JP5110988B2 - Dental silicone-based curable composition - Google Patents

Description

  The present invention relates to a curable composition useful as a dental material, particularly a dental silicone material.

  Examples of the dental silicone material include a denture base lining material and a dental impression material. In either case, the surgeon measures and kneads the necessary amount immediately before use, and cures through appropriate treatment and processing.

Such silicone-based curable compositions mainly include condensation-type silicone-based curable compositions and addition-reactive-type silicone-based curable compositions depending on the difference in the curing reaction of the reactive organopolysiloxane compound contained. The former has a hydroxyl group as a reactive group and cures by causing a condensation reaction in the course of the reaction. However, there is a drawback in that there is a leaving substance such as alcohol.

  The latter has a vinyl group and a Si-H group as reactive groups, and these undergo an addition reaction in the reaction process to cure. Many are used as a composition.

  These dental silicone-based curable compositions are generally very hydrophobic and have excellent coloration resistance, but their properties are often problematic when used as dental silicone materials. was there.

  When the silicone-based curable composition is used as a dental material, most of the objects to be used are in the oral cavity, and most of them are in contact with oral tissues such as oral mucosa and teeth. These are all moistened with saliva and the like, and the dental materials used are desired to be hydrophilic, more preferably moisturizing.

  For example, the dental impression material preferably has hydrophilicity in order to obtain a more uniform and accurate impression. When the silicone-based curable composition is used as an impression material, there is a problem that it is difficult to obtain a precise impression because of its high hydrophobicity.

  In recent years, it has become a mainstream to add a surfactant to a silicone-based curable composition to impart hydrophilicity, which has been improved to a level that is practically acceptable for clinical use. Yes.

  However, when these surfactants are added in a large amount, the impression material paste tends to bleed little by little during storage. When used regularly, there is no particular problem, but when not used for a long time, a slight but transparent surfactant is separated at the tip of the container. In that case, since the surgeon must remove the bleed surfactant immediately before use, it is desired to develop a silicone-based curable composition that does not cause separation even after long-term storage. .

  In addition, the silicone-based curable composition is suitably used as a soft denture lining material. Soft denture lining material is a material that linings dentures that have become incompatible with the oral mucosa due to age, etc., and is a part that directly contacts the oral mucosa in the oral cavity and also has a role to hold the denture in the oral cavity Have.

  Conventionally, as such soft denture lining materials, poly (meth) acrylate-based materials (see, for example, Patent Document 1) and silicone rubber-based materials (for example, see Patent Document 2) are known. Yes.

  A poly (meth) acrylate-based soft lining material generally contains a polymerized cured product of a (meth) acrylate-based radical polymerizable monomer such as methyl methacrylate or ethyl methacrylate. Typical product forms consist of a liquid material mainly composed of (meth) acrylate monomers and a powder material mainly composed of (meth) acrylate polymers such as polymethyl methacrylate. Furthermore, a polymerization initiator is appropriately distributed and mixed in the liquid material and the powder material, and the (meth) acrylate monomer is polymerized by mixing both materials. The (meth) acrylate polymer acts as a kind of filler, and dissolves or swells in the (meth) acrylate monomer at the time of mixing, and has the effect of making the entire composition into a paste or bowl shape. As a result, moderate operability can be obtained.

  Such a poly (meth) acrylate-based polymer cured product is excellent in strength, but does not have the necessary flexibility as a soft lining material as it is, so it is necessary to add a plasticizer. As such plasticizers, plasticizers such as dioctyl phthalate and dibutyl phthalate are mainly used.

  On the other hand, since silicone rubber is inherently highly biocompatible, silicone rubber-based soft lining materials are also widely used. In general, since silicone rubber is a soft material rich in elasticity, such a silicone rubber-based soft denture lining material does not require any additional plasticizer. As a result, silicone-based curable compositions are frequently used as soft denture lining materials. However, dry mucosa of the oral mucous membranes are often used for hyposalivators who have become common in recent years, so-called dry mouth patients. And the remarkably fall of familiarity with the denture accompanying them obstructs the maintenance stability of the denture in the oral cavity. When a soft denture lining material having appropriate hydrophilicity and affinity for such a patient is used, it becomes easy to stabilize the denture in the oral cavity. Therefore, the soft denture lining material having such properties is used. Therefore, the development of a silicone-based curable composition that is the basis for this is desired.

JP 2002-119523 A Japanese Patent No. 3277503

  In the background described above, the present invention is a hydrophilic dental silicone-based curable composition that is resistant to separation of additives and the like even when stored for a long period of time and has excellent storage stability. The challenge is to develop.

  As a result of intensive studies to solve the above problems, the present inventors have found that a branched polyglycerol-modified silicone in which at least one branched polyglycerol chain is bonded to a silicon atom of silicone via a linking group is an existing silicone-based curable composition. It was found that when added to a product, hydrophilicity can be imparted to the composition, and the modified silicone does not separate at all from the composition.

That is, the present invention relates to an organopolysiloxane (A) having at least two organic groups having an unsaturated bond at the terminal, and an organohydrogenpolysiloxane (B) having at least three SiH groups in the molecule. , An organohydrogenpolysiloxane (C) having two SiH groups in the molecule, a hydrosilylation reaction catalyst material (D), a filler (E), and a branched polyglycerol chain via a linking group to the silicon silicon atom There is a dental silicone-based curable composition comprising a composition comprising at least one linked branched polyglycerol-modified silicone (F).

  The dental silicone-based curable composition according to the present invention is characterized by containing a branched polyglycerol-modified silicone, whereby the composition has hydrophilicity, and the modified silicone is difficult to separate and can be stored for a long period of time. Has an excellent effect.

  The dental silicone-based curable composition of the present invention is characterized by containing a branched polyglycerol-modified silicone in which at least one branched polyglycerol chain is bonded to a silicon atom of silicone via a linking group. Of these, known silicones can be used without particular limitation. Among them, dental silicone-based curable compositions that are easily cured in about 10 minutes at room temperature are useful for application to dental materials. Combinations of silicones that cure by are suitable. In particular, the latter is more preferable because there is no by-product such as alcohol and there is no polymerization heat during curing.

