JPH02225407A - Urethane resin for dental use - Google Patents

Abstract

PURPOSE:To provide a urethane resin for dental use, having improved shock- absorbing property of a polymer and useful as an artificial tooth, denture base, etc., especially e.g. dental crown to be attached to an implanted dental implant. CONSTITUTION:The objective polymerizable urethane resin for dental use is expressed by formula I or formula II [R1, R2, R5 and R6 are CH2=CHCOO or CH2=C(CH3)COO; R3, R4, R7 and R8 are H or CH3; X, X1 and X2 are polyisocyanate residue; Y, Y1 and Y2 are residue of polyether polyol or polyester polyol]. The dental resin of formula I can be produced by reacting 1 equivalent of a polyester polyol or polyether polyol with 2 equivalent of a polyisocyanate to obtain an oligomer having isocyanate group at the terminal and urethanizing the oligomer with 2 equivalent of beta-hydroxyethyl (meth)acrylate or beta- hydroxypropyl (meth)acrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a dental resin whose polymer has excellent shock absorption ability, and a dental polymer obtained by polymerizing the same.

[Conventional technology]

Dental resins (herein referred to as monomers) are widely used in the field of dental treatment, and there are, for example, the following modes of use.

(1) Filling/Restoration Here, dental resin is used as the main raw material for polymers (polymer materials) to fill holes left by cavities or to repair parts of teeth chipped due to cavities or accidents. Ru. Dental resins are polymerized in situ (on the tooth).

(2) Adhesion Here, dental resin is used as an adhesive for bonding an artificial tooth crown made of metal, ceramic, or synthetic resin to a natural tooth. The dental resin is polymerized in situ (on the adhesive surface), and adhesive strength is developed through polymerization.

(3) Dental crown Here, dental resin is used as the main raw material for the main polymer (polymer material) that constitutes the artificial tooth crown, such as a veneer. Dental resins are polymerized at the same time or prior to molding.

(4) Denture base Here, dental resin is used as the main raw material for the main polymer (polymer material) that makes up the base of a so-called complete denture. Dental resins are polymerized at the same time or prior to molding.

(5) Artificial Teeth Here, the dental resin is used as the main raw material for the main polymer (polymer material) constituting artificial teeth, temporary crowns, etc. of dentures, so-called complete dentures. Dental resins are polymerized at the same time or prior to molding.

In addition, it is necessary to use various auxiliary materials together with the dental resin depending on the type of Li used.

By the way, as a specific example of such a dental resin, liquid methyl methacrylate having the following structural formula: It has been used as a molecular material).

However, polymers of methyl methacrylate have wear resistance,
There was a dislike for not being satisfied with aspects such as strength.

Therefore, recently, LIDM of unsaturated urethane monomer^
was proposed as a dental resin. UDMA is a product obtained by reacting 2-hydroxyethyl methacrylate as a hydroxy compound and trimethylhexamethylene diisocyanate as a polyisocyanate in chemically equivalent amounts, and the hydroxy group (OH) and the isocyanate group (NGO) has a urethane bond (-NIICOO-) generated by an addition reaction.

llDMA no longer has active NGO groups and is a stable liquid, but it is a type of monomer that has two ethylenically unsaturated double bonds, and it can be vinyl-polymerized to form a solid resin (polymer). be able to.

Therefore, tlDMA is polymerized alone or together with other polymers (including crosslinking monomers having two or more ethylenically unsaturated double bonds), optionally in the presence of inorganic or organic fillers (e.g. silica powder). By doing so, a polymer having excellent wear resistance and strength can be obtained.

[Problems to be Solved by the Invention] However, 1: All of these resins are intended to be used for jacket crowns, fascia tops, m-reading tops, etc., and therefore, the impact absorption ability of the polymer is limited. However, there was a problem in that the impact absorption ability was low.

This problem arises because, especially when an artificial tooth root is implanted in the jawbone and a crown is attached over it, there is no equivalent to the periodontal ligament of a natural tooth, and the crown has poor shock absorption ability. The occlusal pressure is directly transmitted to the alveolar bone, which not only causes discomfort during mastication, but also causes stress to concentrate on the alveolar bone, which may cause bone resorption.

Therefore, an object of the present invention is to improve the shock absorption ability of dental resin polymers.

(Means for Solving the Problems) Therefore, the present invention first provides a polymerizable urethane-based dental resin represented by the following general formula (1): R or -catalytic formula (2).

However, in the formula, R7, R8 and R8 may be the same or different, but Ctlz=CHCOO- group or cut=C(
CI(3)Co.

- represents a group, R2, R#, R? and R, which may be the same or different, represent ■ or C112, and X, ni, and x2 may be the same or different,
Represents a polyisocyanate residue, and y, Yl and yi may be the same or different,
Represents the residue of a polyether polyol or polyester polyol.

