JPH0347864A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a curable composition, composed of an alkenyl group- containing terminal polyether, SiH group-containing polyether, specific silicone oil or polyvinyl ether and platinum-based catalyst and excellent in curability in deep parts and dimensional reproducibility of cured products. CONSTITUTION:A curable composition, composed of (A) an alkenyl group- containing terminal straight-chain or branched polyether, (B) a straight-chain or branched polyether having a polyorganosiloxane with >=1 SiH groups at the terminals and >=2 SiH groups in the molecule, (C) (C1) a silicone oil having <=10000 cSt viscosity at (25 deg.C) or (C2) a polyinyl ether having 10000-20000 weight- average molecular weight and (D) a catalyst selected from platinum, chloroplatinic acid and platinum complexes and containing SiH groups of the component (B) in a molar amount of 0.5-10 times based on the total amount of the alkenyl groups in the composition and the component (C1) in an amount of 1-30wt.% based on the total composition or component (C2) in an amount of 1-50wt.% based on the total composition and the platinum atoms of the component (D) in an amount of 0.1ppm to 5wt.% based on the total amount of the components (A) and (B).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel curable composition. Specifically, it is a curable composition that has excellent curing properties, and the cured product thereof has good hydrophilicity and excellent dimensional reproducibility, and is particularly useful as a dental impression material.

[Conventional technology and problems]

Curable compositions that cure at room temperature to give cured products with rubber elasticity are widely used in applications such as dental impression materials and sealing materials. Among these uses, especially when used as a dental impression material, the cured product is required to have good hydrophilicity in order to increase its affinity with the tooth and gum surfaces in order to take precise impressions. Ru. In addition, in such applications, the curable composition has excellent curing properties that allow it to harden uniformly to the deep part in a short time (hereinafter referred to as deep curing properties), and the cured product has good dimensional reproducibility without plastic deformation during demolding. sexuality is required.

Conventionally, a composition comprising a polyether containing an alkenyl group, a polyorganohydrodiene siloxane having a Si-H group, and a platinum-based catalyst has been used as a curable composition that is hydrophilic and has excellent deep curing properties. Although such a composition has excellent deep curing properties and hydrophilicity, it is said that the above-mentioned polyether and polyorganohydrodiene siloxane have poor compatibility, making it difficult to obtain a completely cured product. Therefore, when the above-mentioned curable composition is used as a dental impression material, there is a problem that plastic deformation occurs when the cured product is removed from the mold, making it impossible to take an accurate impression. It has also been proposed to modify the polyorganohydrogensiloxane with a polyether in order to improve the compatibility between the ether and the polyorganohydrogensiloxane.However, in such a composition, the polyether used for modification Since the residue acts as a plasticizer in the resulting cured product, there is a risk that the surface may become sticky or plastic deformation may occur, and further improvements have been desired.

[Means for solving problems]

The inventors of the present application have conducted extensive research in order to develop a curable composition that has excellent deep curability, and the cured product thereof is hydrophilic and has good dimensional reproducibility. As a result, a linear or branched polyether having an alkenyl group at the end, a polyorganosiloxane residue having one or more Si-H groups at the end, and two or more Si-H groups in the molecule. By blending a silicone oil with a specific viscosity and a catalyst mainly composed of platinum as a catalyst in a specific ratio, or a linear or branched polyether with an alkenyl group at the end. , linear or branched polyethers having polyorganosiloxane residues having one or more Si-H groups at the ends and two or more Si-H groups in the molecule, polyvinyl ethers with specific molecular weights, and catalysts. By blending a platinum-based catalyst in a specific ratio, the above objectives can be achieved, and the composition can be uniformly cured without being affected by moisture, and the viscosity of the composition before curing can be reduced. The present inventors have found that the properties of the resin after curing can be improved and have sufficient flexibility, leading to the completion of the present invention.