  The polyglycerol-modified silicone, which is the greatest feature of the dental silicone-based curable composition in the present invention, is not particularly limited as long as at least one branched polyglycerol chain is bonded to the silicon atom of the silicone via a linking group. Can be used.

  The branched polyglycerol-modified silicone used in the present invention has one or more of the following structural formula (1) as a branching group.

Containing a branched polyglycerol group represented by the formula (hereinafter referred to as group (1)). The branched polyglycerol chain has a structure of a group (1), b glycidol groups represented by the following structural formula (2) (hereinafter referred to as group (2)), c structural formula (3) And a glycerol group represented by the following structural formula (4) (hereinafter referred to as group (4)) as a terminal group. It is.

  It is sufficient that at least one branched polyglycerol chain bonded to the silicon atom of silicone is included, but it is preferable to have at least two branched polyglycerol chains in order to achieve the effect of the present invention. The total number of hydroxyl groups (—OH groups) contained in the branched polyglycerol chain / the total number of silicon atoms constituting the siloxane bond in the silicone is 0.01 to 5, more preferably 0.02 to 3. It is preferable to control the number of branched polyglycerol chains so as to achieve uniform mixing with the silicone-based curable composition.

  In the branched polyglycerol chain, the groups (1), (2) and (3) may be bonded to each other in any sequence. As the number of groups (1) increases, the branched structure develops, and the group (4) is present at the end of each branched chain.

  In the present invention, the average total number of bonds (a + b + c + d) of the groups (1), (2), (3) and (4) in the branched polyglycerol chain is determined by NMR analysis or molecular weight comparison with the precursor silicone described later. It is preferably 3 or more, more preferably 3 to 201, and particularly preferably 3 to 51, in order for the branched polyglycerol-modified silicone of the present invention to maintain appropriate silicone properties.

  In the branched polyglycerol chain, a / (a + b + c + d) is preferably 1/20 to 1/2, and more preferably 1/10 to 1/2, in order to have a sufficient hydrophilic effect.

  The number of groups (1) (that is, a) is preferably 1 to 100, more preferably 2 to 50, in the branched polyglycerol chain. The number of groups (4) (that is, d) is preferably 2 to 101, more preferably 3 to 51, in the branched polyglycerol chain. The number of groups (2) (ie, b) and the number of groups (3) (ie, c) are the same or different and are preferably 0 to 198, more preferably 0 to 96. .

  In the branched polyglycerol-modified silicone of the present invention, the linking group that bonds the silicon atom of the silicone and the aforementioned branched polyglycerol chain is preferably a divalent group having an ether group or an ester group.

The divalent group having an ether group is preferably a group represented by the general formula (5) (hereinafter referred to as a linking group (5)). In the linking group (5), the (R ¹ ) _p side is bonded to the silicon atom of the silicone chain, and the (AO) _q side is bonded to the branched polyglycerol chain.
-(R < ¹ >) _p- O- (AO) _q- (5)
(Wherein R ¹ may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms, an alkenylene group, or an arylene group having 6 to 22 carbon atoms, preferably 1 carbon atom) -22 linear or branched alkylene group or alkenylene group, AO is an alkyleneoxy group having 1 to 4 carbon atoms (also referred to as oxyalkylene group) or an aryleneoxy group having 6 to 10 carbon atoms (also referred to as oxyarylene group). Preferably an alkyleneoxy group having 1 to 4 carbon atoms, p is a number of 0 or 1, q is a number of 0 to 30, and q AOs may be the same or different.)
The divalent group having an ester group is preferably a group represented by the general formula (6) (hereinafter referred to as a linking group (6)). In the linking group (6), the R ² side is bonded to the silicon atom of the silicone chain, and the (AO) _r side is bonded to the branched polyglycerol chain.
_{^{-R 2 -COO- (AO) r -}} (6)
(Wherein R ² may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms, an alkenylene group, or an arylene group having 6 to 22 carbon atoms, preferably 1 carbon atom) -22 linear or branched alkylene groups or alkenylene groups, r is a number from 0 to 30, AO is as defined above, and r AOs may be the same or different.
In the linking groups (5) and (6), the arylene group in R ¹ and R ² includes an alkylene arylene group, an arylene alkylene group, and an alkylene arylene alkylene group. R ¹ and R ² are preferably an alkylene group or alkenylene group having 1 to 16 carbon atoms, particularly preferably 1 to 12, and methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene. , Octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene group and the like. Among these, ethylene, propylene, or trimethylene group is more preferable, and ethylene group or trimethylene group is particularly preferable from the viewpoint of easy synthesis.

  p is 0 or 1, but 1 is preferable from the viewpoint of ease of synthesis. q and r are the same or different and are preferably 0 to 15 and particularly preferably 0 to 5. From the viewpoint of ease of synthesis, 0 is most preferable.

  The q AOs and the r AOs are the same or different, and may be alternating, random, block, or a periodic arrangement other than these, or may be combined in any form. AO is preferably an ethyleneoxy group, a propyleneoxy group or a phenyleneoxy group, and more preferably an ethyleneoxy group.

  In the linking group (5) and the linking group (6), the linking group is bonded to the branched polyglycerol chain on the oxygen side of the alkyleneoxy group or aryleneoxy group of AO, and on the alkylene or arylene side of the alkyleneoxy group or aryleneoxy group. It binds to the ether group or ester group contained in

As substituents in R ¹ and R ² , a hydroxy group, an amino group (1 to 22 carbon atoms), an imino group (1 to 22 carbon atoms), a carboxy group, an alkoxy group (1 to 22 carbon atoms), an acyl group ( C1-C22) etc. are mentioned.

