JPS5931484B2 - Resin for outer layer of veneer crown or jacket crown - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin for the outer layer of a veneer layer or jacket crown.

For details, refer to the general formula (where R is a saturated aliphatic hydrocarbon residue having 2 to 5 carbon atoms, R' is an unsaturated aliphatic hydrocarbon residue having 2 to 4 carbon atoms, and n is 1 to 3 is a positive number)
This is a resin for the outer layer of the veneer or jacket crown, which is composed of an unsaturated carbonate homopolymer or a copolymer containing 50% (by weight) or more of the above unsaturated carbonate monomer unit.

The methacrylate polymer referred to in the present invention includes homopolymers of methacrylate monomers and copolymers obtained by copolymerizing different types of methacrylate monomers or methacrylate monomers and other copolymerizable monomers. It is a generic term.

Traditionally, veneering and jacket crowns are wide (used in the dental industry).

The veneer is generally a cast metal crown with resin built up on the surface.

For example, first, an opaque layer with good adhesiveness is formed in contact with a metal cast crown, then a dentin layer is formed on top of the opaque layer to reproduce the color tone of natural teeth, and finally, a transparent color is reproduced, It is used in a form with an enamel layer formed to protect the dentin layer.

The jacket crown is used in the form of a metal cast crown or a resin, in which the opaque layer, dentin layer, and enamel layer are sequentially built up.

Generally, each layer is formed by separately preparing a powdered resin component and a liquid or paste monomer component, and thoroughly kneading the two components by a dentist or technician.

Therefore, the powdered resin component can be said to be an extremely important factor, since it not only affects the workability of dentists and technicians, but also greatly affects the long-term use of dentures.

In particular, the outermost layer of the veneer or jacket crown not only protects the inner layer, but also undergoes significant surface changes due to abrasion caused by toothbrushes and the like, so surface stability plays an extremely important role in terms of appearance.

However, although conventional veneer crowns or jacket crowns have been technologically advanced, they cannot completely prevent the water absorption of the resin, cannot remove dirt, and especially have insufficient abrasion resistance. It was not possible to prevent wear caused by toothbrushes.

That is, the greatest technical challenge was to develop a resin that is wear-resistant and non-hygroscopic for the outer layer of either the front cover or the jacket crown.

The present inventors have conducted extensive research to solve the above technical problems.

As a result, the general formula R'0CO(-R-0-)-nCOR
' (However, R is a saturated aliphatic hydrocarbon residue having 0 to 5 carbon atoms, R' is an unsaturated aliphatic hydrocarbon residue having 2 to 4 carbon atoms, and n is a positive residue having 1 to 3 carbon atoms. A homopolymer of unsaturated carbonate represented by 50 (
The present inventors have now completed the present invention by discovering that when a copolymer powder containing at least 5% by weight is used on the veneer or in the outer layer of the jacket crown, extremely good abrasion resistance and moisture absorption resistance are exhibited.

That is, the present invention has the general formula R'OCO(7R-0)-nCOR
'10 (However, R is a saturated aliphatic hydrocarbon residue having 2 to 5 carbon atoms, R' is an unsaturated aliphatic hydrocarbon residue having 2 to 4 carbon atoms, and n is 1 to 3 carbon atoms. A resin for the outer layer of the veneer or jacket crown, which is composed of a homopolymer of unsaturated carbonate represented by (a positive number) or a copolymer containing 50% (by weight) or more of the above unsaturated carbonate monomer unit. be.

The present invention also provides the above general formula R'OCO(7R-0-)-n
A veneer or jacket crown made of a mixture of a homopolymer of unsaturated carbon 111 0 0 carbonate represented by COR' or a copolymer containing 50% (by weight) or more of the unsaturated carbonate monomer unit and a methacrylate polymer. The company also provides resins for the outer layer.

The resin for the outer layer of the veneer or jacket crown used in the present invention has the general formula R'0CO(-R-0几COR'100 (where R is a saturated aliphatic hydrocarbon residue having 2 to 5 carbon atoms). , R' is an unsaturated aliphatic hydrocarbon residue having 2 to 4 carbon atoms, and n is a positive number of 1 to 3) or the unsaturated carbonate monomer unit It is a copolymer containing 50% (by weight) or more of

The homopolymer or copolymer can also be used in combination with a methacrylate polymer.

Homopolymers or copolymers of the above-mentioned unsaturated carbonates are known.

For example, unsaturated carbonate homopolymers or copolymers are used as synthetic resin lenses in glasses, optical equipment, and the like.

