JPS615A - Impression material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to an impression material mainly composed of alginate.

Impression materials made by adding hardening agents such as calcium sulfate and fillers such as diatoms to alginate are called alginate-based impression materials or alginate impression materials, and are mainly used for tooth molding during dental treatment and restoration. It is used for taking. The above alginate-based impression materials have good impression accuracy.
It has characteristics such as being able to reproduce minute details and being easy to manipulate for impressions, and is most commonly used as a dental impression material.

However, alginate-based impression materials have the disadvantage of poor storage stability due to moisture in the atmosphere and raw material powder during manufacture and moisture taken in from the atmosphere after opening. That is, the gelation time and the elasticity after gelation change over time due to the presence of water. Therefore, when manufacturing alginate-based impression materials, the utmost care must be taken to control the moisture content in the raw material powder and the humidity within the manufacturing facility during the rainy season and during hot and humid times. Furthermore, before a user can use the product, the product must be tightly sealed and stored in a place with good humidity, and it must be used up as quickly as possible.

In order to overcome these drawbacks of alginate-based impression materials, it is necessary to prevent these reactions from proceeding. Therefore, (1) During production, raw materials for production are stored in a hermetically sealed container, and raw materials with a high moisture content are sufficiently dried and stored in a hermetically sealed container. (2) If the humidity inside the manufacturing facility during manufacturing is high, it is necessary to take measures such as dehumidifying or stopping Ft manufacturing. Furthermore, when using the product, once opened, it must be stored in a desiccator containing a desiccant such as silica gel.

However, the method of sealing, drying, or dehumidifying the raw materials before producing the button requires a large amount of equipment and space, and is not economical. In addition, it is inconvenient to store the product in a desiccator with only one desiccant in it due to the lateral pressure used.

Furthermore, it must be removed from the desiccator every time it is used.
At that time, it is exposed to moisture in the atmosphere, absorbs moisture from the atmosphere, and gradually deteriorates. To make matters worse, ordinary users store alginate-based impression materials in a desiccator containing a desiccant agent (which is rarely done in practice. The reality is that they are preserved.

Therefore, every time you open the bottle, you are exposed to fresh air containing moisture.
1. Impression material deteriorates faster.

The present inventor has conducted intensive research to solve the above-mentioned cracking and instability in use of alginate-based impression materials economically and easily. reached.

That is, the present invention comprises: (1) alginate, (li) calcium sulfate and/or lead silicate, (ii+) filler, and (tV) (A)
Hydrocarbon having 8 or more carbon atoms (13) A silane coupling agent selected from the group consisting of a titanate coupling agent and (D) a hydrophobic polymer having a contact angle with water of 45°1' This is an impression material characterized by containing at least one kind of additive as a main component.

As the (1) alginate, (ii) calcium sulfate and/or lead silicate, (m > filler) used in the present invention, known fillers used in conventional alginate-based impression materials can be used without any restriction. Specifically, examples of alginates that are particularly preferably used include sodium alginate, potassium alginate, and triethanolamine alginate. Calcium dihydrate, Calcilla sulfate J, hemihydrate, anhydrous calcium sulfate, etc. are used.Also, lead silicate can be used in combination with calcium sulfate or alone. For materials and materials, inorganic fillers such as metal or metalloid oxides or hydroxides, clay minerals, etc. can be used.

Specific examples of fillers used in the present invention include diatomaceous earth, talc, silica, aluminum hydroxide, and the like.

The amounts of (I) alginate, (It) calcium sulfate and/or lead silicate, and (i++ > filler) to be used are not particularly limited and may be selected from conventionally known ranges. For example, these 5fi!
The proportion of alginate in the total amount is 5 to 25%, calcium sulfate and/or lead silicate is 5 to 5%.
H1! -%, and the remainder may be selected as filler material.

The fourth component of the impression material of the present invention is.

(A) a hydrocarbon having 8 or more carbon atoms; (B') a silane coupling agent; (b)) a titanate coupling agent; and (1)) a hydrophobic polymer having a contact angle with water pressure of 45° or more. At least 1M4 additive.

The hydrocarbon used in the present invention must have 8 or more carbon atoms. When the number of carbon atoms is less than 8, volatility is high;
These hydrocarbons are difficult to add to impression materials and retain in impression materials, making it impossible to obtain impression materials with sufficient moisture resistance.Also, these hydrocarbons have a chain structure or a cyclic structure. can be used. As for those with a chain structure,
Both chained and branched compounds can be used, and both saturated and unsaturated compounds can be used. As those having a cyclic structure, alicyclic hydrocarbons or aromatic hydrocarbons can be used. Hydrocarbons in which a chain structure and a cyclic structure are combined can also be used.