Among these, a preferable linking group is a linking group represented by the following general formula (7) (hereinafter referred to as linking group (7)). In the linking group (7), the trimethylene side is bonded to the silicon atom of the silicone chain, and the oxygen atom side is bonded to the branched polyglycerol chain.
_{-CH 2 CH 2 CH 2 -O-} CH 2 CH 2 O- (7)
In the branched polyglycerol-modified silicone of the present invention, the linking group that bonds the silicon atom of the silicone chain and the aforementioned branched polyglycerol chain preferably contains an oxyphenylene group. Among such linking groups, a group represented by the following general formula (8) (hereinafter referred to as linking group (8)) or a group represented by the general formula (9) (hereinafter referred to as linking group (9)). Is preferred. In the linking group (8), the (R ³ ) _u side is bonded to the silicon atom of the silicone chain, and the (AO) _v side is bonded to the branched polyglycerol chain. In the linking group (9), the (R ⁴ ) _z side is bonded to the silicon atom of the silicone chain, and the (AO) _x and (AO) _y sides are bonded to the branched polyglycerol chain.

(In the formula, R ³ is an optionally substituted linear or branched alkylene group or alkenylene group having 1 to 22 carbon atoms, u is a number of 0 or 1, and v is a number of 0 to 30. Number, AO indicates the above meaning, and v AOs may be the same or different.)

(In the formula, R ⁴ may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms or an alkenylene group, z is a number of 0 or 1, and x is a number of 0 to 30. Number, y is a number from 0 to 30, AO is as defined above, and x and y AOs may be the same or different.)
In the linking group (8) and linking group (9), (R ³ ) _u and (R ⁴ ) _z are the silicon atom of the silicone chain and the phenylene group of the oxyphenylene group contained in the linking group of the present invention. R ³ and R ⁴ are preferably an alkylene group or alkenylene group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, Hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene group and the like. Among these, ethylene, propylene, or trimethylene group is more preferable, and ethylene group or trimethylene group is particularly preferable from the viewpoint of easy synthesis.

  u and z are 0 or 1, but 1 is more preferable from the viewpoint of ease of synthesis.

  In the linking group (8) and the linking group (9), AO is an oxyalkylene group or an oxyarylene group that connects the branched polyglycerol chain and the oxygen atom of the oxyphenylene group contained in the linking group of the present invention. And bonded to the branched polyglycerol chain on the oxygen side of the oxyalkylene group or oxyarylene group, and bonded to the oxygen atom of the oxyphenylene group on the alkylene or arylene side of the oxyalkylene group or oxyarylene group. As AO, an oxyethylene group, an oxypropylene group or an oxyphenylene group is preferable, and among these, an oxyethylene group is particularly preferable.

  v, x and y are each a number of 0 to 30, preferably 0 to 15, and more preferably 0 to 5. From the viewpoint of ease of synthesis and ease of reaction, 0 is most preferable. When v, x and y are non-zero numbers, v AOs, x AOs, and y AOs may be the same or different. It may be an alternating type, a block type, a periodic arrangement other than these, or a random type.

In the linking group (8), the bonding mode of the oxygen atom and the (R ³ ) _u group (the silicon atom on the silicone chain when u is 0) bonded to the phenylene group of the oxyphenylene group is ortho-position to each other. , Meta-position and para-position, or a mixture thereof. In the linking group (9), any one of two oxygen atoms bonded to the phenylene group of the oxyphenylene group and (R ⁴ ) _z group (a silicon atom on the silicone chain when z is 0) For the two, the bonding mode may be any of the ortho position, the meta position, and the para position, or a mixture thereof.

  Among the oxyphenylene group-containing linking groups of the present invention, the most preferable one is a linking group represented by the following general formula (10) (hereinafter referred to as linking group (10)). In the linking group (10), the trimethylene side is bonded to the silicon atom of the silicone chain, and the oxygen atom side is bonded to the branched polyglycerol chain.

  In the linking group (10), the bonding mode of the oxygen atom and trimethylene group bonded to the phenylene group of the oxyphenylene group may be any of ortho, meta, and para positions, or a mixture of these. However, from the viewpoint of ease of synthesis, the ortho position, the para position, or a mixture thereof is more preferable.

  The silicone forming the branched polyglycerol-modified silicone of the present invention is derived from a polysiloxane having two or more silicon atoms, and the shape of the polysiloxane is any of linear, branched, and cyclic. Also good. Moreover, the number average molecular weight of polysiloxane becomes like this. Preferably it is 300-700,000, More preferably, it is 300-200,000, More preferably, it is 1000-20,000. The number average molecular weight can be determined by a gel permeation chromatograph (hereinafter referred to as GPC) method, a light scattering method, or the like, which will be described later.

  The branched polyglycerol-modified silicone of the present invention is preferably a linear silicone represented by the following general formula (11) (hereinafter referred to as silicone (11)).

(Wherein R ⁵ , R ⁶ , R ⁷ , t R ⁸ , t R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are the same or different and are each a linking group to which a branched polyglycerol chain is bonded; A linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms, or an aryl group having 6 to 22 carbon atoms, which may have a substituent and may be substituted with a fluorine atom Wherein at least one of R ⁵ , R ⁶ , R ⁷ , t R ⁸ , t R ⁹ , R ¹⁰ , R ¹¹ , R ¹² is a linking group to which a branched polyglycerol chain is bonded. t represents a number from 0 to 10,000.)
In the silicone (11), R ⁵ , R ⁶ , R ⁷ , t R ⁸ , t R ⁹ , R ¹⁰ , R ¹¹ , R ¹² other than the linking group to which the branched polyglycerol chain is bonded are A linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms which may have the same or different substituents and may be substituted with a fluorine atom, or the number of carbon atoms Examples of the alkyl group having 6 to 22 carbon atoms and having 1 to 22 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, trifluoropropyl and the like. Examples of the alkenyl group having 1 to 22 carbon atoms include a vinyl group and an allyl group. Examples of the alkoxy group having 1 to 22 carbon atoms include methoxy, etho Shi, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and a phenoxy group. In these, a C1-C12 linear or branched alkyl group, a vinyl group, an allyl group, or a C6-C12 aryl group is preferable, More preferably, a C1-C3 alkyl group or A phenyl group, particularly preferably a methyl group, a propyl group or a phenyl group. Among these, a methyl group is more preferable from the viewpoint of versatility and price, but a phenyl group is more preferable from the viewpoint of heat resistance.