The above Y may consist of the general formula: Ys Rq-Y*, in which case P is polymethylene tit: (Cllz) -
(n≧2), and V and Yl may be the same or different, and represent a residue of a polyether polyol or a polyester polyol.

Second, the present invention provides a dental polymer obtained by polymerizing the dental resins of general formulas 1 to H. The dental resin of general formula 2 I is synthesized, for example, as follows.

First, (11 polyester polyol or polyether polyol, which is widely used in polyurethane resin technology)
An oligomer with an isocyanate (-NGO) group at the end is synthesized by reacting the same amount with 2 equivalents of polyisocyanate, and (2) this is mixed with 2 equivalents of β-hydroxyethyl (meth)acrylate or β-hydroxypropyl (meth)acrylate. React acrylate and urethane.

In this specification, the expression "(meth)acrylic...-" means "methacrylic..." or "acrylic..."
means one or both (mixture).

Further, the dental resin of the general formula (2) is synthesized, for example, as follows.

First, (1) A starting material widely used in polyurethane resin technology: 2 equivalents of polyester polyol or polyether polyol are reacted with 1 equivalent of polyisocyanate to form a hydroxyl terminal (-Oll).
or carboxyl group (-C00II), and then (2) synthesize this with 2 equivalents of β-hydroxyethyl (meth)acrylate or β-hydroxypropyl (-C00II).
By performing an etherification or esterification reaction with meth)acrylate, a dental resin of the general formula (2) can be obtained.

In this case, the general formula can be one of the starting materials: Ys
R? The precursor of the organic group of Yl can be synthesized, for example, by ring-opening addition polymerization of a cyclic ester or oxirane compound using polymethylene glycol (generally having 2 to 8 carbon atoms), which is widely used in polyurethane resin technology, as an initiator. can do.

As raw materials for the above production method, for example, the following are used.

(1) Polyisocyanate: Aliphatic isocyanate such as ethylene diisocyanate, propylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate-1, transcyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isoborone diisocyanate, dicyclohexylmethane diisocyanate (hydrogenated MDi) ), methylene bis(4-cyclohexyl isocyanate), methylcyclohexane diisocyanate, bicyclohebutane triisocyanate trimethylhexamethylene diisocyanate (2,2,3-)limethyl and 2,3.3-)limethyl, and mixtures of both are also used. alicyclic isocyanates, tolylene diisocyanate, tolylene diisocyanate, naphthylene-1,5 diisocyanate, diphenylmethane diisocyanate-1, polymethylboriphenylpolyisocyanate, methylbenzene diisocyanate, xylylene diisocyanate, etc. or aromatic polyisocyanates.

Depending on the form of use, it is also possible to use broncated polyisocyanates whose isocyanate groups are blocked and unblocked by heat during polymerization.

(2) Polyether polyol: ■For example, ethylene glycol, diethylene glycol,
Propylene glycol, 1,4-phthylene gelylcol,
Aliphatic or alicyclic polyhydric alcohols such as glycerin, hexanetriol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, dipropylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, decamethylene glycol, or ■ For example, ethylene oxide, ethylene oxide, A product with a molecular weight of about 100 to 6,000 obtained by addition polymerizing one or more aliphatic oxides such as propylene oxide and butylene oxide.

(3) Polyester polyol: Polyhydric alcohol and aliphatic or alicyclic polycarboxylic acid (e.g., malonic acid, maleic acid, succinic acid, adipic acid, glutaric acid, pimelic acid, sebacic acid, oxalic acid, Hexahydrophthalic acid, etc.) with a molecular mt of about 00 to 6000.

Alternatively, those having a molecular weight of about 100 to 6,000 obtained by ring-opening polymerization of cyclic esters such as propiolactone, butyrolactone, and caprolactone.

(4) Cyclic esters: propiolactone, butyrolactone, caprolactone, etc.

(5) Oxirane compounds: ethylene oxide, propylene oxide, butylene oxide, etc.

In addition, when reacting a polyol and a polyisocyanate, an active hydrogen compound may be used together depending on the case. Examples of such active hydrogen compounds include ethylene glycol, diethylene glycol, propylene glycol,
1.4-butylene glycol, glycerin, hexanetriol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, dipropylene glycol, neopentyl glycol, 1.6-hexamethylene glycol, decamethylene glycol, l,2-polybutadiene Examples include polyol, 1,4-polybutadiene polyol, polychloroprene polyol, butadiene-acrylonitrile copolymer polyol, polydimethylsiloxane dicarbinol, and the like.

Most of the dental resins of the present invention are in liquid form, but solid (powder) ones may be used in liquid form by dissolving or dispersing them in other liquid resins (monomers) or in a solvent, depending on the form of use. It is preferable.