The present invention provides (A) a linear or branched polyether having an alkenyl group at the end (hereinafter also referred to as an alkenyl group-containing polyether); (B) a polyorganosiloxane residue having one or more Si-H groups; Linear or branched polyether having two or more Si-H groups in the molecule (hereinafter also referred to as Si-H group-containing polyether) (C) A polyether with a viscosity of 10.000 centistokes (25
°C) a silicone oil as follows; and (D) at least one catalyst selected from the group consisting of platinum, chloroplatinic acid, and a platinum complex, the composition comprising: The amount of -H groups is 0.5 to 10 mole times the total amount of alkenyl groups in the composition, and the silicone oil (C) is 1 to 30% by weight of the entire composition. , and (D
) The platinum atoms in the platinum-based catalyst are O, lppm based on the total amount of polyether (A) and polyether (B).
5% by weight of the curable composition.

The present invention also provides (A) a linear or branched polyether having an alkenyl group at its end (hereinafter also referred to as alkenyl group-containing polyether) (B) a polyorganosiloxane residue having one or more Si-H groups. Linear or branched polyether having a group at the end and two or more Si-H groups in the molecule (hereinafter also referred to as Si-H group-containing polyether) (C) Weight average molecular weight 10,000 to 200 10,000 polyvinyl ether and (D) at least one catalyst selected from the group consisting of platinum, chloroplatinic acid, and platinum complexes, wherein the Si-H group in the polyether (B) is The amount is 0.5 to 1O times the total amount of alkenyl groups in the composition, and the polyvinyl ether (C) is 0.1 to 50% by weight of the entire composition. , and the platinum atoms in the platinum-based catalyst (D) are 0 relative to the total amount of the polyether (A) and the polyether ('B),
The curable composition has a proportion of 1 ppm to 5% by weight.

In addition, in the present invention, the terminus of a linear or branched polyether refers to two or more 10R-bonds (however, R-bonds)
represents an alkylene group having one or more carbon atoms).

In the present invention, the alkenyl group-containing polyether is
There are no particular restrictions on the polyether as long as it is a linear or branched polyether having an alkenyl group at the end.

Such alkenyl group-containing polyethers are generally represented by the following general formula %. In the above formula (I), A is a divalent to hexavalent saturated hydrocarbon group having 1 to IO carbon atoms.

Since the valence of A refers to a substituent of a saturated hydrocarbon, the saturated hydrocarbon group may have at least 2 substituents and a maximum of 6 substituents. If the number of substitutions exceeds 6, it is not preferable because rubber elasticity cannot be imparted when the target curable composition is cured. Most preferably, the number of substituents, that is, the valence of A, is 2 or 3.
and the number of carbon atoms in the saturated hydrocarbon group is 2 to 4. A substituent may be present on any carbon atom of the saturated hydrocarbon group, but when the number of carbon atoms is 2 or more, it is preferable from the viewpoint of stability that 2 or more substituents are not present on one carbon atom. .

In the above general formula (I), R1 is a linear or branched alkylene group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and in the alkylene group, a in the general formula (I) is 2 or more. When , different alkylene groups may be used. Also, a is I~30
b is an integer of 0, and b is an integer of 2 to 6. Therefore, when a is 2 or more, the average degree of polymerization is indicated using -0-R,- as a unit, and when a is 2 or more, the units can take the form of random polymerization or block polymerization.

In addition, B in the above general formula (I), R, R, R5 and R6 are the same or different hydrogen atoms or have 1 to 1 carbon atoms.
is an alkyl group of lO, and d is an integer from 1 to 10)
They are the same or different unsaturated groups represented by Above R2~
When R6 is an alkyl group, an alkyl group having 1 to 4 carbon atoms, ie, a methyl group, an ethyl group, a propyl group, a butyl group, etc., is particularly preferably used.

As is clear from the above description, the polyether represented by the general formula (I) is an unsaturated polyether having at least two or more alkenyl groups at its terminals. The presence of two or more alkenyl groups at the terminal means that the general formula (I
This is an important requirement for curing by crosslinking reaction with the Si-H group-containing polyether shown in I). When the curable composition of the present invention is used, for example, as a dental impression material, the molecular weight of the alkenyl group-containing polyether is 200.
It is preferable that the molecular weight of the alkenyl group-containing polyether is 20 or more in order to handle it as a liquid.
．． It is preferable to set it as 000 or less.