In the silicone (11), the substituents that R ^{5 to} R ¹² may have include a phenyl group, a phenol group, a hydroxy group, a carboxy group, an amino group (0 to 14 carbon atoms), an imino group, and (aminoethyl). ) Amino group, (dimethylaminoethyl) amino group, polyoxyalkylene group, mercapto group, and epoxy group. When it has these substituents, a propyl group is particularly preferable as R ^{5 to} R ¹² .

In the silicone (11), at least one of R ⁵ , R ⁶ , R ⁷ , t R ⁸ , t R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , preferably 1 to 10, more preferably 1 to 5 is a linking group to which a branched polyglycerol chain is bonded. This linking group may be located at any of the side chain, one end and / or both ends of the silicone (11), or may be a mixture thereof.

One selected from the group consisting of R ^{5 to} R ⁷ and one selected from the group consisting of R ^{10 to} R ¹² represent a linking group to which a branched polyglycerol chain is bonded, and the remaining R ^{5 to} R ⁷ and When R ^{10 to} R ¹² , t R ⁸ , and t R ⁹ represent other groups, the branched polyglycerol-modified silicone of the present invention becomes a branched polyglycerol-modified silicone of both end substitution type, and is used in water and other It is very preferable that they are interconnected in a solvent and easily adopt a higher order structure. In that case, it is particularly preferable that the remaining R ^{5 to} R ⁷ and R ^{10 to} R ¹² , t R ⁸ , and t R ⁹ are methyl groups.

  As described above, the total number of hydroxyl groups (—OH groups) contained in the branched polyglycerol chain / the total number of silicon atoms constituting the siloxane bond in the silicone is 0.01 to 5, more preferably 0. It is preferable from the viewpoint of uniform mixing with the silicone-based curable composition to control the number of branched polyglycerol chains to be 0.02 to 3.

  T in silicone (11) shows the number of 0-10,000, Preferably it shows the number of 1-3000, Most preferably, it shows the number of 5-500.

  The number average molecular weight of the branched polyglycerol-modified silicone of the present invention is preferably 500 to 500,000, particularly preferably 750 to 200,000. The method for measuring the number average molecular weight is based on GPC (polystyrene or polyethylene glycol equivalent) as described later.

  The branched polyglycerol-modified silicone of the present invention has a total number of silicon atoms (Si) in the silicone and groups (1), (2), (3) and (4) in the branched polyglycerol chain (hereinafter referred to as glycerol group number). ) (G) ratio (G / Si) is preferably 0.001 to 50, more preferably 0.05 to 10, and particularly preferably 0.1 to 3.

  In the branched polyglycerol-modified silicone of the present invention, a small amount of ethyleneoxy groups and / or propylene is included in the branched polyglycerol chain as long as the silicone characteristics and the hydrophilic properties are not significantly inhibited. An oxy group may be present. Ethyleneoxy groups and / or propyleneoxy groups may be present randomly in the branched polyglycerol chain, or a plurality of ethyleneoxy groups and / or propyleneoxy groups form a chain and block in the branched polyglycerol chain. May be present. In this case, the block composed of a plurality of ethyleneoxy groups and / or propyleneoxy groups may be present in the vicinity of the linking group of the branched polyglycerol chain, may be present at the terminal, or may be present in the middle. You may do it. When the ethyleneoxy group and / or propyleneoxy group is present, the ethyleneoxy group and / or propyleneoxy group is preferably present in an amount of 0.001 to 0.5 molar equivalents relative to 1 molar equivalent of the glycerol group. More preferably, it is present at 0.02 to 0.2 molar equivalent.

  The production method and confirmation method of the branched polyglycerol-modified silicone, which is the most characteristic component in the dental silicone-based curable composition of the present invention described above, are known from Japanese Patent Application Laid-Open No. 2004-339244. What is necessary is just to manufacture and use it suitably. In the present invention, the branched polyglycerol-modified silicone most preferably used is “Sofcare GS-G” (trade name; manufactured by Kao Corporation), which is a compound belonging to the silicone (11) [bis (polyglyceryl- 3-oxyphenylpropyl) dimethicone] is commercially available.

  The addition amount of the branched polyglycerol-modified silicone is 0.1 to 20 parts by weight, more preferably 0.3 to 100 parts by weight of the total amount of unreacted reactive organopolysiloxane components in the silicone-based curable composition. -10 parts by weight is preferred.

Next, other components contained in the dental silicone-based curable composition in the present invention will be described. The dental silicone-based curable composition, since it is preferable to cure optionally easily and in a short time to be used as dental materials, are applied addition polymerization type silicone causing curing reaction at room temperature.

  A combination of a silicone-based curable composition that causes an addition reaction is generally a combination of an organopolysiloxane having an unsaturated bond at a terminal, a hydrogen polysiloxane having a hydrogen atom directly connected to a silicon atom, and a polymerization catalyst. is there.

  Organopolysiloxane having at least two organic groups having an unsaturated bond at the terminal (hereinafter abbreviated as component (A)) is an organopolysiloxane having at least two organic groups having an unsaturated bond at the terminal. If it is polysiloxane, the structure of the other organic group which exists in a molecule | numerator will not be restrict | limited, A linear or branched structure may be sufficient, and also these mixtures may be sufficient.

  Examples of the organic group having an unsaturated bond at the terminal present in the component (A) molecule include a vinyl group, an allyl group, a 1-butenyl group, and an ethynyl group. Most preferred is a vinyl group attached to an atom. These organic groups having terminal unsaturated bonds may be present at the end or in the middle of the molecular chain of the organosiloxane, or both, but the cured elastic body has excellent physical properties. In order to have properties, at least one is preferably present at the end of the molecule.

  Examples of the organic group bonded to the silicon atom other than the organic group having an unsaturated bond at the above-described end present in the component (A) molecule include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group. Group, aryl group such as phenyl group, substituted alkyl group such as chloromethyl group, 3,3,3-trifluoropropyl group, etc. are exemplified, but among these, it is easy to synthesize and has good physical properties after curing A methyl group is most preferred from the viewpoint of imparting properties.

  The number of siloxane units constituting the molecule of component (A) (corresponding to the degree of polymerization) is not particularly limited, but is suitable for a dental impression material, that is, has an appropriate hardness after curing, and sufficient In order to obtain elongation and mechanical strength, the number of the siloxane units is preferably 50 to 5000, and particularly preferably 100 to 2000.

