, arachidic acid, eic acid, behenic acid, etc. Of these, those having 16 to 20 carbon atoms are more preferable, and stearic acid and oleic acid having 18 carbon atoms are most preferable from the viewpoint of dispersibility in the hardener paste.
The polyglycerin constituting the polyglycerin fatty acid ester is a dimer to 12mer, that is, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, hepta, as long as the HLB is within the above range. Glycerin, octaglycerin, nonaglycerin, decaglycerin, undecaglycerin, and dodecaglycerin are preferable. Among them, octamer to 10mer octaglycerin, nonaglycerin, and decaglycerin are preferable from the viewpoint of dispersibility in a hardener paste. More preferred.
Further, the number of esterified hydroxyl groups in polyglycerin is appropriately selected in order to obtain a desired HLB, although it depends on the number of glycerin monomers, and generally 1 to 8 substituted compounds are used. It is done.

Specific examples of the polyglycerol fatty acid ester having an HLB of 2.0 to 6.0 include, but are not limited to, the following, and these polyglycerol fatty acid esters include two types A combination of the above may also be used.
Pentaglycerol monopentadecyl ester Pentaglycerol monopalmitate Triglycerol monomargarate Diglycerol monostearate Diglycerol monooleate Diglycerol monoisostearate Tetraglycerol monostearate Tetraglycerol monooleate Hexaglycerol tristearate ester Decaglycerol pentastearate ester Decaglycerol pentaisostearate Decaglycerol pentaoleate Decaglycerol pentanonadecanoic acid Decaglycerol trieic acid ester Decaglyceryl tribehenate

Among the above-mentioned polyglycerin fatty acid esters, those having a range of HLB = 3.0 to 4.0 from the viewpoint of dispersibility of solid content (powder component) in the hardener paste, such as decaglycerin pentastearic acid ester (HLB = 3.5), decaglycerin pentaisostearate (HLB = 3.5), and decaglycerin pentaoleate (HLB = 3.5) are suitable.

The blending amount of the polyglycerin fatty acid ester is not particularly limited, but in order to express particularly high thixotropy, (A) 1 to 50 parts by weight, particularly 5 to 20 parts per 100 parts by weight of calcium sulfate (anhydrous salt equivalent). A range of parts by mass is preferred.

(C) a poorly water-soluble organic dispersion medium;
The poorly water-soluble dispersion medium used in the present invention is used for making a solid (powder material) containing calcium sulfate (A) into a paste. In this case, calcium sulfate (A) is cured (gelled) by reacting with water. Therefore, in order to prevent hardening of calcium sulfate during storage and to enhance storage stability over a long period of time, this dispersion medium is hardly water-soluble and has a water solubility of, for example, 5 g or less in 100 g of water at 20 ° C. It is necessary to be. The solubility is preferably 0.4 mg or less.

Such a poorly water-soluble organic dispersion medium should have such fluidity that the calcium sulfate powder can be made into a paste without inhibiting the hardening due to the reaction between calcium sulfate and alginate in the presence of water. Although not particularly limited, generally, hydrocarbon compounds, aliphatic alcohols, cyclic alcohols, fatty acids, fatty acid salts, fatty acid salt esters, hydrophobic polymers and the like are preferably used. These poorly water-soluble organic dispersion media may be used alone or in combination of two or more.
Hereinafter, suitable examples of these various poorly water-soluble dispersion media will be shown.

Examples of the hydrocarbon compound include aliphatic chain hydrocarbons such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, kerosene, 2,7-dimethyloctane, 1-octene, cycloheptane, Examples thereof include alicyclic hydrocarbon compounds such as 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 fatty acids 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 ester include ethyl octoate, butyl phthalate, oleic glyceride; vegetable oils such as olive oil and sesame oil; animal fats such as liver oil and whale oil;

Examples of the hydrophobic polymer include polysiloxane (so-called silicone oil). Typical examples of such polysiloxanes include polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, polyphenylhydrogensiloxane, and the like.

In the present invention, what is particularly suitable as the above-mentioned poorly water-soluble dispersion medium varies slightly depending on the application.
For example, when using a hardener paste for use as an impression material, particularly a dental impression material, it is listed above from the viewpoints of manufacturing cost, harm to the living body, influence on taste when taking impressions of teeth, etc. Among the poorly water-soluble dispersion media, it is preferable to use a hydrocarbon compound or a hydrophobic polymer, and it is most preferable to use liquid paraffin or silicone oil.
In addition, when using a curing material paste for uses such as a nipple pack for livestock, from the viewpoint of exhibiting the above-described over-curing suppression effect for a long period of time, those having a high boiling point among the above listed dispersion media are preferable, Those having a boiling point at 1 atm of 100 ° C. or more, particularly 150 to 600 ° C., such as octane, nonane, decane, 1-hexanol, oleic acid glyceride, liquid paraffin, silicone oil, etc. are preferable. Considering safety and the like, hydrocarbon compounds and hydrophobic polymers are preferable, and liquid paraffin and silicone oil are most preferable.