The dental resin of the present invention is characterized in that it is capable of vinyl polymerization and is thereby cured. Therefore, the resin of the present invention can be used in various ways as explained in (1) to (5) in the [Prior Art] section. In that case, the dental resin of the present invention is not limited to a solid one, and depending on the purpose, other dental resins such as methyl methacrylate (MMA) or UD may be used.
Can be used in combination with M^.

When the resin of the present invention or a mixture with other resins (monomers) is polymerized and cured, optionally organic or inorganic fillers such as silica powder, glass powder, PMMA (polymethyl methacrylate) bar, crosslinked PMMA powder,
The filler, which may be mixed with quartz powder, fine ceramic powder, etc., can increase the hardness and wear resistance of the polymer or reduce the water absorption rate of the polymer, depending on the type and amount.

■The resin of the present invention, ■A mixture with other resins (Nanatsumar), or ■A mixture of these resins with an organic or inorganic filler is polymerized and the resulting polymer is pulverized by a conventional method. The resin of the present invention or other resins or a mixture of both may be used in dental treatment.

Depending on the mode of use, it is necessary to polymerize the resin of the present invention or a mixture with other resins (seven polymers) at room temperature, so tri-n-butylborane peroxide or peroxide may be used as a polymerization initiator or polymerization accelerator. - Tertiary amine-based redonx catalysts are used.

Since polymerization is initiated at room temperature, it is mixed immediately before use and the mixture polymerizes in situ within or on the tooth.

Since this method is busy and has poor work efficiency, polymerization is also carried out by irradiating it with ultraviolet rays or, more recently, with visible light.
In this case, a photodegradable polymerization initiator such as d, l-camphorquinone, α-diketone, etc. is used. In this case, the composition containing the resin of the present invention is filled into the inside of the tooth or placed on the surface of the tooth, and then irradiated with light to polymerize and harden (solidify).

The resin of the present invention is particularly useful for dental crowns attached to implanted dental implants, artificial teeth, denture bases, etc., since the polymer has excellent shock absorption ability.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

[Example 1.・-・-・・・・・・・Example of Claim 1] (1) Adipic acid and ethylene glycol are subjected to an ester reaction in an equivalent ratio of about 1:1.2 to form a molecule. 1
About 1.500 polyester polyols (bifunctional) were synthesized.

(2) Next, 1 equivalent of the polyol is reacted with 2 equivalents of isophorone diisocyanate to form an oligomer (prepolymer) with an incyanate (-NGO) group at the end.
was synthesized.

(3) 2 equivalents of β- to 1 equivalent of the oligomer (bifunctional)
The dental resin of this example was synthesized by performing a urethane reaction with hydroxyethyl methacrylate.

This resin was in a liquid state and had two C═C double bonds per molecule, and was capable of vinyl polymerization.

[Example 2...------------Example of Claim 1] (1) Commercially available polyethylene propylene glycol with a molecular weight of about 1,500 (bifunctional, molar ratio of ethylene propylene is 1X1) I got it.

(21) Next, 1 equivalent of the polyol is reacted with 2 equivalents of isophorone diisocyanate to form an oligomer (prepolymer) with an isocyanate (-NGO) group at the end.
was synthesized.

(3) 2 equivalents of β per 1 equivalent of the oligomer (bifunctional)
-Hydroxyethyl methacrylate-urethane reaction was performed to synthesize the dental resin of this example.

This resin was in a liquid state and had two C═C double bonds per molecule, and was capable of vinyl polymerization.

[Example 3 - - - - - - - - - - - Example of claim 2] (1) Ring-opening addition polymerization of T-butyrolactone to trimethylene glycol as an initiator In this way, a polyester polyol (bifunctional) having about 1,000 molecules per molecule was synthesized.

(2) Next, 1 equivalent of the polyol was reacted with 2 equivalents of isophorone diisocyanate to synthesize an oligomer (prepolymer) having an isocyanate (-NGO) group at the end.

(3) 2 equivalents of β- to 1 equivalent of the oligomer (bifunctional)
The dental resin of this example was synthesized by performing a urethane reaction with hydroxyethyl methacrylate.

This resin was liquid and contained two C-C double bonds per molecule, and was capable of vinyl polymerization.

[Example 4...------------Example of claim 2] (1) Using ethylene glycol as an initiator, propylene oxide is subjected to ring-opening addition polymerization to form a molecule of 1
Approximately 800 polyether polyols (bifunctional) were synthesized.

(2) Next, 1 equivalent of the polyol is reacted with 2 equivalents of isophorone diisocyanate to form an oligomer (prepolymer) with an isocyanate (-NGO) group at the end.
was synthesized.