  If the typical thing of the component (A) used for this invention is shown concretely,

(However, Ph represents a phenyl group). Note that the order of bonding of the repeating structural units in the above-mentioned compounds and the compounds used in the examples and comparative examples described later is completely arbitrary, and the number of repeating structural units shown in the structural formula is simply the total amount of each structural unit. It is only an average.

  The organohydrogenpolysiloxane (hereinafter abbreviated as component (B)) having at least three SiH groups in the molecule of (B) in the present invention functions to form a rubber elastic body by crosslinking the component (A). It is an ingredient with In order to react with the component (A) to form a crosslinked structure, at least three SiH groups are required in the molecule. When the number is less than 3, a crosslinked structure is not obtained and a rubber elastic body cannot be obtained.

  The structure of the component (B) is not particularly limited as long as it has 3 or more SiH groups in the molecule. The organic group bonded to the silicon atom other than the hydrogen atom present in the component (B) molecule is not particularly limited, and the organic group present in the molecule of the component (A) (having an unsaturated group at the terminal) The methyl group is most preferable because it is easy to synthesize and gives good physical properties after curing. Such component (B) may be linear, branched or cyclic, or a mixture thereof.

  The number of siloxane units having no SiH group constituting the component (B) molecule (corresponding to the degree of polymerization) is not particularly limited, but has a property suitable as a dental impression material, that is, an appropriate hardness after curing. In order to obtain sufficient elongation and mechanical strength, the number of siloxane units is preferably 2 to 2000, particularly 5 to 500.

  If the typical thing of the component (B) used for this invention is shown concretely,

The organohydrogenpolysiloxane shown by these is mentioned. In the component (B) used in the above-mentioned compounds and the examples and comparative examples described later, the order of bonding of each repeating structural unit in the molecule is completely arbitrary as in the case of the component (A).

  The organohydrogenpolysiloxane having two hydrogen atoms bonded to silicon atoms in the molecule (C) used in the present invention (hereinafter abbreviated as component (C)) has two SiH groups in the molecule. Any organohydrogenpolysiloxane can be used without limitation. The organic group bonded to a silicon atom other than a hydrogen atom is the same as the component (B) described above, and a methyl group is most preferable because it is easy to synthesize and gives good physical properties after curing. . Such component (C) may be linear, branched or cyclic, or a mixture thereof.

  The number of siloxane units having no SiH group constituting the component (C) molecule (corresponding to the degree of polymerization) is not particularly limited, but has a property suitable as a dental impression material, that is, has an appropriate hardness after curing. In order to obtain sufficient elongation and mechanical strength, the number of the siloxane units is preferably 0 to 1000, particularly 5 to 500.

  If the typical thing of the component (C) used for this invention is shown concretely,

The organohydrogenpolysiloxane shown by these is mentioned. In the component (C) used in the above-mentioned compounds and the examples and comparative examples described later, the order of bonding of each repeating structural unit in the molecule is completely arbitrary as in the case of the component (B).

  In the dental impression material of the present invention, the blending ratio of the components (A), (B) and (C) is not particularly limited as long as it is sufficiently cured, but expresses an appropriate elastic strain as an impression material. Therefore, the ratio of the total number of SiH group hydrogen atoms of the component (C) is 0.05 to 2 times the total number of SiH group hydrogen atoms of the component (B), and the component (B And the ratio of the total number of hydrogen atoms of the SiH group of component (C) to 0.5 to 5 times the total number of terminal unsaturated bonds of component (A). This is because if the total number of hydrogen atoms of the SiH groups of component (B) and component (C) is too small relative to the total number of terminal unsaturated groups of component (A), the curability may be insufficient. In addition, when the amount is too large, excessive hydrogen atoms of SiH groups remain, which may cause foaming due to generation of hydrogen during curing or change with time. Therefore, a particularly preferred blending ratio is such that the total number of hydrogen atoms of the SiH group of component (C) is 0.1 to 1 times the total number of hydrogen atoms of the SiH group of component (B). In addition, it is desirable that the total number of SiH group hydrogen atoms of the component (B) and the component (C) is 2 to 4 times the total number of terminal unsaturated bonds of the component (A).

  In addition, organopolysiloxanes that contain only one organic group with an unsaturated bond at the end and organohydrogenpolysiloxanes that contain only one SiH group in the molecule within a range that does not significantly affect the physical properties. May be added.

  The component (D) hydrosilylation reaction catalyst (hereinafter abbreviated as component (D)) used in the present invention can be used without limitation as long as it is used in a normal hydrosilylation reaction. For example, chloroplatinic acid And alcohol-modified products thereof, platinum vinylsiloxane complexes, and the like. In order to improve the storage stability, a material having a small amount of chloro such as a platinum-vinylsiloxane complex is preferable.

  The amount of component (D) is not particularly limited, but is generally 0.1 to 0.1 parts by weight based on 100 parts by weight of the total amount of unreacted reactive organopolysiloxane components in the silicone-based curable composition in terms of platinum weight. What is necessary is just to set it as the range of 1000 ppm, and 40-500 ppm is more preferable. When the blending amount is less than 0.1 ppm, the crosslinking reaction between the unsaturated bond-containing silicone of component (A) and component (B) and the SiH siloxane of component (C) does not proceed sufficiently, and when it exceeds 1000 ppm, Precipitation of platinum black tends to cause problems such as yellowing of the cured product or blacking of the cured product, or difficulty in controlling the crosslinking reaction.

  The component (E) filler used in the present invention (hereinafter abbreviated as component (E)) is a silicone rubber reinforcing material obtained from component (A), component (B), component (C) and component (D). To work as.

  As the component (E), generally, silica-based powders such as pulverized quartz, fused silica, wet silica, dry silica, diatomaceous earth, polyorganosilsesquioxane fine particles, aluminum oxide, aluminum silicate, iron oxide, zinc oxide, calcium carbonate, Zirconium oxide, carbon black and the like can be mentioned, and these can be used alone or in combination of two or more as required.