The blending amount of the hardly water-soluble dispersion medium is not particularly limited, but in general, it is preferably in the range of 10 to 200 parts by weight, particularly 20 to 100 parts by weight per 100 parts by weight of calcium sulfate (anhydrous salt). .

The curing material paste of the present invention containing each of the above components (A) to (C) exhibits high thixotropic properties, for example, has a high viscosity exceeding 1000 poise when left standing, and has a long time in a packaging container. Even when stored in a sealed state, sedimentation and separation of solid content (calcium sulfate) in the paste can be effectively suppressed, and when a high load is applied to this hardener paste, the viscosity is greatly reduced and high fluidity is exhibited. .
For example, the curing material paste of the present invention has the following formula (1) by appropriately selecting the type and blending amount of each component described above.
TI = η _A / η _B (1)
In the formula, η _A is a shear rate of 0.1 / s using a cone plate viscometer.
Viscosity measured at (25 ° C.)
η _B is a shear rate of 1.0 / s using a cone plate viscometer.
Viscosity measured at (25 ° C.)
The thixotropy index TI defined by can be adjusted to 1.5 or more, particularly 1.8 or more, and most preferably 2.0 or more.

<Base material paste>
The base material paste which is kneaded with the above-described curing material paste to form a curable composition contains an alginate (D) and water (E) as essential components.

(D) alginate;
As already mentioned, alginate is a component that reacts with calcium sulfate (A) in the above-mentioned hardener paste in the presence of water to form a cured product, and is known per se, for example,
i) Alginate alkali metal salts such as sodium alginate and potassium alginate,
ii) ammonium alginate such as ammonium alginate, triethanolamine alginate,
Etc. can be used.
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, two or more types of alginate can be mixed and used.
The molecular weight of the alginate is not particularly limited, but in general, the molecular weight is preferably such that the viscosity of the aqueous solution containing 1% by weight of the alginate is in the range of 50 cps to 100 cps (23 ° C.).

(E) water;
Water is a component necessary for the curing reaction (gelation) of calcium sulfate (A) and alginate (D), and tap water, ion-exchanged water, distilled water, and the like are used.
The amount of water used is preferably in the range of 100 to 4000 parts by weight, particularly 500 to 2000 parts by weight per 100 parts by weight of alginate.
In addition, this water can also mix | blend the one part quantity (for example, 1000 mass parts or less) at the time of kneading | mixing a base material paste and a hardening material paste.

Such a base paste has a mass ratio (A / D) in terms of anhydrous salt of calcium sulfate (A) in the hardener paste and alginate (D) in the base paste of 10/100 to 2000. / 100, particularly 100/100 to 1000/100, and is used after being kneaded with a hardener paste.

<Other ingredients>
In the present invention, various additives can be blended in any of the curing material paste and the base paste in accordance with the use and required characteristics within a range not impairing the above-described high thixotropy.

A typical example of such an additive is a masking agent.
The masking agent is used particularly when an alginate curable composition comprising a kneaded material of the above-described curing material paste and base paste is applied to a dental impression material. This impression material (alginate curable composition) Is used to suppress discomfort given to the patient when the product is inserted into the patient's mouth.
That is, since the above-mentioned polyglycerin fatty acid ester (B) is contained in the impression material inserted into the oral cavity, when this is inserted into the oral cavity, the patient feels a unique taste (bitterness, astringency). There is a case. By relieving such a unique taste with a masking agent, discomfort given to the patient is suppressed.

Examples of such masking agents include sweeteners such as aspartame, sucralose, thaumatin, stevia, maltitol, erythritol, xylitol, sorbitol, palatinose, and trehalose; And oligosaccharides such as dextrin, β-cyclodextrin, γ-cyclodextrin and the like. Among them, saccharides such as stevia, xylitol, and trehalose are preferable from the viewpoint of alleviating the bitter taste of polyglycerin fatty acid ester and anti-caries.

In addition, when a disaccharide such as trehalose is used among the above saccharides, there is an advantage that in addition to the masking effect, the impression accuracy is improved and the drying resistance of the cured product after taking the impression is improved. That is, trehalose has a skeleton similar to alginic acid and has high hydrophilicity, and therefore enters in a state where water is retained in the molecular chain space of the impression material cured product. As a result, shrinkage of the cured body due to molecular chain aggregation is suppressed, and the evaporation of moisture due to drying is effectively suppressed by trehalose, resulting in improved drying resistance and effectively preventing deformation of the cured body due to drying. Thus, high impression accuracy can be maintained.