Specific examples of hydrocarbons having 8 or more carbon atoms that can be suitably used in the present invention are as follows.

For example, octane, nonane, decane, dodecane, pentadecane, octadecane, 1-octene, 1-nonene, 1
-Aliphatic chain hydrocarbons such as decene and 1-dodecene; dimethylcyclohexane, inpropylcyclohexane.

cyclooctane, cyclononane, p-menthane, 1-p
- Menten 2. Alicyclic hydrocarbons such as d-limonene and α-terbinene; aromatic hydrocarbons such as brobylbenzene, xylene, methylene, allylbenzene, naphthalene, anthracene, and the like.

Next, as the silane coupling agent, any known silane coupling agent can be used without any restriction. Generally, the silane coupling agent represented by the following formula (1) can be suitably used in the present invention.

x14cn2se83. +X2)s (1
) (However, xl is a hydrogen atom,...a rogen atom, a vinyl group, an acryloyloxy group, a methacryloyloxy group, a mercapto group, an amino group, and X2 is a...a rogen atom or -04-R, + O) -R2 group (where Rt u alkylene group or Rztt alkyl group is shown, m is 0 or an integer of 1 or more), and t is an integer of 0 or 1 or more. ) In the above general formula (1), the halogen atoms represented by xl and x2 include fluorine, chlorine, bromine, and iodine atoms. Furthermore, in the general formula (1), R1
The alkylene group represented by and the alkyl group represented by R2 preferably have 1 to 5 carbon atoms from the viewpoint of easy availability of the silane coupling agent. Furthermore, in general above] (in (1), and m may be an integer of 0 or 1 or more, but from the viewpoint of ease of obtaining the silane coupling agent, it should be 0 or t or an integer of 1 to 5. is preferred.

Preferably used in the present invention 1. Specific examples of the silane coupling agents obtained are as follows.

It is.

For example, C1CH2CH25i (OCJ(5), ,
CH2=CH8i Cmu.

CT(2=CJ(8i(OCH2CH20CHx)B'
.

H8C) 12GHzCH28i (OCHs).

NHzCH2CH2CH28i (OCR20Hs),
.

NH2CH2CH2NHCH2CH28i (OCHs)
5 +NH2C0N) (CH2CH2CH28i C
0CH2CHs)s, etc.

Further, as the titanate coupling agent used in the present invention, any known titanate coupling agent can be used without any restriction. Generally, titanate coupling agents that can be suitably used in the present invention are those represented by the following formula (2) or (3).

(Yz O)n Tl (Y2) 4-n
(2) (However, in formula 1, n is 1 or 2; when n = 1, ¥1 is an alkyl group or an alkenyl group; R6+ R7 and R8 are a hydrogen atom or an alkyl group (however, R9 is an alkyl group or ) (However, Y5 r Y4 is an alkyl group or a luknyl group.) In the above general formula (2), the alkyl group and alkenyl group represented by Yl: Rs + R4+Rs+R6+R
The alkyl group represented by y r RB; the alkyl group and alkenyl group represented by R9 are not limited in their carbon spread, and may be used even if they contain carbon atoms. However, due to the ease of obtaining the titanate coupling agent, the argyl group represented by Yl has 1 to 16 carbon atoms, and the alkenyl group represented by Yl has 2 to 16 carbon atoms, R4+ R4+ R5+ R6
+ The alkyl group represented by R7 and R8 has 1 to 4 carbon atoms
, an alkyl group represented by R9.

The alkenyl group preferably has 5 to 2 carbon atoms.

In addition, in the -J2 general formula (3), the alkyl group and alkenyl group represented by Y5 + Y4 are not particularly limited in the number of carbon atoms, but for the same reason as above, the alkyl group or alkenyl group has 5 to 2 carbon atoms.
Preferably, it is 0.

Specific examples of titanate coupling agents that can be suitably used in the present invention are as follows. For example (JT, CTT(CHs)OTi(OCOC17H5s
), .

etc.

Next, 1d as a hydrophobic polymer with a contact angle ht of 45° or more with respect to water, a contact angle h 45° measured by the method described below.
Any polymer may be used as long as the angle is 5° or more. Specific examples of such hydrophobic polymers having a contact angle of 45° or more with respect to water are as follows.