More specifically, typical alkenyl group-containing polyethers used in the present invention are CH2=CHO+
CH2CH20-+-V+ CH2CH2CH2CH2
0h7 CH=CH.

(-CH2CH2CH2CH20h CH2CH=CH
2゜ ■ ■ CH3 CH=CHCO+ CH2CH20-+;+-CH2C
H2CH2CH,O-TCCH Cl,.

C.I.

C.I.

CH.

+ CH2CH2CH2CH20CH2C=CH2゜CH, CH=CHCH2O+CH2CH2CH, CH,
O South-CH2CH=CHCH3゜3 5 16 CH2CH=CH2 CH20-(CH2CH20+TT+cH2CH2CH
2CH2bCH2CH=CH2CHO-ECH2CH2
0 bookscn2cn2co2cn2o-)]TCH2CH=
CH2CH20-(CH2CH20WCH2CH2CH
2CH2h CH2CH=CH2゜(However, l is 3~
250, m, n, x, y and 2 are 1 or more and X'+ Y'+ Z'+ X21 y2 and z2 are 0
The above integers, m+n and X+V+Z are 3 to 250, x
'+x', y'+y', z'+z2 is 1 or more, and x
'+x'+y'+y2+z'+z2 is 250 or less. ) etc.

The above alkenyl group-containing polyethers are those in which an alkenyl group is bonded to a polyether chain having two or three terminals, but the present invention is not limited to these. 8 Polyether chains having 4 to 6 terminals to which alkenyl groups are bonded can also be used.

In addition, one or two alkenyl group-containing polyethers may be used.
It is also possible to use a combination of more than one species.

However, considering the ease of industrial production and ease of handling, among the above alkenyl group-containing polyethers,
Particularly preferred are those represented by the general formula (where xl is an integer of 5 to 200).

These alkenyl group-containing polyethers used in the present invention can be easily produced by known methods. For example, there is a method in which a terminal hydroxyl group of a commercially available polyether is reacted with a compound having an alkenyl group and an active group such as a halogen group capable of reacting with the hydroxyl group under known conditions. 4. For example, there is a method in which the terminal hydroxyl group of polyether is converted into an alcoholade using sodium metal, and then 9 allyl chloride is added to form an ether bond through a dechlorination reaction.

In the present invention, the Si-H group-containing polyether is S
There are no particular restrictions on the polyether as long as it is a linear or branched polyether that has a polyorganosiloxane residue having one or more i-H groups at the end and has two or more Si-H groups in the molecule.

Generally, such Si-H group-containing polyethers are siloxane-substituted polyethers represented by the general formula % ([).

The number of saturated hydrocarbon groups is 1 to 10, preferably 2 to 4.

If the valence exceeds 6, the curable composition of the present invention cannot be imparted with rubber elasticity when cured, so it is generally not preferred.

Further, R7 in the general formula (n) is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, like R1 in the general formula (I), and the alkyl group may be different alkyl groups when e is 2 or more. Therefore, when e is 2 or more, the polyester chain having -0-R7- as a unit can take a random polymerization form or a block polymerization form.

Furthermore, in the general formula (n), E is the same or different, R11 and R111 are the same or different hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and g is an integer of 1 to 10. It is a different kind of alkylene group. In the above formula, Rs, RI+ R1°, R1, and Ra
t is R2-R6 of the formula represented by B in the general formula (I)
same or different hydrogen atoms or carbon atoms 1-1
0, preferably 1 to 4 alkyl groups can be selected.

Further, in general formula (n), e is 1 to 30, preferably 1 to 1
An integer of 0 is preferably selected, and f is an integer of 2 to 6, preferably 2 to 3.

Furthermore, G in the above general formula (n) represents the following (i) to (ii)
) are the same or different types of siloxane groups.

That is, +1+a HR+.