Although the compounding quantity of a masking agent is not specifically limited, In order to exhibit a masking effect (effect which reduces bitterness and astringency) satisfactorily, it is 0.5 mass with respect to 100 mass parts of polyglyceryl fatty acid ester (A). It is preferable to blend at least part. Further, even if a masking agent is added in a certain amount or more, there is no particular problem, but the masking effect is saturated. Therefore, the masking agent is preferably used in the range of 0.5 to 500 parts by mass, more preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the polyglycerol fatty acid ester.
In addition, when trehalose is used and importance is attached to the effect of improving the impression accuracy and the improvement of drying resistance, the amount of trehalose used is 100 to 2000 parts by mass, particularly 400 to 1200 parts by mass, per 100 parts by mass of alginate. It is preferable that the amount is within the range used.

Furthermore, the non-reducing sugars (non-reducing sugars) exemplified in the masking agent exemplified above enter the intramolecular chain space of the cured product while retaining moisture, so that the cured product has elasticity. Furthermore, since the drying of moisture is also suppressed, the elasticity of the cured body can be maintained over a period of time required for a teat pack, for example. Therefore, the use of such a non-reducing sugar is extremely effective for the use of a nipple pack, and can form a nipple pack (cured film) that adheres well to the nipple for a period of time to prevent infection.

In addition, the saccharide | sugar (non-reducing saccharide | sugar) which does not show reducibility means the property which does not show a reducing action with respect to heavy metal ions, such as silver and copper, in alkaline aqueous solution. That is, reducing saccharides are detected by a Torens reagent, a benectin reagent or a Fering reagent using a reducing action on heavy metal ions, but non-reducing sugars cannot be detected by these reagents. For example, among the aforementioned masking agents, oligosaccharides and disaccharides (for example, trehalose and sucrose) are applicable. In particular, trehalose is also optimal for nipple pack applications.
The amount of non-reducing sugars suitable for use in such nipple packs is preferably in the range of 100 to 2000 parts by weight, particularly 400 to 1200 parts by weight per 100 parts by weight of alginate.

The above-mentioned masking agent and non-reducing sugar may be blended in either or both of the hardener paste and the base paste, but it is preferable to blend in the base paste from the viewpoint of solubility in water.

Furthermore, examples of the additive other than the masking agent and the non-reducing sugar include a gelling regulator and a filler.
These additives can be appropriately added to either one or both of the base paste and the curing material paste. However, among these, the filler is preferably added to both the base paste and the curing material paste, and the gelling modifier is preferably added to the curing material paste.

The gelation modifier can adjust (delay) the reaction rate (curing rate) between the alginate and the gelling agent. For this reason, in the use of dental impression materials, the work time required from the preparation of an alginate curable composition (impression material), which is a kneaded product of a hardener paste and a base paste, to taking an impression in the oral cavity is reduced. The curing time can be adjusted so that it can be ensured. Moreover, in the use of a nipple pack, the curing time can be adjusted so as to ensure the working time until it is applied to the nipple of livestock.

As the gelation modifier, a known gelation modifier can be used without limitation. For example, typical gelation modifiers are:
a) trisodium phosphate, tripotassium phosphate, sodium pyrophosphate,
Phosphates containing alkali metals such as sodium tripolyphosphate,
b) oxalates containing alkali metals such as sodium oxalate and potassium oxalate;
c) carbonates containing alkali metals such as sodium carbonate and potassium carbonate;
These are used singly or in combination of two or more.

The blending amount of the gelling modifier can be appropriately selected according to other blending components and required curing time, but generally 1 to 30 parts by weight, particularly 3 to 15 parts per 100 parts by weight of alginate. More preferably within the range of parts by mass. By setting the blending amount of the gel modifier within the above range, it becomes easy to adjust the curing time substantially corresponding to the work time until the cured body (impression mold and nipple pack) is formed, and effective curing is effective. Can be prevented.

Moreover, a filler is used in order to adjust the physical property of hardened | cured material.
As such a filler, viscous minerals such as diatomaceous earth and talc are typical, but oxides such as silica and alumina can also be used. The blending amount of the filler is not particularly limited, but is preferably in the range of 50 to 2000 parts by mass, more preferably in the range of 100 to 1000 parts by mass per 100 parts by mass of the alginate.

In addition, in the use of impression materials, inorganic fluorine compounds such as potassium titanium fluoride and potassium silicofluoride, as well as oxidation from the viewpoint of adjusting the strength of the cured body and preventing the surface of the gypsum model from being roughed during impression collection and gypsum model manufacture. Metal oxides such as magnesium and zinc oxide, and amino acid compounds such as amino acid / formaldehyde condensates can be used. These additives can also be used for adjusting the strength of the cured body in the application of nipple packs.
Such an additive can also be blended in both the base paste and the curing material paste.

Further, when the base paste and the curing material paste are mixed and kneaded, an unsaturated carboxylic acid polymer is preferably blended in order to easily control the rate of change in viscosity. Moreover, any 1 type or multiple types of additive selected from a fragrance | flavor, a coloring agent, a pH adjuster, an antibacterial agent, antiseptic | preservative, etc. can be mix | blended as needed.
Furthermore, in addition to the above additives, a fragrance, a colorant, an antibacterial agent, an antiseptic, a pH adjuster, and the like can be appropriately blended.
These additives can also be blended in both the base paste and the curing material paste.