For example, polyvinyl compounds, polydienes.

Polyacetylene 17, polyamide, polyester.

Mention may be made of polyurethane, polycarbonate, polysulfone, polysiloxane, and the like. Examples of the above polyvinyl compounds include polyethylene, polypropylene, polyvinyl chloride, polyvinyl fluoride, polystyrene, polyacrylonitrile, and polymethyl acrylate.

Examples include polymethyl methacrylate, polymethoxyethylene, polyvinyl butyrate, polyvinyl butyral, and the like. Moreover, as the above-mentioned polysiloxane, one represented by the following general formula (4) is preferably used.

(However, Rla + R++ + R+2 and R, +3
is a hydrogen atom.

It is an alkyl group or a phenyl group, and ZJ+Z2 is a hydrogen atom, a hydroxyl group, an alkyl group, or a phenyl group, and p is an integer of 1 or more. ) In the above general formula (4), alkyl groups having various carbon numbers can be used without limitation, but those having 1 to 5 carbon atoms are preferred from the viewpoint of easy availability of polysiloxane.
-9 In the above general formula (4), p may be an integer of 1 or more, but for the same reason as above, it is preferably an integer of 1 to 30.

Specific examples of polysiloxanes that are generally preferably used in the present invention include dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane.

It is more preferable that the hydrophobic polymer used in the present invention has a contact angle with water of 80° or more. When the contact angle of the hydrophobic polymer is large - t1, absorption of moisture in the atmosphere is suppressed, and as a result, changes in the physical properties of the binding material are reduced.

Polymers with a contact angle of 80° or more include polyethylene, polypropylene, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polystyrene, polybutadiene, polyacetylene, nylon, polyethylene terephthalate, There are polysiloxanes, etc.

The amount of the above additives used will vary depending on whether the additive is liquid or solid and also on the particle size of (1) alginate, (ii) calcium sulfate and/or lead silicate, (+++) filler, etc. However, in consideration of the moisture resistance of the impression material, its miscibility with water, and the permanent deformation of the impression material mixture, it is generally determined that the amount is 0.01 to 5.0% by weight in the impression material. It is preferably added, and more preferably in a range of 0.05 to 1.0% by weight.

In addition to the above-mentioned components, magnesium oxide, zinc oxide, etc. are added to the impression material in an amount of 1% to 1% to 2% by weight in order to reduce the permanent set of the kneaded impression material. It is preferable to do so.

In addition, in order to reduce the permanent set while minimizing the decrease in the elastic strain of the impression material mix, and to improve the smoothness of the surface of the plaster model, hexafluoro titanium acid salt, hexafluorozircone #salt,
It is also a preferred embodiment to add hexafluorosilicate or the like. Furthermore, adjusting the gelation time to an appropriate range, for example, about 1 to 5 minutes (-1%), in order to improve crop yield,
It is preferable to add phosphates such as 5th phosphate, birophosphate, tripolyphosphate, and hexameglylate, oxalate, carbonate, and the like. These phosphorus! ! i, salt.

It is preferable that oxalates and carbonates are added to the impression material in an amount of 0.05 to 5.0% by weight.

When the alginate impression material to which the phosphate or oxalate is added absorbs moisture, the gelation time regulating effect of the phosphate or oxalate decreases. Therefore, the moisture-resistant effect of the present invention is particularly remarkable for impression materials containing phosphate or oxalate.

As the method for mixing the components of the impression material of the present invention described above, any conventionally known powder mixing method or powder and liquid mixing method may be used without any limitation. That is, when the additive is a liquid, a method of adding the additive directly to powder and heating it can be mentioned. If the additive is solid, add it directly to the powder,
Although mixing or pulverizing may be used, it is preferable to dissolve the additive in an organic solvent, add and mix this solution to the powder, and then evaporate and evaporate the organic solvent.

The mixing order of each component is not particularly limited. It is also possible to mix all the components at once, or (1) alginate, (:1
) calcium sulfate and/or lead silicate and (iii)
A method of adding and mixing an additive into a mixture of fillers, or at least one of (1) alginate, (ii) calcium sulfate and/or lead silicate, and (+++) filler.
It is possible to adopt a method of adding and mixing additives to the components in advance and then mixing these.

Among the components of the impression material of the present invention, (1) alginate and (ii) calcium sulfate and 7' or lead silicate tend to react by absorbing moisture. Therefore, as a method for warming up each component of the impression material of the present invention, it is preferable to mix at least one of (:) alginate and (li) calcium sulfate and/or lead silicate with an additive in advance. , is suitable because it can effectively exhibit the moisture resistance of the impression material.