  Moreover, the surface of these fillers may be polyorganosiloxanes such as polydimethylsiloxane and octamethylcyclotetrasiloxane, hexamethylsilazane and 1,1,3,3-tetramethyl-1,3-divinyl as necessary. Those treated with an organosilicon compound such as silazanes such as silazane and organosilanes such as vinyltriethoxysilane can be used.

A suitable addition amount of component (E) is 4 to 500 parts by weight with respect to 100 parts by weight of the total amount of unreacted reactive organopolysiloxane components in the silicone-based curable composition, and a more preferred addition amount is 7 -30 parts by weight.
High molecular weight polyorganosiloxane raw rubber, paraffin wax, and the like can be added to the dental silicone-based curable composition in this patent. Furthermore, black platinum or fine palladium can be added as a hydrogen gas absorbent as required.

  Moreover, you may add another additive in the range which does not reduce the physical property remarkably. Such additives include reaction inhibitors, ultraviolet absorbers, plasticizers, pigments, antioxidants, antibacterial agents and the like.

  The dental silicone-based curable composition of the present invention is used as a dental material. The silicone-based curable composition can be widely used from a soft material to a relatively hard material by changing its components.

  Among them, the curable composition in the present invention is suitably used for dental impression materials and dental soft denture lining materials.

  For example, agar, alginate, polysulfide rubber, polyether, and the like are used as dental impression materials in addition to silicone, but agar, alginate impression materials or their associated impressions have clinically appropriate elasticity. However, there are disadvantages such as large permanent deformation, large dimensional change due to evaporation of moisture, and low tear strength. In addition, polysulfide rubber has a strong smell and slow curing, so it is limited to special use impressions. Polyether rubber impression material has a drawback of low elasticity and water absorption and expansion.

  In contrast to the above impression material, an impression material produced using a silicone-based curable composition generally has excellent curability, has very little shrinkage upon curing, does not produce by-products, is tasteless and odorless, and generates heat. While it has a very excellent property of being almost nonexistent, its high hydrophobicity has been a major issue.

In recent years, it has become the mainstream to impart a hydrophilic property by adding a surfactant to the above addition type silicone, which has been improved to a level that is practically not problematic for clinical use. When these surfactants are added in a large amount, the impression material paste tends to bleed little by little during storage. When used regularly, there is no particular problem, but when not used for a long time, a slight but transparent surfactant is separated at the tip of the container. In that case, it must be used after removing the surfactant part that the operator bleeds immediately before use.

  Since the dental silicone-based curable composition in the present invention has hydrophilicity by blending with a modified silicone, it can be suitably used to solve the above problems.

  As a method of using the dental silicone-based curable composition of the present invention as a dental impression material, the component (A), the component (B) and / or the component (C), and the component (D) usually do not coexist at the same time ( That is, a hydrosilylation reaction does not occur during storage), for example, modified silicone, component (A), component (D), component (E), and paste former containing additives as necessary, modified silicone, It is prepared as a two-pack type consisting of paste (B) containing component (A), component (B) and / or component (C), component (E), and additives as necessary. It is common to use. As a manufacturing method of paste former and B, it can be obtained by weighing a proper amount of necessary components and kneading until uniform with a general kneader such as a kneader or planetary.

  Moreover, a dental soft denture lining material is mentioned as what can be optimally used as a dental material by the dental silicone type curable composition in this invention.

  Soft denture lining material is a material that linings dentures that have become incompatible with the oral mucosa due to age, etc., and is a part that directly contacts the oral mucosa in the oral cavity and also has a role to hold the denture in the oral cavity Have.

  As soft denture lining materials, poly (meth) acrylate-based materials and silicone rubber-based materials are mainly known.

  Poly (meth) acrylate-based soft denture lining materials are generally composed of a polymer cured product of a (meth) acrylate-based radical polymerizable monomer such as methyl methacrylate or ethyl methacrylate. Since it does not have the flexibility required as a material, it is necessary to add a plasticizer such as dioctyl phthalate or dibutyl phthalate.

  On the other hand, since silicone rubber is inherently highly biocompatible, silicone rubber-based soft lining materials are also widely used. In general, since silicone rubber is a soft material rich in elasticity, such a silicone rubber-based soft denture lining material is frequently used because it does not require a separate plasticizer.

  On the other hand, for low salivary secretors who have become common in recent years, so-called xerostomia patients, a significant decrease in familiarity with dentures associated with dry oral mucosa has hindered the maintenance and stability of dentures in the oral cavity. ing. When a soft denture lining material having appropriate hydrophilicity and affinity for such a patient is used, it becomes easy to stabilize the denture in the oral cavity. Therefore, the soft denture lining material having such properties is used. Therefore, the development of a silicone-based curable composition that is the basis for this is desired.

  The dental silicone-based curable composition of the present invention has hydrophilicity due to the effect of the modified silicone compound, and is particularly useful as a soft denture lining material for patients with dry mouth as described above.

  As a method of using the dental silicone-based curable composition of the present invention as a soft denture lining material, component (A), component (B) and / or component (C), and component (D) usually do not coexist at the same time. Forms (ie, no hydrosilylation reaction occurs during storage), for example, modified silicone, component (A), component (D), component (E), and paste former containing additives as necessary, and modified silicone , Component (A), component (B) and / or component (C), component (E), and, if necessary, prepared as a two-packed mold containing paste additives, and both are mixed immediately before use. Is generally used. As a manufacturing method of paste former and B, it can be obtained by weighing a proper amount of necessary components and kneading until uniform with a general kneader such as a kneader or planetary.

  The soft denture lining material also includes a mucosa-adjusting material made of particularly soft silicone rubber among silicone resins.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

The components (A) to (F) used in Examples and Comparative Examples are shown below.
・ Component (A) [Unsaturated siloxane]
The components (A) used are summarized in Table 1 below.

・ Ingredients (B) and (C)
The component (B) SiH siloxane and component (C) SiH siloxane used are summarized in Table 2.