The above-mentioned hardener paste and base paste can be manufactured using a known stirring mixer that can be used for paste manufacture. As such a stirring mixer, for example, a rotating container type mixing and kneading machine such as a ball mill; a horizontal mixer, a kneader, an internal mixer, a screw kneader, a Henschel mixer, a universal mixer, a Ladige mixer, a butterfly mixer, etc. A fixed container type mixing and kneading machine having an axis or a vertical axis can be used.

<Curable composition preparation kit>
The curable material paste of the present invention is kneaded with a base material paste immediately before use, and this kneaded product (alginate curable composition) is applied to an impression material or a teat pack, and an appropriate amount of water (E ) Can be replenished.

However, generally, it is divided into a packaging container containing a curing material paste and a packaging container containing a base paste, and is sold and used as a curable composition preparation kit. That is, a general user takes out a predetermined amount of a curing material paste and a base paste from these packaging containers according to the use, kneads them, and prepares an alginate curable composition according to the use. Is applied to a predetermined part to form a cured body according to the application.

In such a curable composition preparation kit, the mixing ratio Rm (X / Y) of the base paste (X) and the curing material paste (Y) is generally set in the range of 1 to 4 on a mass basis. It is preferable to keep it. That is, when the base paste and the hardener paste are kneaded at such a mixing ratio Rm, the quantitative ratio of each component, for example, the quantitative ratio of calcium sulfate (A) and alginate (D) is within the predetermined range described above. The blending composition of the curing material paste and the base material paste is set so as to be inside.
As a matter of course, the above-mentioned mixing ratio Rm must be displayed as information to the user in accordance with the product package or the instruction manual.

Kneading of the basic paste and the curing material paste can be performed using a known mixing stirrer, but in general, automatic paste kneading that can automatically knead two pastes at a constant ratio. It is preferable to use an apparatus. That is, the hardener paste of the present invention has high thixotropy and exhibits high fluidity when a large load is applied. Therefore, the discharge amount and the like can be controlled with high accuracy, and kneading with the base paste is also possible. This is because it can be easily performed.

Typical examples of the automatic paste kneading apparatus as described above are those sold by Tokuyama Dental Co., Ltd. under the trade name “Tokuyama AP Mixer”, and further, Japanese Patent Application Laid-Open Nos. 4-250838 and 5-103967. JP-A-8-24273, JP-A-8-140998, JP-A-9-276295, JP-A-2000-116675, JP-A-2001-112785, JP-A-6-57422, JP-A-6-61246, Automatic kneading apparatuses proposed by Japanese Utility Model Laid-Open Nos. 6-18684, 2000-140600, 2001-299778, and the like can also be used.

The kneaded product of the base paste and the curing material paste obtained as described above, that is, the alginate curable composition, is applied to a predetermined part according to the use, and the curing is completed in this state. The time from the time of kneading to the completion of curing (curing time) is set to an appropriate time depending on the use by using the above-mentioned gelation regulator, etc., but generally 1 to 10 minutes, especially 2 About 8 minutes.

For example, when a kneaded product is used as an impression material, the kneaded product (alginate curable composition) is placed on a dedicated tray, and the kneaded product placed on the tray is pressed against an object such as a tooth. Take an impression on things. Thereafter, the kneaded material having the collected impression is cured, and post-processes such as making a plaster model based on the cured product are performed.

The tray used for placing the kneaded material is not particularly limited, but generally a metal or resin-made tray is used. As the metal, stainless steel, tin alloy, aluminum, brass which is plated or resin-coated, or the like is used. As the resin, polymethacrylic acid ester is representative.

On the other hand, when the kneaded product is applied to a teat pack, the kneaded product may be applied to a domestic teat by a dipping method, a brush coating method, a spraying method or the like and cured to form a cured film.
Thereby, about the livestock for milking, such as a cow and a goat, the infection to the mastitis etc. from a teat can be prevented effectively.

The excellent effects of the present invention will be described by the following experimental examples.
In the following experimental examples, Experiment I is an evaluation for a dental impression material, and Experiment II is an evaluation for a domestic nipple pack.