(3) 2 equivalents of β- to 1 equivalent of the oligomer (bifunctional)
The dental resin of this example was synthesized by performing a urethane reaction with hydroxyethyl methacrylate.

This resin was in a liquid state and had two C═C double bonds per molecule, and was capable of vinyl polymerization.

[Example 5--...--------Claim No. 3
Example] (1) 2 equivalents of the polyester polyol synthesized in (1, 1) of Example 1 are reacted with 1 equivalent of inphorone diisocyanate to form a terminal with hydroxyl (-
An oligomer (prepolymer) of the 011) group was synthesized.

(2) 2 equivalents of β per 1 equivalent of the oligomer (bifunctional)
The dental resin of this example was synthesized by carrying out an etherification reaction with -hydroxyethyl methacrylate.

This resin was in a liquid state and had two C═C double bonds per molecule, and was capable of vinyl polymerization.

[Example 6・～・・−・−・・−・−・Example according to claim 3] (1) 1 equivalent of isophorone diisocyanate was added to 2 equivalents of the polyether polyol obtained in Example 2 (1). By reacting, the terminal becomes hydroxyl (-Old
) An oligomer (prepolymer) of i was synthesized.

(2) 2 equivalents of β per 1 equivalent of the oligomer (bifunctional)
The dental resin of this example was synthesized by carrying out an etherification reaction with -hydroxyethyl methacrylate.

This resin was in a liquid state and had two C═C double bonds per molecule, and was capable of vinyl polymerization.

[Example 7 - Example of polymerized product] Prepare 100 parts by weight of the resins of Examples 1 to 6, add 1 part by weight of benzoyl peroxide as a polymerization initiator, and uniformly The mixture was heated at 120° C. for 15 minutes to polymerize.

The physical properties of the obtained polymer are shown in Table 1 below.

In Table 1, in the comparative example, commercially available uDMA was used as the resin.

Table 1 (*The lower the flexural modulus, the better the impact absorption ability) (Example 8--1--------Example of polymer) Prepare 100 parts by weight of the resins of Examples 1 to 6, and 5 as an inorganic filler
50 parts by weight of iOxa powder (average particle size 1 to 50 μm) and 1 part by weight of benzoyl peroxide as a polymerization initiator were added and mixed uniformly.
Polymerization was performed by heating for 5 minutes.

The physical properties of the obtained polymer are shown in Table 2 below.

In Table 2, in the comparative example, commercially available LIDMA was used as the resin.

Table 2 [Example 9---------- Examples of polymers] The polymers obtained in Examples 7 and 8 were pulverized and the average particle size was 10 to 5.
0 μm filler, and 80 parts by weight of this filler was
100 parts by weight of DMA and 1 part by weight of benzoyl peroxide as a polymerization initiator were added and mixed uniformly, and the mixture was heated at 120° C. for 15 minutes to polymerize.

The physical properties of the obtained polymer are shown in Table 3 below.

In Table 3, in the comparative example, commercially available UDMA was used as the resin.

Table 3 (*The lower the flexural modulus, the better the impact absorption ability) (*The lower the flexural modulus, the better the impact absorption ability) [Effects of the Invention] As described above, the resin of the present invention, when polymerized, To provide a polymer with high elastic modulus, that is, excellent shock absorption ability.

Therefore, the resin and polymer of the present invention are particularly useful as main materials for dental crowns attached to artificial tooth roots, artificial teeth, denture bases, and the like.

Claims (1)

[Claims] 1. A polymerizable urethane dental resin represented by the following general formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼. However, in the formula, R_1 and R_2 may be the same or different,
CH_2=CHCOO- group or CH_2=C(CH_3)COO- group, R_3
and R_4 may be the same or different, and represent H or CH_3, and X_1 and X_2 may be the same or different,
It represents a polyisocyanate residue, and Y represents a polyether polyol or polyester polyol residue. 2. The polymerizable urethane dental resin according to claim 1, wherein the Y has the general formula: Y_3-R_9-Y_4. However, in the formula, R_9 is a polymethylene chain, and Y_3 and Y_4 may be the same or different,
Represents the residue of a polyether polyol or polyester polyol. 3 A polymerizable urethane dental resin represented by the following general formula II: ▲Mathematical formula, chemical formula, table, etc.▼ However, in the formula, R_5 and R_6 may be the same or different,
CH_2=CHCOO- group or CH_2=C(CH_3)COO- group, R_7
and R_8 may be the same or different, and represent H or CH_3, X represents a polyisocyanate residue, and Y_1 and Y_2 may be the same or different,
Represents the residue of a polyether polyol or polyester polyol. 4. A dental polymer obtained by polymerizing the dental resin according to claims 1 to 3.