Therefore, in the present invention, these known materials can be used as they are.

Of course, in the present invention, the method of producing the unsaturated carbonate and the method of polymerizing or copolymerizing the unsaturated carbonate are not limited, and any method may be used.

To illustrate these typical methods, the following methods are preferably employed.

For example, unsaturated carbonates are produced by reacting chloroformic acid ester obtained by the reaction of alcohol with phosgene with unsaturated alcohol; A method for producing an unsaturated carbonate by reacting a reaction product with an unsaturated organic halide; A method for producing an unsaturated carbonate by reacting an alkali metal carbonate, an alcoholic unsaturated organic halide, and carbon dioxide gas, etc. There is.

The object of the present invention is, as mentioned above, a resin for the outer layer of a veneer or jacket crown.

Therefore, the carbonate must be an unsaturated carbonate that can be polymerized.

In this sense, R' in the above general formula is most preferably an unsaturated aliphatic hydrocarbon residue having 2 to 4 carbon atoms.

Generally, carbonates in which R' is a vinyl group, that is, an unsaturated aliphatic hydrocarbon residue having 2 carbon atoms, have limited industrial production methods, and are highly polymerizable, so carbonates with 3 carbon atoms are generally used.
~4 unsaturated aliphatic hydrocarbon residues are most widely used.

In addition, unsaturated carbonates in which R' is an unsaturated hydrocarbon residue having 5 or more carbon atoms tend to have poor polymerizability and may be difficult to manufacture. It is often inferior to saturated carbonate.

Similarly, R in the above general formula is preferably a saturated aliphatic hydrocarbon residue having 2 to 5 carbon atoms, preferably 2 to 4 carbon atoms.

Further, in the general formula, n is a positive number from 1 to 3, depending on the raw material for producing the unsaturated carbonate.

Examples of typical unsaturated carbonates include monoethylene glycol bis (allyl carbonate), diethylene glycol bis (vinyl carbonate), diethylene glycol bis (allyl carbonate), triethylene glycol bis (allyl carbonate), diethylene glycol bis (methallyl carbonate), Unsaturated carbonates such as dipropylene glycol bis (allyl carbonate), diethylene glycol bis (allyl carbonate), dipentane diol pis (allyl carbonate), and diethylene glycol bis (butenyl carbonate) are preferably used.

The unsaturated carbonate polymer used is one obtained by polymerizing the unsaturated carbonate alone or by mixing it with other copolymerizable monomers in the presence of a radical initiator such as benzoyl peroxide, isopropyl peroxydicarbonate, etc. Bye.

Monomers copolymerizable with the unsaturated carbonate-1 are not particularly limited, and generally include methyl methacrylate,
Alkyl methacrylate monomers such as ethyl methacrylate, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate; bisphenol A dimethacrylate;
Bisphenol A diglycidyl methacrylate, 2.2
-Bisphenol A such as bis(4-methacryloxyethoxyphenyl)furopane, 2,2-bis(4-methacryloxyisopropoxyphenyl)propane, 2,2-his(4-methacryloxypropoxyphenyl)propane, etc.
Dimethacrylate monomer: ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-
Glycol dimethacrylate monomers such as butadiol dimethacrylate and neopentyl glycol dimethacrylate are used.

Further, in the present invention, the methacrylate polymer used in combination with the unsaturated carbonate homopolymer or copolymer is not particularly limited, and any known methacrylate polymer can be used.

The most commonly used methacrylate polymers are the alkyl methacrylate monomers and bisphenol A.
A homopolymer obtained by polymerizing dimethacrylate monomers and glycol dimethacrylate monomers alone, a copolymer obtained by copolymerizing the above monomers, or a copolymerization of the above monomers and other copolymerizable monomers. Copolymers can be suitably used.

The unsaturated carbonate copolymers and methacrylate copolymers generally contain 50 unsaturated carbonate monomer units and methacrylate monomer units.
(by weight) % or more is preferably used, and it is generally preferable to use a copolymer containing 70 to 99 (weight) % of the above monomer units.

The copolymerization composition is not critical, and the above composition may be determined based on the monomer mixing ratio when producing the copolymer.

The unsaturated carbonate homopolymer or copolymer or the mixture of the unsaturated carbonate homopolymer or copolymer and the methacrylate polymer can be prepared as described above (by kneading these resins with liquid or paste monomers). used.

Therefore, it is generally used in powder form.