<Abbreviations for raw materials>
Abbreviations of various raw materials used in experimental examples to be described later are as follows.
1. Alginate;
Alg-K:
Potassium alginate (1% aqueous solution viscosity (20 ° C) 600 mPa · sec)
Alg-Na:
Sodium alginate (1% aqueous solution viscosity (20 ° C.) 120 mPa · sec)

2. Polyglycerol fatty acid ester;
HGSE:
Hexaglycerin tristearate (HLB = 2.5)
DGSE:
Decaglycerin pentastearate (HLB = 3.5)
DGISE:
Decaglycerin pentaisostearate (HLB = 3.5)
DGOE:
Decaglycerin pentaoleate (HLB = 3.5)
DIGMOE:
Diglycerin monooleate (HLB = 5.5)
DGMRE: (Comparison)
Decaglycerin monolaurate (HLB = 15.5)
DGTOE: (Comparison)
Decaglycerin trioleate (HLB = 7.0)
DGTSE: (Comparison)
Decaglycerin tristearate (HLB = 7.5)

3. Poorly water-soluble dispersion medium;
Liquid paraffin viscosity (20 ℃) 150mPa ・ sec
Solubility in water <0.001 mg / L (almost insoluble)
Boiling point 450 ° C (1 atm)
SO:
Silicone oil (polydimethylsiloxane)
Viscosity (20 ° C) 300 mPa · sec
Solubility in water <0.001 mg / L (almost insoluble)
Boiling point 250 ° C (1 atm)

4). Non-reducing sugars;
Cdex-α:
α-Cyclodextrin Cdex-β:
β-cyclodextrin

5. Other;
P3Na:
Trisodium phosphate FTK:
Potassium titanium fluoride MT-10:
Amorphous silica with a particle size of 0.02 μm (treated with methyltrichlorosilane)
SG:
Glyceryl stearate (HLB = 3.0)
MSPG:
Propylene glycol monostearate (HLB = 3.5)

<Measurement or evaluation method>
Measurements or evaluations of various physical properties of samples prepared in the following experimental examples were performed by the following methods.

(1) Curing material paste viscosity;
After the prepared hardener paste (about 240 ml) was put into a glass beaker (capacity: 300 ml), the beaker was left in an incubator set at a temperature of 25 ° C. for about 1 hour.
Thereafter, the viscosity (initial viscosity V, Poise) of the curing material paste was measured using a rotary viscometer (Viscotester VT-04F manufactured by RION) in an incubator.
Next, the prepared hardener paste was filled in an aluminum paste pack, and stored in an incubator set at a temperature of 25 ° C. with the paste outlet facing up. When a predetermined period (one year and two years later) has elapsed, the curing material paste is removed from the paste outlet (about 240 ml), and the viscosity of the curing material paste (viscosity after storage) is determined in the same manner as described above. V1, V2, Poise) were measured.

(2) Thixotropic index TI;
Place an appropriate amount of the adjusted curing material paste on a cone plate viscometer (CS rheometer CVO120HR manufactured by BOHLIN), start measuring viscosity while maintaining at 25 ° C, and start measuring at shear rate 0.1 / s The viscosity (η _A ) after 60 seconds was measured. Next, the viscosity (η _B ) 60 seconds after the start of measurement at a shear rate of 1.0 / s was measured by the same method. The viscosity was measured under the conditions that the cone diameter was 2 cm and the cone inclination angle was 1 °. The viscosity was substituted into the following formula (1) to calculate the thixotropy index (TI).
TI = η _A / η _B (1)

(3) Curing material paste discharge amount for 10 seconds;
As an automatic paste kneading apparatus, “AP mixer II” manufactured by Tokuyama Dental Co., Ltd. was prepared.
In this kneading apparatus, a pack (paste pack) filled with the prepared curing material paste is set, the pump is operated for a while, the paste is filled inside the mixer in the apparatus, the curing material pump is started for 10 seconds, The weight of the curable material paste discharged during that time (initial amount of curable material paste discharged for 10 seconds) was measured.
On the other hand, the paste pack was stored in an incubator in which the temperature was set to 25 ° C. with the paste take-out port directed downward. When a predetermined period (one year and two years later) passed, the 10-second discharge amount of the cured material paste after storage was measured by the same method as described above.

(4) Impression accuracy (fine line reproducibility);
In the above automatic paste kneading apparatus, the cured material paste pack and the substrate paste pack filled with the prepared curing material paste or the substrate paste were set.
The kneaded product (impression material paste) obtained from this kneading apparatus was subjected to a fine line reproducibility test in accordance with the method described in JIST6513.
In other words, the impression material paste is placed on a fine wire reproducibility test mold with thin lines with a width of 50 μm and a width of 20 μm, left in 35 ° C. water for 6 minutes, the cured impression material is removed, and plaster is placed on the impression surface. It was kept in 100% humidity for 1 hour, and it was observed using a microscope whether thin lines having a width of 50 μm and a width of 20 μm were reproduced on the impression surface of the cured gypsum, and evaluated according to the following evaluation criteria.
Fine line reproducibility evaluation criteria;
A: A fine line having a width of 20 μm is reproduced without interruption.
○: A thin line having a width of 50 μm is reproduced without interruption.
Δ: A thin line having a width of 50 μm is confirmed, but is broken in some places.
X: A thin line having a width of 50 μm cannot be confirmed.