The impression material of the present invention can be used for making molds of various shapes.

For example, it can be used to make a mold of the shape of a tooth in dental treatment and restoration, and it can also be used to make a prototype of the shape to be cast in the production of a mold for metal casting. obtain. Furthermore, in plastic molding, it can also be used to make a prototype of the shape to be molded.

Since the impression material of the present invention described above has improved moisture resistance, changes in gelling time are suppressed even when stored for a long time or in a high humidity state. Moreover, when the impression material of the present invention is kneaded with water, the dissolution rate in water is delayed (h'), and the gelation reaction is suppressed until each component of the impression material is sufficiently uniformly kneaded with water. Ru.

Therefore, it also has the advantage of being able to mix well with water (
-I am.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

The compositions and test methods of the alginate-based base materials in the following Comparative Examples and Examples are shown in Table 1 below.

Table 1 (1) Test method Mixing ratio of impression materials with the above composition (water weight/impression material weight)
2.9, and the gelation time of the kneaded product was measured. The gelation time was measured by the method specified in JIS'r6505.

(2) Contact angle measurement method The contact angle was measured using a droplet method. In other words, a water droplet with a contact diameter of 3 m or less is created on the horizontal smooth surface of a polymer, and at the point of contact between the water droplet and the polymer, the angle between the cut line drawn on the water droplet and the surface of the polymer that includes the water droplet is The angle of the surface was measured and used as the contact angle. All measurements were performed in an atmosphere of 20°C. When the polymer was a liquid, the polymer was applied to a glass surface and the contact angle with respect to the coating was measured.

Comparative Example A composition blended with compositions A and B shown in Table 1 was prepared, a kneaded product was obtained according to the above test method, and a part of the kneaded product was used to determine the gelation time immediately after blending. It was measured. On the other hand, the remaining sample was exposed to an atmosphere at a temperature of 23° C. and a relative humidity of 90% for 50 hours, and then the gelation time was measured in the same manner. The results were shown on the second display.

Table 2 Examples 1 to 24 Alginate, calcium sulfate, or lead silicate, respectively, and additives were first mixed to form compositions A, B, and C shown in Table 1 and various types shown in Table 3. An impression material consisting of the following additives was prepared. The amount of the additive was expressed as a proportion of the total weight in the impression material, and is also shown in Table 3.

This impression material was kept at a temperature of 23°C as in the comparative example.

After being exposed to an atmosphere of 90% relative humidity for 50 hours, the gelation time was measured. The results are shown in Table 6.

The following margin Examples 25 to 46 Impression materials were prepared in the same manner as in Examples 1 to 24, except that the additives were dissolved in the solvents shown in Table 4 to a predetermined concentration, and the solvent was evaporated after addition and mixing. was prepared.

Using this impression material, gelation time was measured in the same manner as in the comparative example, and the results are shown in Table 4.

Below is the blank Example 47 Potassium alginate, CaS04' 2 H20
*Cas Os ・2 H20+ ZnO+ My O
p K2Z r To 100 layers of each component of F6 + diatomaceous earth, 10 parts by weight of ethyl dichloride solution containing 10 wt% polystyrene was added and mixed, and by volatilizing the ethylene dichloride, each raw material powder was mixed with Boristine 17. The body was covered. Using these raw materials, an impression material consisting of the composition and polystyrene was prepared. The impression material was placed in a π atmosphere at a temperature of 23°C and a relative humidity of 90% for 24 hours in the same manner as in the comparative example, and then the gelation time was measured.
The gelation time was 1 minute and 56 seconds.

Example 48 An impression material was prepared by simultaneously mixing each component shown in Composition A in Table 1 and liquid paraffin in an amount of 0.5% by weight in the resulting impression material. The gelation time was measured after the impression material was placed in an atmosphere with a temperature of 3°C and a relative humidity of 90% for 50 hours and 1 minute and 54 seconds, as in the comparative example. Met.

Claims (1)

[Claims] (1) (i) alginate, (ii) calcium sulfate and/or lead silicate, (iii) filler, and (iv) (
At least one selected from the group consisting of A) a hydrocarbon having 8 or more carbon atoms, (B) a silane coupling agent, (C) a titanate coupling agent, and (D) a hydrophobic polymer having a contact angle with water of 45° or more. An impression material characterized by containing a seed additive as a main component.