(1) −←SiO→−□SiO−←SiO→,
SiMe3R14RIS Rat (However, h and i are integers of O to 8, h+i-1 to 8, R1:l% R14, R15, and R16 are methyl groups or phenyl groups, and R13 and RI4 are
In the above cases, they may be different types.<, RI6 may be different types when i is 2 or more, R17 is a hydrogen atom, methyl group, or phenyl group, and when i is 2 or more, must be different species<, Me is a methyl group)
R+ s (Rzo) 3-h 22 (where, j is an integer from 0 to 8, k is an integer from 1 to 3, and j
-1 to 9 in ten, RIB , RI9, R2゜, R
2I and R2□ are a methyl group or a phenyl group, and R
111 and R19 can be different types when j is 2 or more, R21 and R2□ are different when k is 2
In the above cases, different types may be used) R23R2S R26Rze (However, p and q are integers from O to 4, p+q-1 to 4, and R23, R24, R2S, RZM and R2ff
is a methyl group or a phenyl group, and RZ4 and R2S may be different types when p is 2 or more.<, R2? Haq
When q is 2 or more, they may be different types, and R28 is a hydrogen atom, a methyl group, or a phenyl group, and when q is 2 or more, they may be different types.) The following is a blank space. In particular, the siloxane group shown in (ii) above exhibits the most excellent effect when the curable composition of the present invention is used as a dental impression material.

It is preferable that the curable composition of the present invention has a molecular weight of 400 or more, and in order to handle it as a liquid, the molecular weight should be 25.0 or more.
It is preferable to set it to 00 or less.

Typical examples of such Si-H group-containing polyethers are as follows: 3, 2, 5, 6, 7, 22, 8 (l is 3 to 60 and m is m).

I I I 2 is 1 or more Integer, m + n = 3~60° x + y 10z = 3~90, ph is a phenyl group.

) etc.

In addition, the above St H group-containing polyethers are polyethers H having 0, 2 and 3 terminals, and 54-) 1 group is added to 1 group.
Although polyorganosiloxane residues having 4 or more terminals are bonded, the present invention is not limited to these, and one or more 5r-H groups are bonded to a polyether chain having 4 or more terminals. It is also possible to use polyorganosiloxane residues bonded thereto. Moreover, it is also possible to use one type or a combination of two or more types of Si-H group-containing polyethers.

In the following margins, especially considering the ease of industrial manufacturing method and ease of handling, among the above Si-H group-containing polyethers, the general formula [However, y' is an integer from 3 to 50, and J and L are the same or different types of L (where Me is a methyl group)]
-H group-containing polyethers are preferred.

In the curable composition of the present invention, the Si-H group-containing polyether has extremely good compatibility with the alkenyl group-containing polyether, so that a homogeneous cured product can be obtained, and at the end of the polyether chain. Polyorganosiloxane residues having one or more Si-H groups are bonded together, and almost no polyether residues exist, so there is no molding effect caused by the polyether residues, resulting in a cured product with good dimensional reproducibility. can be obtained. This Si-H group-containing polyether can be easily produced by a known method.

That is, the above-mentioned alkenyl group-containing polyether and S
Obtained by reacting a polyorganosiloxane having two or more i-H groups in the presence of a platinum-based catalyst such as chloroplatinic acid at a ratio such that the molar ratio of polyorganosiloxane molecules to alkenyl groups is 1 or more. . In addition, in the present invention, even if the reaction of the 5t-H group-containing polyether during production is not complete and some products containing unreacted alkenyl groups remain, the alkenyl groups are still present in the curable composition. Since it acts as a crosslinking group, it can be used without any problems. The Si-H group-containing polyether obtained by the above method has poor storage stability because it contains a platinum-based catalyst (and when stored for a long period of time, the 5t-H group decomposes and reacts, causing thickening and thickening). Problems such as gelation may occur.To solve this problem, the Si-H group-containing polyether is brought into contact with a solid basic substance such as sodium hydrogen carbonate to neutralize and decompose the platinum-based catalyst. Alternatively, the platinum-based catalyst may be adsorbed and removed by bringing the Si-H group-containing polyether into contact with an adsorbent such as silica gel.

(It is not particularly limited as long as it is 225°C.

The curing reaction of the curable composition is easily inhibited by moisture;
Even if the inside is cured, only the surface often remains uncured due to the influence of moisture. However, by blending the silicone oil, it is less affected by moisture (and can be hardened even to the surface.) This curable composition is especially used in environments where there is a large amount of moisture, such as dental impression materials. If so, the silicone oil is an important ingredient.