Next, the curing material paste pack was stored in an incubator set at a temperature of 25 ° C. with the paste outlet opening upright.
When a predetermined period (one year later, two years later) has passed, the hardener paste is set again in the automatic paste kneader, and the impression accuracy (thin line reproducibility) of the hardener paste after storage in the same manner. Evaluated.

(5) Evaluation of relaxation for bitterness and astringency A curing material paste pack and a base material paste pack were set in the paste automatic kneading apparatus.
The paste in which the hardener paste and the base material paste were kneaded was discharged onto a metal tray for taking an upper jaw impression, and the upper jaw impressions of 10 subjects were taken by a normal method. During the impression taking process, the degree of bitterness and astringency was evaluated according to the following criteria.
Criteria for bitterness and astringency;
○: No subject who confirmed that they were concerned about bitterness and astringency was confirmed.
Δ: There were 1 to 3 subjects who answered that they were concerned about bitterness and astringency.
X: There were 5 or more subjects who answered that they were concerned about bitterness and astringency.

<Experiment I>
(Example 1)
As calcium sulfate (A), 25 g of calcium sulfate anhydrous salt (anhydrous gypsum) and 10 g of calcium sulfate dihydrate (dihydrate gypsum), as polyglycerol fatty acid ester (B), 3.5 g of HGSE, poorly water-soluble dispersion As a medium (C), 20 g of liquid paraffin was weighed and kneaded for 1 hour using a small kneader (Aiko mixer manufactured by Aiko Sangyo Co., Ltd.) to prepare a hardener paste.
With respect to the obtained hardener paste, the viscosity, the thixotropy index TI, and the discharge amount for 10 seconds were evaluated.

Further, 10 g of Alg-K as the alginate (D) and 180 g of distilled water as the water (E) were weighed and stirred for 1 hour using a small kneader to prepare a base paste.
The whole amount of the base paste and the curing material paste was kneaded using the above-described automatic paste kneader, and the obtained kneaded product was evaluated for impression accuracy (thin line reproducibility).
Further, after the preparation, the same evaluation was performed on the curing material paste stored in a 25 ° C. incubator for 1 year and 2 years, respectively.

(Examples 2 to 11)
Except for changing the composition of the hardener paste or base paste as shown in Table 1, the hardener paste, base paste and kneaded material were prepared in the same manner as in Example 1, and various measurements were performed.

(Comparative Examples 1 to 6)
Except having changed the composition of the hardening material paste as shown in Table 2, the hardening material paste, the base material paste, and the kneaded material were prepared in the same manner as in Example 1, and various measurements were performed.

For Examples 1 to 11 and Comparative Examples 1 to 6, the composition of the curing material paste and the base material paste, and the mixing ratio Rm of the base material paste and the curing material paste are shown in Table 1 or Table 2, and the curing material paste viscosity, Tables 3 and 4 show the evaluation results of the discharge amount of the curing material for 10 seconds and the impression accuracy (thin line reproducibility).
Moreover, the thixotropy index TI of the hardening material paste in each Example and Comparative Example was as follows.





Example 1: 1.56
Example 2: 2.12
Example 3: 2.13
Example 4: 2.20
Example 5: 1.55
Example 6: 2.01
Example 7: 2.08
Example 8: 1.93
Example 9: 2.89
Example 10: 3.81
Example 11: 1.82
Comparative Example 1: 1.02
Comparative Example 2: 1.04
Comparative Example 3: 1.34
Comparative Example 4: 1.14
Comparative Example 5: 1.08
Comparative Example 6: 1.09

The curing material pastes of Examples 1 to 11 satisfy all the requirements of the present invention, but good initial impression accuracy could be obtained by kneading with the base material paste.
In addition, these pastes have a very high thixotropy (thixotropy index of 1.5 or more) and good fluidity (10-second discharge rate) despite their very high viscosity. I understand. In addition, even after these curing material pastes are stored for a long period of time, no significant fluctuations in viscosity and fluidity (10-second discharge amount) are observed, the initial values are maintained, and good impression accuracy is obtained. Yes.

In Example 7, trehalose was blended in an amount of 550 parts by mass per 100 parts by mass of alginate, but a better result was obtained in terms of impression accuracy compared to other impression materials. In addition, bitterness and astringency were sufficiently relaxed.

On the other hand, Comparative Example 1 does not contain a polyglycerin fatty acid ester having an HLB of 2.0 to 6.0. For this reason, if the curing material paste is left for a long period of time, the powder component in the curing material paste settles and separates, so that the viscosity of the curing material paste is increased and the fluidity (10-second discharge amount) is greatly reduced. Is no longer available.

In addition, the curing material pastes of Comparative Examples 2 to 4 contain a polyglycerin ester, but all have an HLB outside the range of 2.0 to 6.0. For this reason, none of the hardener pastes can obtain sufficient thixotropy, and when left for a long period of time, its viscosity increases and fluidity (10-second discharge rate) is greatly reduced, resulting in improved impression accuracy. It is no longer available.