The components (D) to (F) used are as follows.
-Component (D): [hydrosilylation reaction catalyst substance]
Platinum-divinyldisiloxane complex / component (E): [filler]
Fumed silica "Leosil ZD-30ST" (manufactured by Tokuyama)
Silicic anhydride (Wako Pure Chemical Industries)
Component (F): [Branched polyglycerol-modified silicone]
Sofcare GS-G (manufactured by Kao Corporation) [Bis (polyglyceryl-3-oxyphenylpropyl) dimethicone]
In the comparative examples, the following compounds were used as an alternative to component (F).

Dimethylpolysiloxane
(TSL451-10, Toshiba Silicone, abbreviated as DMS)
Polyoxyethylene lauryl ether (Wako Pure Chemical Industries, abbreviated as POL).

In Examples and Comparative Examples, dental silicone-based curable compositions were evaluated by the following methods.
(1) Evaluation of hydrophilicity In a constant temperature room at 23 ° C., weighed out equal amounts of paste formers and cocoons having the compositions shown in the comparative examples of each example, kneaded both with a spatula for 30 seconds, and then the diameter. A cured body having a thickness of 20 mm and a thickness of 2 mm was prepared. The contact angle after 30 seconds with a 2 mm diameter distilled water droplet was measured with a contact angle measuring instrument (manufactured by Matsunaga Kagaku). The smaller the contact angle, the higher the hydrophilicity of the cured body.
(2) Method of measuring hardness Shore A hardness, which is an index of flexibility, was measured based on JIS-K7215 (durometer type A). The measurement was performed when the mixture was allowed to stand at 37 ° C. overnight after kneading.
(3) Liquid Separation from Paste by Storage The presence or absence of liquid separation from the paste was observed for 1 month each in the constant temperature room of 23 ° C.

  Evaluation was performed in the following three stages.

  A: No liquid separation was observed at all.

  B: A slight liquid float was visually observed.

C: Separation of a transparent liquid was confirmed.
(4) Soft denture lining material adsorption retention evaluation test Each of the compounds shown in Table 4 with the polymerization ratio was weighed and mixed for about 4 hours with a planetary mixer (manufactured by Inoue Seisakusho). Each paste was weighed in an equal amount, and both were kneaded and evaluated by the following method.

Create a denture base for the maxilla with teeth (“Acron” manufactured by GC) and line the paste paste prepared by the above method on the surface. The shape of the mucous membrane was marked on the lining material. It was immersed in water at 37 ° C. for 24 hours. Immediately before the experiment, the saliva in the oral cavity is wiped off and the oral cavity is temporarily dried, then the lining material is placed in the oral cavity with the lining material side facing, and the time until it falls from the upper jaw (maintenance) Time). This experiment was repeated 5 times, and the average value was taken as the maintenance time.
(5) Impression material impression accuracy evaluation test The mixture was mixed with a planetary mixer (manufactured by Inoue Seisakusho) for about 4 hours to obtain paste A and B. Each paste was weighed in an equal amount, and both were kneaded and the impression accuracy was evaluated by the following method.

  In a constant temperature room of 23 ° C., weighed out equal amounts of paste formers and mortars having the composition shown in Table 4 and kneaded both with a spatula for 30 seconds, and then applied to a fine wire reproducibility evaluation jig (conforming to JIS T6513). A slightly larger amount of paste prepared and kneaded in advance by the above-described method was placed, immediately pressed with a glass plate, and then cured in a constant temperature water bath at 35 ° C.

  After curing, the sample was removed from the jig, and the sample was immediately observed visually or using a magnifying glass, and the finest line reproducing the full length of 25 mm was taken as the value of impression accuracy. Note that the fine line reproducibility evaluation jig is provided with fine lines having a width of 75, 50, and 20 μm, and the finer the line, the more accurate the sample, the higher the impression accuracy.

Example 1
A paste upper and a paste end for soft denture lining materials were prepared with the compositions shown in Table 3, respectively. The preparation was performed using a planetary mixer. These pastes were weighed out in equal amounts and quickly kneaded using a spatula. Each obtained kneaded product was evaluated. The results are shown in Table 4.

  As shown in Table 4, it was found that the contact angle with water was 68 °, which is hydrophilic. In addition, it is said that it is hydrophobic if the contact angle with water usually exceeds 90 °, and hydrophilic if it is 90 ° or less. Moreover, it was hold | maintained with respect to the dry oral-mucosal surface for 20 second, and it was shown that the retention strength is rising. It was also found that the hardness was 33 and it had sufficient characteristics as a soft lining material. Furthermore, liquid separation from the paste was not observed even after storage for 1 month.

Examples 2-3
Evaluation was performed in the same manner as in Example 1 except that the addition amount of the branched polyglycerol-modified silicone as the component (F) was changed. The composition is shown in Table 3, and the result is shown in Table 4.

  As shown in Table 4, it was shown that all the compositions were hydrophilic when the contact angle was 90 ° or less, and the retention force on the oral mucosal surface was increased. All had hardness suitable for soft denture lining materials. Furthermore, liquid separation from the paste was not observed even after storage for 1 month.

Examples 4-6
Evaluation was performed in the same manner as in Example 1 except that the branched polyglycerol-modified silicone of component (F) was added to the paste end side and the amount added was changed. The composition is shown in Table 3, and the result is shown in Table 4.

  As shown in Table 4, it was shown that all the compositions were hydrophilic when the contact angle was 90 ° or less, and the retention force on the oral mucosal surface was increased. All had hardness suitable for soft denture lining materials. Furthermore, liquid separation from the paste was not observed even after storage for 1 month.

Example 7
Evaluation was performed in the same manner as in Example 1 except that the branched polyglycerol-modified silicone of component (F) was distributed and added to the side of the paste A and B. The composition is shown in Table 3, and the result is shown in Table 4.

  As shown in Table 4, it was shown that the contact angle was 67 ° and it became hydrophilic, and the retention force on the oral mucosa surface was also increased. The hardness was 33, which was suitable for a soft denture lining material. Furthermore, liquid separation from the paste was not observed even after storage for 1 month.

Examples 8-14
Evaluation was performed in the same manner as in Example 1 except that the type or blending amount of the unsaturated siloxane of component (A) and components (B) and (C) organohydrogenpolysiloxane was changed. The composition is shown in Table 3, and the result is shown in Table 4.