However, silicone oil with a viscosity exceeding 10,000 cSt (25° C.) does not have the above effect. In addition, taking into account the ease of compatibility with the polyethers, which are essential components of the present invention, and the operability of the composition, the most preferable viscosity range is lO~tooocst (2.5°C).
It is. Examples of the silicone oil include dimethyl silicone, dimethyldiphenyl silicone, fluorosilicone, and various other modified silicones, but those having active groups (such as amino groups and mercapto groups) that inhibit the hydrosilylation reaction are not preferred. Most preferably dimethyl silicone is employed.

The fourth component constituting the curable composition of the present invention is a catalyst component. As the catalyst component, at least one selected from the group consisting of platinum, chloroplatinic acid, and platinum complexes can be used. These catalyst components are widely used and well-known compounds,
In the present invention, there are no particular limitations, and any known materials can be appropriately selected and used. In general, known catalysts for hydrosilylation reactions can be used. Typical platinum complexes that are particularly suitable for use include, for example, complexes of platinum and olefins, complexes obtained from the reaction of chloroplatinic acid and vinyl group-containing polysiloxane, platinum-phosphorous complexes, etc. can be mentioned.

The curable composition of the invention according to the first claim includes the above-mentioned alkenyl group-containing polyether, Si-H group-containing polyether,
The silicone oil and the catalyst can be blended appropriately (there are no restrictions on the addition order, addition method, etc.).
Si-H group-containing polyether and alkenyl group-containing polyether such that the amount of Si-H group in the i-H group-containing polyether is present in a ratio of 0.5 to 10 mole times the total amount of the alkenyl group. The proportion with polyether is determined. Above S
If the ratio of i-H groups is less than 0.5 mole times, the alkenyl groups will be in large excess, and a large amount of uncrosslinked polyether chains with unreacted alkenyl groups will remain after curing, resulting in a reduction in the dimensions of the resulting cured product. Reproducibility decreases. Moreover, when the ratio exceeds 10 times the mole, the dimensional reproducibility of the obtained cured product is significantly reduced, which is particularly preferable in applications requiring high dimensional reproducibility such as dental impression materials, which are the object of the present invention. .

5 6 In the present invention, S in the Si-H group-containing polyether
The amount of iH groups can be measured by known methods. For example, dissolve the sample in isopropyl alcohol,
Next, potassium hydroxide may be added to this and the amount of hydrogen gas generated may be calculated. Furthermore, the amount of alkenyl groups in the curable composition can also be measured by a known method. For example, it is common to measure according to the method for measuring total unsaturation according to JIS K1557. Further, the amount of Si-H groups and the amount of alkenyl groups may be calculated from a theoretical average composition formula derived from the structure of the alkenyl group-containing polyether and the raw material for producing the Si-H group-containing polyether.

The amount of silicone oil in the curable composition may be determined so that it is present in an amount of 1 to 30% by weight of the total composition. When the amount is less than 1% by weight, the effect of protecting the surface of the cured product from the influence of moisture is low. In addition, if it exceeds 30% by weight, the compatibility with the polyether components described above will be low (
, causing problems such as separation during storage.

Further, in the curable composition of the present invention, the catalyst has a platinum atom content of 0.1 with respect to the total amount of the alkenyl group-containing polyether and the Si-H group-containing polyether.
ppm to 5% by weight, preferably 0.1 to 11000p
What is necessary is to determine that they exist at a ratio of p. When the proportion of platinum atoms is less than Q, L ppm, the curing reaction hardly progresses. Further, even if the ratio exceeds the above upper limit, the effect of adding a large amount cannot be obtained.

The polyvinyl ether in the present invention is not particularly limited as long as it has a weight average molecular weight in the range of 10,000 to 2,000,000. When a curable composition is used as a dental impression material, it needs to have sufficient viscosity before curing to transmit pressure during pressure contact. Sufficient viscosity cannot be obtained only by containing polyether.