Comparative Examples 5 and 6 are cases where a surfactant other than polyglycerin fatty acid ester is used, but in any case, sufficient thixotropy cannot be obtained and the curing material paste is left for a long period of time. In addition, the viscosity is increased and the fluidity (10-second discharge amount) is greatly reduced, making it impossible to obtain impression accuracy.

(Examples 12 to 14 and Reference Examples 1 and 2)
Except for changing the composition of the hardener paste or base paste as shown in Table 5, the base paste and the hardener paste were adjusted in the same manner as in Example 1 to evaluate the bitterness and astringency at the time of impression taking. went. Table 5 shows the composition and results of the impression material.

Examples 12 to 14 are examples in which a masking agent (trehalose or xylitol) was blended in the base paste, but no bitterness or astringency was felt when taking an impression.

On the other hand, in Reference Example 1 and Reference Example 2, since the masking agent was completely blended, there were people who felt bitterness and astringency during impression collection.

<Experiment II>
The following experiment was conducted in order to show the effect when the alginate curable composition obtained from the curing material paste of the present invention was applied to a teat pack.
In this experiment, various measurements and evaluations were performed by the following methods.

(1) Overcurability evaluation (visual evaluation, dimensional distortion)
The curing material paste and the base paste are weighed into a kneading cup, and kneaded using a spatula so that no bubbles are mixed to prepare a mixed paste (curable composition).
This mixed paste is filled in a Teflon (registered trademark) mold placed on an acrylic plate, and further, the acrylic plate is pressed on the top surface of the filled mixed paste, and the pressed acrylic plate is fixed using a clip, After leaving for 3 minutes, the cured product (gel product) was removed from the mold to prepare a sample piece (width: 57 mm, length: 19 mm, height: 3 mm).
Immediately after the preparation of the sample piece, the dimensions (horizontal, vertical, height) of the sample piece were measured using a measuring microscope (“STM6” manufactured by Olympus), and the initial volume (V1 / mm ³ ) of the sample piece was calculated. .

Next, wrap the sample piece with a cloth soaked with emulsion (freshly squeezed raw milk), store it in a 25 ° C. incubator, take out the sample piece after one day, and check the surface condition according to the following evaluation criteria. Visual evaluation was made.
Overcured visual evaluation criteria;
○: Wrinkles and cracks are not seen at all, and it is indistinguishable from the initial state.
Δ: Wrinkles can be confirmed, which is different from the initial state.
×: Innumerable wrinkles were confirmed, cracks were also confirmed, clearly different from the initial state.

Moreover, the dimension (width, length, height) of the sample piece was measured by the same method as the initial stage, and the volume (V2 / mm ³ ) after 1 day was calculated. The dimensional strain was calculated by the following formula.
Dimensional strain (%) = (V1-V2) / V1 × 100
The sample piece is again wrapped in a cloth soaked with emulsion (freshly squeezed raw milk), stored in a 25 ° C. incubator, and overcurability (visual evaluation, (Dimensional distortion) was evaluated.

(2) Hardened body elasticity evaluation (elastic strain);
(2-1) Measurement of initial elastic strain A mixed paste (curable composition) of a curing material paste and a base paste is prepared in the same manner as in the case of overcuring evaluation.
After placing the plastic ring A (inner diameter 31 mm, outer diameter 38 mm, height 16 mm) on the upper surface of the acrylic plate (length 45 mm × width 45 mm), the above-mentioned mixed paste is filled in the plastic ring A and simultaneously with this filling. Time measurement started.
Furthermore, after filling the plastic ring A with the mixed paste, immediately after inserting a small plastic ring B (inner diameter 13 mm, outer diameter 25 mm, height 20 mm) into the plastic ring A, the plastic ring B is inserted into the plastic ring B. The above mixed paste was filled.

Next, after pressing the upper surface of the plastic ring B with another acrylic plate, the plastic ring B and the two acrylic plates arranged at both ends thereof were sandwiched and fixed with a small vise.
Then, 30 seconds after the start of time measurement, the plastic ring B (with the mixed paste filled inside), both ends of which are pressed and fixed by an acrylic plate with a vise, is placed in an incubator at 25 ° C., The plastic ring B was taken out 15 minutes after being put in the incubator (15 minutes and 30 seconds after the start of time measurement). Thereby, a columnar cured material sample cured in the plastic ring B was obtained.

Next, a compression tester (made by Nippon Mec Co., Ltd., impression material elasticity comparison tester A-002) is prepared.
The columnar cured material sample obtained above is set in a compression tester so that a load is applied from the central axis direction of the sample, and after 16 minutes have elapsed from the start of time measurement, the compression test is performed according to the following procedure. did.