The degree of the powdery state is not particularly limited and may be pulverized if necessary, but generally the average particle size is 1 to 1.
The 350μ range is most widely used.

The technique for turning the polymer into a powder is not particularly limited (the polymer may be ground to an appropriate particle size using a grinder), but it is also possible to obtain a powdered polymer when producing the polymer. .

In addition, when using a mixture of a homopolymer or copolymer of the unsaturated carbonate and a methacrylate polymer, the homopolymer or copolymer of the unsaturated carbonate is
It is suitable to use 0 (weight) % or more, preferably 50 (weight) % or more.

The above polymer is a resin for the outer layer of a veneer or jacket crown, and is used by kneading it with a paste or liquid monomer.

The pasty or liquid monomer is not particularly limited, and any monomer may be used as long as it can be kneaded with the polymer and molded as the outer layer of the veneer pair or jacket crown.

Generally, methyl methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 2.2bis(4(2-,7!tacryloxyethoxy)phenyl)propane, bisphenol A dimethacrylate, etc. are preferably used.

It is also a preferred embodiment to add a small amount of peroxide such as benzoyl peroxide.

The addition of pigments, inorganic fillers, etc. during the kneading does not harm the resin for the outer layer of the veneer pair or jacket crown of the present invention, and can be appropriately selected and used as required.

The inner layer of the veneer pair or jacket crown in the present invention is not particularly limited (it may be used by kneading a known resin and liquid or paste monomer).

For example, as the resin, polymethyl methacrylate, polyallyl diglycol carbonate, and polycarbonate may be used alone or in combination.

Moreover, the liquid or paste monomers mentioned above can be used.

As is clear from the examples described later, the resin of the present invention has extremely good hardness and abrasion resistance, good water resistance, and extremely good compressive strength.

Therefore, when the resin of the present invention is used for the outer layer of a veneer or jacket crown, the surface remains in good condition with no scratches even after an abrasion test, and is extremely durable compared to conventional products, protecting the inner layer. It is stable over a long period of time and exhibits excellent effects.

EXAMPLES In order to explain the present invention more specifically, Examples and Comparative Examples will be described below, but the present invention is not limited to these Examples.

The physical properties of the resin of the present invention in the Examples are the results of the following tests conducted on the resin for forming the enamel layer, liquid monomer, and additives kneaded in accordance with the Examples.

(1) Hardness Test Purinel hardness was measured using a micro Purinel hardness meter under a load of 25 kg and a loading time of 30 seconds.

(2) After adjusting the water absorption test sample to a constant weight, immerse it in distilled water at 37°C for 7 days,
The weight increase due to water absorption was divided by the surface area to determine the amount of water absorbed.

(3) Abrasion test A toothbrush type abrasion tester was used to conduct a test piece that had absorbed water.

Wear conditions are 23℃, load 3001, wear distance 450
077Z (20 cIrLX 22,500 times), and the wear amount was calculated by dividing by the specific gravity and calculating the wear depth.

White Lion (trade name) toothpaste was used as the anti-friction material, and Bannet Lion (trade name) (nylon material) was used as the toothbrush.

(4) Compression test The compressive strength of the dried test piece was measured using a universal testing machine.

(5) Surface roughness test ■ Using a Tokyo Seimitsu surface roughness meter (Surfcom 200A), measure the surface roughness in the direction perpendicular to the wear direction for the sample after the above wear test according to JIS BO6.
The roughness was measured according to the "10-point average roughness" method of 01-1976.

Further, the abbreviations used in Examples and Comparative Examples are as follows.

MMA; methyl methacrylate BAC; diethylene glycol bis(allyl carbonate) PMMA; polymethyl methacrylate PBAC; polydiethylene glycol bis(allyl carbonate) PBO; benzoyl peroxide BMPEPP; 2,2-bis(4-methacryloxypropoxyphenyl)furopane DEDMA; diethylene glycol Dimethacrylate BMEPP; 2,2-bis(4-methacryloxyethoxyphenyl)propane BGMA; 2,2-bis(para-27-hydroxy-3
′-methacryloxypropoxyphenyl)propane
.