  As shown in Table 4, it was shown that all the compositions were hydrophilic when the contact angle was 90 ° or less, and the retention force on the oral mucosal surface was increased. All had hardness suitable for soft denture lining materials. Furthermore, liquid separation from the paste was not observed even after storage for 1 month.

Comparative Example 1
Without adding the branched polyglycerol-modified silicone of component (F), other components were prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The composition is shown in Table 3, and the result is shown in Table 4.

  As shown in Table 4, the contact angle with water was 110 °, and it was found to be extremely hydrophobic. Further, no adsorption was observed on the dried oral mucosal surface, and it was found that there was almost no holding power in such a state.

Comparative Examples 2-3
The branched polyglycerol-modified silicone of component (F) is changed to a linear polysiloxane having no glycol moiety, and other components are prepared in the same manner as in Example 1, and the paste is prepared in the same manner as in Example 1. Evaluation was performed. The composition is shown in Table 3, and the result is shown in Table 4.

  As shown in Table 4, it was found that all the compositions had a contact angle with water of 110 ° and were extremely hydrophobic. Further, no adsorption was observed on the dried oral mucosal surface, and it was found that there was almost no holding power in such a state.

Comparative Example 4
The component (F) branched polyglycerol-modified silicone was changed to a surfactant, and other components were prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The composition is shown in Table 3, and the result is shown in Table 4.

  As shown in Table 4, although it showed high hydrophilicity and holding power, liquid separation by storage was remarkable.

Example 15
An impression material paste former and paste paste B were prepared with the compositions shown in Table 5, respectively. The preparation was performed using a planetary mixer. These pastes were weighed out in equal amounts and quickly kneaded using a spatula. Each obtained kneaded product was evaluated. The results are shown in Table 6.

  As shown in Table 7, it was found that the contact angle with water was 38 °, and it was hydrophilic. Note that it is desirable that the contact angle with water is less than 70 ° as the impression material. Also, the impression accuracy was 20 μm which is the lower limit of measurement, and it was found that the impression material has high impression accuracy. Furthermore, liquid separation from the paste was not observed even after storage for 1 month.

Examples 16-17
Evaluation was performed in the same manner as in Example 15 except that the addition amount of the branched polyglycerol-modified silicone as the component (F) was changed. Table 5 shows the composition and Table 6 shows the result.

  As shown in Table 6, all the compositions were hydrophilic when the contact angle was 70 ° or less. Also, the impression accuracy was 20 μm which is the lower limit of measurement, and it was found that the impression material has high impression accuracy. Furthermore, liquid separation from the paste was not observed even after storage for 1 month.

Examples 18-20
Evaluation was performed in the same manner as in Example 15 except that the branched polyglycerol-modified silicone of component (F) was added to the paste end side and the amount added was changed. Table 5 shows the composition and Table 6 shows the result.

  As shown in Table 6, all the compositions were hydrophilic when the contact angle was 70 ° or less. Also, the impression accuracy was 20 μm which is the lower limit of measurement, and it was found that the impression material has high impression accuracy. Furthermore, liquid separation from the paste was not observed even after storage for 1 month.

Example 21
Evaluation was performed in the same manner as in Example 15 except that the branched polyglycerol-modified silicone of component (F) was distributed and added to the side of the paste A and B. Table 5 shows the composition and Table 6 shows the result.

  As shown in Table 6, the contact angle was 37 °, which was hydrophilic. Also, the impression accuracy was 20 μm which is the lower limit of measurement, and it was found that the impression material has high impression accuracy. Furthermore, liquid separation from the paste was not observed even after storage for 1 month.

Examples 22-28
Evaluation was performed in the same manner as in Example 15 except that the type or blending amount of the unsaturated siloxane of component (A) and the components (B) and (C) organohydrogenpolysiloxane was changed. Table 5 shows the composition and Table 6 shows the result.

  As shown in Table 6, all the compositions were hydrophilic when the contact angle was 70 ° or less. Also, the impression accuracy was 20 μm which is the lower limit of measurement, and it was found that the impression material has high impression accuracy. Furthermore, liquid separation from the paste was not observed even after storage for 1 month.

Comparative Example 5
Without adding the branched polyglycerol-modified silicone of component (F), other components were prepared in the same manner as in Example 15 and evaluated in the same manner as in Example 1. Table 5 shows the composition and Table 6 shows the result.

  As shown in Table 6, the contact angle with water was 80 °, and it was found that the impression material lacks hydrophilicity. It was also found that the impression accuracy can only be reproduced up to 75 μm and the accuracy is not sufficient.

Comparative Examples 6-7
The branched polyglycerol-modified silicone of component (F) is changed to a linear polysiloxane having no glycol moiety, and other components are prepared in the same manner as in Example 15, and the paste is prepared in the same manner as in Example 15. Evaluation was performed. Table 5 shows the composition and Table 6 shows the result.

  As shown in Table 6, the contact angle with water was 80 ° in any composition, and it was found that the impression material was insufficient in hydrophilicity. It was also found that the impression accuracy can only be reproduced up to 75 μm and the accuracy is not sufficient.

Comparative Example 8
The branched polyglycerol-modified silicone of component (F) was changed to a surfactant, and other components were prepared in the same manner as in Example 15 and evaluated in the same manner as in Example 15. Table 5 shows the composition and Table 6 shows the result.

  As shown in Table 6, although it showed high hydrophilicity and high impression accuracy, liquid separation by storage was remarkable.

Claims (3)

Organopolysiloxane (A) having at least two organic groups having an unsaturated bond at the end thereof, organohydrogenpolysiloxane (B) having at least three SiH groups in the molecule, SiH groups in the molecule At least one branched polyglycerol chain is bonded to the silicon atom of the organohydrogenpolysiloxane (C) having two silanes, the hydrosilylation reaction catalyst material (D), the filler (E), and the silicone via a linking group. branched polyglycerol-modified silicone (F) dental silicone curable composition comprising a composition containing. A dental silicone impression material prepared using the dental silicone-based curable composition according to claim 1 . A dental silicone soft denture lining material prepared using the dental silicone-based curable composition according to claim 1 or 2 .