Furthermore, if the material does not have sufficient flexibility after hardening, problems such as distortion may occur when it is removed from the oral cavity. However, by blending an appropriate amount of polyvinyl ether, it is possible to develop a viscosity according to the purpose, and it acts as a plasticizer inside the cured product to provide sufficient flexibility. When a polyvinyl ether having a weight average molecular weight of less than 2,000,000 is used, the effect of imparting the above-mentioned viscosity and flexibility is low, and it is industrially difficult to produce a polyvinyl ether having a weight average molecular weight of less than 2,000,000.

As the polyvinyl ether, viscous or flexible resinous polyvinyl methyl ether, polyvinylethyl ether, or polyvinyl isobutyl ether having a weight average molecular weight of 100,000 to 1,000,000 is preferably employed.

The curable composition of the invention according to the second claim includes the above-mentioned alkenyl group-containing polyether, Si-H group-containing polyether,
The polyvinyl ether and the catalyst may be blended as appropriate, and there are no restrictions on the addition order, addition method, etc. Generally, the composition ratios suitably used are as described above for components other than polyvinyl ether.

The amount of polyvinyl ether in the curable composition may be determined so that it is present in a proportion of 0.1 to 50% by weight of the total composition. When the amount is less than 0.1% by weight, both the effect of modifying the viscosity before curing and the effect of improving flexibility after curing are low. If it exceeds 50% by weight, the viscosity before curing will be too high, making it difficult to manipulate, and problems will occur, such as becoming sticky after curing.

Known inorganic and organic fillers may be added to the curable composition of the present invention in order to improve workability before curing or to improve various physical properties after curing. Examples of such inorganic fillers include fumed silica, crushed silica, diatomaceous earth, quartz powder, glass fiber, carbon black, iron oxide, zinc oxide, titanium oxide, alumina, magnesia, calcium carbonate, magnesium carbonate, and zinc carbonate. be done. Examples of the organic filler include pulverized polymers and powdered polymers. However, Si
Since the Si-H group of the 4-group-containing polyether undergoes a dehydrogenation condensation reaction in an alkaline atmosphere, an alkaline filler such as magnesia, calcium carbonate, or magnesium carbonate is added to the Si-H group-containing polyether in advance. (It should be noted that the above-mentioned inorganic filler may be used as it is, or the surface may be treated with a silane coupling agent, etc.) Also, the amount of filler added is not particularly limited. It may be used within a range that does not significantly deteriorate the physical properties of the resulting cured product.Generally, the total amount of alkenyl group-containing polyether and Si-H group-containing polyether is 100%.
The range is preferably 500 parts by weight or less. Furthermore, in the curable composition of the present invention, if the amount of hydrogen in the Si-H group is relatively large compared to the amount of alkenyl groups, hydrogen gas may be generated as a by-product during curing. In such cases, in order to prevent the surface condition of the obtained cured product from becoming rough due to the hydrogen gas, palladium, platinum, nickel, magnesium,
It is preferable to add metal powders such as zinc or those supported on a carrier. The amount of the hydrogen absorbent added may be 0.1 to 100 ppm in terms of metal atoms in the curable composition.

In the curable composition of the present invention, other additives may be added to the extent that the physical properties of the resulting cured product are not significantly deteriorated. Such additives include plasticizers, pigments, antioxidants, mold release agents, adhesion promoters, surfactants, and the like.

The curable composition of the present invention is cured at room temperature or under heating. Therefore, among the curable compositions of the present invention that cure at room temperature, a mixture of an alkenyl group-containing polyether and a platinum complex is packaged, and this and the Si-H group-containing polyether or the Si-H group-containing polyether or the Si- It is desirable to store the mixture of the H group-containing polyether and the alkenyl group-containing polyether in another package in a so-called two-component type, and then take out appropriate amounts of both at the time of use and mix them together. Further, the curable composition that cures under heating may be a two-component type as mentioned above, or a platinum-based catalyst that acts only during heating, such as a platinum-based complex such as a platinum-phosphorus complex, may be selected. , a so-called l-wave type in which three components are mixed in advance and stored. The heating temperature at this time is desirably 150° C. or lower in consideration of the durability of the polyether chain. Silicone oil and polyvinyl ether may be blended on either liquid side 1 2 or may be blended so that they are present on both sides.