First, at the same time as applying a load of 100 gf / cm ² to the cured product sample, time measurement is started from this point (at the start of the compression test).
The dial gauge value A (mm) after 30 seconds from the start of the compression test was read. Further, during the period from the start compression tests up to 60 seconds to 70 seconds, a load to be applied to the cured product samples were increased from 100 gf / cm ² to 1000 gf / cm ^2, further elapses 70 seconds to 100 seconds In the meantime, the load applied to the cured sample was kept at 1000 gf / cm ² .
And the value B (mm) of the dial gauge when 100 seconds passed from the start of the compression test was read.

From the read dial gauge values A and B, elastic strain (εe) was calculated by the following equation.
Elastic strain (εe) = (AB) / 20 × 100 (%)
And the average value of each elastic strain obtained by implementing the same evaluation 3 times about the same hardened | cured material sample was made into the elastic strain (initial stage) of hardened | cured material.

(2-2) Measurement of elastic strain after storage for a predetermined period From a mixed paste (curable composition) of a curing material paste and a base paste, a cylindrical cured product by the same method as the initial elastic strain measurement method A sample was obtained. The cured product sample was stored in a 25 ° C. incubator for a predetermined period.
After a predetermined period, the cured product sample was taken out from the incubator, and the elastic strain (εe) after the predetermined period was obtained by the same measurement method as the initial elastic strain. And the average value of each elastic strain obtained by implementing the same evaluation 3 times about the same gelled material sample was made into the elastic strain (after storage) of hardened | cured material.

(Example 1)
Weigh 100 g of Alg-K as the alginate (D), 1500 g of distilled water as the water (E), 600 g of trehalose as the non-reducing sugar (F), and 295 g of diatomaceous earth as the other components. A base paste was prepared by kneading for 1 hour using an Aiko mixer.
On the other hand, each component was kneaded for 1 hour using the above-mentioned small kneader to prepare a hardener paste.
Hardener paste formulation;
Calcium sulfate (A): 400 g of anhydrous gypsum Polyglycerin fatty acid ester (B): 40 g of DGSE
Slightly water-soluble dispersion medium (C): 200 g of fluid P1
Other ingredients:
60g MgO
40g FTiK
40 g ZnO
8g P3Na
55g diatomaceous earth 30g MT-10

The obtained hardener paste had a thixotropy index TI of 2.14.

The above base paste and curing material paste are kneaded with an automatic kneader (using “AP mixer III” discharge range 3 manufactured by Tokuyama Dental Co., Ltd.) at a kneading ratio Rm = 2.86, and a curable composition for nipple packs. The curable composition was subjected to overcurability evaluation and cured body elasticity evaluation.
The composition of the base paste and the curing material paste is shown in Table 6, and the evaluation results of the cured composition are shown in Table 7.

(Examples 2 to 6)
A curable composition for teat packs was prepared in the same manner as in Example 1 except that the composition of the curing material paste and the base paste, or the kneading ratio of both pastes was changed as shown in Table 6, and was overcured. Evaluation and cured body elasticity evaluation were performed, and the results are shown in Table 7.

In the curable composition for teat packs in these examples obtained by kneading the curing material paste of the present invention with the base paste, overcuring of the surface of the cured body when contacted with an aqueous solution containing calcium ions is suppressed. Good condition was maintained for more than 4 days. Moreover, the elasticity of the cured body was kept in a good state for 5 days or more.

Claims (10)

(A) calcium sulfate;
(B) a polyglycerol fatty acid ester having an HLB of 2.0 to 6.0;
And (C) a hardly water-soluble dispersion medium;
A hardening material paste characterized by containing. The hardener paste according to claim 1, wherein the poorly water-soluble dispersion medium has a solubility in 100 g of water at 20 ° C of 5 g or less. The hardener paste according to claim 1, comprising polyglycerin fatty acid ester (B) in an amount of 1 to 50 parts by mass per 100 parts by mass of calcium sulfate (A). The hardening material paste according to claim 1, comprising the hardly water-soluble dispersion medium (C) in an amount of 10 to 200 parts by mass per 100 parts by mass of calcium sulfate (A). The curing material paste according to claim 1, wherein the polyglycerin fatty acid ester (B) is at least one selected from decaglycerin pentastearic acid ester, decaglycerin pentaisostearic acid ester, and decaglycerin pentaoleic acid ester. Following formula (1);
TI = η _A / η _B (1)
In the formula, η _A is a viscosity (25 ° C.) measured at a shear rate of 0.1 / s using a cone plate viscometer,
η _B is a viscosity (25 ° C.) measured at a shear rate of 1.0 / s using a cone plate viscometer.
The hardener paste according to claim 1, wherein the thixotropy index TI defined by is 1.5 or more. (D) alginate;
And (E) water;
A kit for preparing an alginate curable composition, comprising: a base material paste comprising: and a curing material paste according to claim 1. The alginate curable composition preparation kit according to claim 7, wherein trehalose is blended in at least one of the curable material paste and the base paste. The alginate curable composition preparation kit according to claim 7, which is used for forming a dental alginate impression material. The kit for preparing an alginate curable composition according to claim 7, which is used for forming a nipple pack for livestock.