[Operation and effect of the invention]

The curable composition provided by the present invention has excellent deep curability, and the cured product thereof has hydrophilicity and good dimensional reproducibility and dimensional stability. That is, in the curable composition of the present invention, the curing reaction proceeds under the action of the catalyst, so that it is uniformly cured regardless of whether it is shallow or deep.

Furthermore, since the composition is mainly composed of polyether chains, the cured product thereof has hydrophilicity. Furthermore, since the polyether in the curable composition has alkenyl groups or Si-H groups at all ends, by adjusting the number of moles of both groups, the polyether acts as a plasticizer in the cured product. The amount of ether residue can be extremely reduced, so the cured product has excellent dimensional reproducibility, with no sticky surface and less plastic deformation. Since the curing reaction is an addition reaction of Si--H groups to alkenyl groups, curing is completed quickly and no eliminated components are generated, resulting in good dimensional stability over time.

Furthermore, by blending silicone oil with a specific viscosity, the curable composition of the present invention is less susceptible to moisture, particularly moisture, and hardens uniformly. Furthermore, by appropriately adjusting the blend of polyvinyl ether with a specific molecular weight, it is possible to freely improve and adjust the viscosity from good fluidity before curing to putty-like, while at the same time making use of the flexibility after curing. It can be freely prepared depending on the purpose.

The curable composition of the present invention having the above characteristics can be used in a wide range of fields, but is particularly useful as a dental impression material. In addition, due to its excellent biocompatibility due to its hydrophilicity, it is useful not only as a dental impression material, but also as a denture fit test material (fit checker), a mucous membrane conditioning material, and the like.

〔Example〕

Examples will be shown to further specifically explain the present invention; however,
The present invention is not limited to these examples.

3 4 In the Examples and Comparative Examples, the curable compositions were evaluated by selecting from the following methods depending on the purpose.

(1) Hydrophilicity In a room adjusted to a temperature of 23° C. and a humidity of 50%, 10 μl of pure water is placed on the smooth surface of the cured product, and after 15 minutes, the contact angle with water is measured using a contact angle measuring device. The closer this value is to θ°, the higher the hydrophilicity, and the closer this value is to 90° or more, the lower the hydrophilicity.

(2) Dimensional reproducibility American Dental Association Specification
5specification) NIll
Permanent set, compressive set, and dimensional change were measured according to the measurement method of No. 9. The smaller the value of permanent set, the better the dimensional reproducibility, and the larger this value, the more severe the plastic deformation.

Further, the larger the compressive strain value is, the softer the cured product is, and the smaller the compressive strain value is, the less flexible it is. The dimensional change is a value indicating the deformation of the cured product over time, with a positive value indicating linear expansion and a negative value indicating linear contraction.

(3) Properties and operability The viscosity of the composition before curing was measured using a high shear rheometer. In the case of a two-part composition, the two parts were mixed and immediately measured. In addition, when the surface of the obtained cured product is uncured and has tackiness, it is called "poor surface curing."
"Good surface hardening".

In addition, in the Examples and Comparative Examples, the molar ratio of (amount of Si-H groups in the S-H group-containing polyether)/(total amount of alkenyl groups in the curable composition) is the Si-H/AL ratio. For abbreviation, the ratio of platinum atoms in the platinum-based complex to the total amount of the alkenyl group-containing polyether and the Si-H group-containing polyether is abbreviated as Cpt.

In addition, in the following examples, the average formula of alkenyl group-containing polyether and Si-H group-containing polyether is:
Structure and composition of raw materials of the polyether and chemical analysis methods (determination of alkenyl group amount and Si-H group amount, measurement of molecular weight and molecular weight distribution by liquid chromatography, infrared spectroscopy, nuclear magnetic resonance) This is a structural formula derived from a spectrum, etc.), and is a formula showing an averaged structure of the polyether.

<Effect of adding silicone oil> Examples 1 to 4, Comparative Examples 1 to 4 5 parts of Si-H group-containing polyether represented by the average formula (Si-H
/AL ratio -1.0) and 100 parts of quartz powder are mixed, and silicone oil of the type and amount shown in Table 1 is added to prepare a paste. Here, 95 parts of an alkenyl group-containing polyether represented by chloroplatinic acid (hereinafter, parts by weight are expressed unless otherwise specified), and 0.1 parts of an average platinum complex (containing 34% by weight of platinum atoms).
Add 2 parts (Cpt=400 ppm), temperature 23°C,
The mixture was mixed indoors at 50% humidity. The results are also shown in Table 1.

7 8 <Effect of adding polyvinyl ether> Examples 5 to 8. Comparative Examples 5-8 Mixed indoors with an average formula of 50%. The results are also shown in Table 2.

44 parts of alkenyl group-containing polyether represented by the formula, 56 parts of the Si-H group-containing polyether represented by the average formula
H/AL ratio -1.0) and 10 parts of fumed silica were mixed, and polyvinyl ether of type and amount as shown in Table 2 was added to prepare a paste. Next, 0.1 part of the platinum complex used in Example 1 (Cpt = 340 ppm
) In addition, the temperature was 23°C and the humidity was 0.1 (Addition of silicone oil and polyvinyl ether) Examples 9 to 12. Comparative Example 9 Average formula (where a, b, and c are integers greater than or equal to 0, and a+b+c
= 66) 48 parts of alkenyl group-containing polyether represented by the average formula (a, b, c are the same as above) 52 parts of Si-H group-containing polyether (Si
-H/AL ratio -1,0), viscosity 100cst (25°C
), 5 parts of polyvinylethyl ether having a weight average molecular weight of 200,000, and 25 parts of diatomaceous matter were mixed to prepare a paste. Catalyst of type and amount as shown in Table 3 was then added and mixed. The results are also shown in Table 3.

3 4 Examples 13 to 4.3, Comparative Examples 10 to 15 Impression materials made of the following curable compositions were constructed using the alkenyl group-containing polyethers and Si-H group-containing polyethers shown in Table 4, respectively. did.

Equal amounts of paste A and paste B of the above impression material were taken out and kneaded, and each physical property was measured. Furthermore, an intraoral impression was taken using the above-mentioned impression material, and the condition of the impression surface was evaluated based on foam traces and adhesiveness.

In addition, a crown (dental cast crown) was created based on the above impression, and its accuracy was evaluated based on its compatibility.

Foam traces, tackiness and precision were evaluated according to the following criteria.

(1) Foaming traces A...not present at all B...slightly present °C...many 6 7 (2) Adhesiveness A...all (absent B...somewhat C) - Strong adhesion (3) Accuracy A: The crown fitted well B - The crown did not fit slightly C: The crown did not fit at all The results are shown in Table 5.

8

Claims (1)

[Scope of Claims] 1) (A) A linear or branched polyether having an alkenyl group at the end; (B) A polyorganosiloxane residue having one or more Si-H groups at the end; -Linear or branched polyether (C) having two or more H groups in the molecule; viscosity of 10,000 centistokes (25°C)
The following silicone oil (D) A composition comprising at least one catalyst selected from the group consisting of platinum, chloroplatinic acid, and a platinum complex,
The amount of Si-H groups in the polyether (B) is 0.5 to 10 times the total amount of alkenyl groups in the composition, and the silicone oil (C) is in the composition. The proportion is 1 to 30% by weight of the total, and the platinum atoms in the catalyst (D) are 0.1 ppm to 5 weight percent based on the total amount of the polyether (A) and the polyether (B). %
A curable composition having a ratio of . 2) (A) A linear or branched polyether having an alkenyl group at the end; (B) A polyorganosiloxane residue having one or more Si-H groups at the end, and a Si-H group in the molecule. (C) a polyvinyl ether having a weight average molecular weight of 10,000 to 2,000,000; and (D) at least one member selected from the group consisting of platinum, chloroplatinic acid, and platinum complexes. A composition comprising a catalyst, wherein the amount of Si-H groups in the polyether (B) is 0.5 to 10 times the total amount of alkenyl groups in the composition, (C) polyvinyl ether is 0.1 to 50% by weight of the entire composition
The ratio is such that the platinum atoms in the catalyst (D) are (
A curable composition having a proportion of 0.1 ppm to 5% by weight based on the total amount of polyether A) and polyether (B).