TEDMA; ) diethylene glycol dimethacrylate PTBAC; polytriethylene glycol bis(allyl carbonate) PDEDMA; polydiethylene glycol dimethacrylate) PBMEPP; poly 2,2-bis(4-methacryloxyethoxyphenyl)propanePBMPEMMA; 2,2-bis( Copolymer of 4-methacryloxyethoxyphenyl)propane (10 wt%) and methyl methacrylate DAP; diallyl phthalate DAIP; diallyl isophthalate Example 1 Polymethyl methacrylate powder with a molecular weight of 250,000 (trade name Hyvar D-250ML, on a board) Industrial) 100 parts by weight, 57 parts by weight of titanium oxide and 1.6 parts by weight of vanadium yellow as pigments.
Parts by weight, Iron Chrome Tea 1.6 parts by weight, Fast Yellow 1
Add 1.6 parts by weight of 0G to obtain powder for opaque, and mix this powder with 60 parts by weight of epoxy ester (product name 40EM, Kyoeisha Yushi) and 40 parts by weight of isobutyl methacrylate in a 1:1 weight ratio in a kneading dish. The well-kneaded mixture was then piled up on the top surface of the metal casting to form an opaque layer.

Next, add 1 part by weight of benzoyl peroxide to 100 parts by weight of polymethyl methacrylate powder with a molecular weight of 500,000 (trade name Hybar D-250M Negami Industries), and add 0 parts by weight of titanium oxide as a pigment.
．． 8 parts by weight, 0.07 parts by weight of Navel Yellow Akakuchi, 0.1 part by weight of Navel Yellow Yellow Kuchi, 0.0 part by weight of cobalt oxide
Add 3 parts by weight to make a powder for dentin, and add BM to this powder.
60 parts by weight of PEPP (trade name D-2,6E Shin Nakamura Chemical) and 40 parts by weight of DEDMA (trade name NK-2G Shin Nakamura Chemical)
The mixed solution with parts by weight was well kneaded in a kneading dish at a weight ratio of 1:1, and the resulting mixture was piled up on the opaque layer to form a dentin layer.

In the dentin layer, a powder obtained by adding 0.88 parts by weight of titanium oxide and 0.04 parts by weight of Navel Yellow Akakuchi as pigments to 100 parts by weight of the resin shown in the column of resin type, and a liquid monomer shown in the column of liquid composition in Table 1. 1:1 (weight ratio) (BPO
The mixture was kneaded using a kneading plate (containing 1% by weight) and the mixture was piled up on the dentin layer to form an enamel layer.

That is, a front cover consisting of an opaque layer, a dentin layer and an enamel layer was produced.

The physical properties of the polymer used at this time to form the outer layer, ie, the enamel layer, on the vestment were as shown in Table 1.

Tables 1 & 12 show P as a resin for enamel layer for comparison.
These are the results of a similar implementation using MMA.

In addition, the type of resin in Table 1 uses a polymer of unsaturated carbonate represented by the general formula R'0COofR-08COR', but for simplicity, the numbers in the above formula and the number of carbon atoms are used. It was displayed as

The abbreviations for the number of carbon atoms above mean the following examples.
2 The same procedure as in Example 1 (Table IA4) was carried out except that a copolymer of diethylene glycol bis(allyl carbonate) and the comonomer shown in Table 2 was used instead of the resin in Example 1 (Table IA4).

The results were as shown in Table 2.

However, in the column of resin type in Table 2, monomers and comonomers and their composition ratios are shown.

Example 3 The same procedure as Example 1 was carried out except that a mixture of resins as shown in Table 3 was used in place of the resin in Example 1 (Table 1, Section 4).

The results were as shown in Table 3.

Example 4 A copolymer of BAC and ② used in Example 2 (Tables 2 & 2), a copolymer of MMA and BMPEPP (BMPEPP
Example 1 using a mixture (unit content: 70% (weight)) (copolymer ratio of BAC and MMA: 70% (weight))
It was carried out in the same way.

As a result, the wear depth of the polymer that forms the enamel layer x 1
O-3crrL) was 4.2, and the water absorption amount after 7 days (m97
m') was 1.32.

Claims (1)

[Scope of Claims] 1 General formula (where R is a saturated aliphatic hydrocarbon residue having 2 to 5 carbon atoms, R' is an unsaturated aliphatic hydrocarbon residue having 2 to 4 carbon atoms, (n is a positive number from 1 to 3)) or a copolymer containing 50% (by weight) or more of the unsaturated carbonate monomer unit. Resin for the outer layer of the crown. 2 Unsaturated carbonate is diethylene glycol bis(
The resin for the outer layer of a front cover layer or jacket crown according to claim 1, which is made of triethylene glycol bis(allyl carbonate) or triethylene glycol bis(allyl carbonate). 3(1) General formula (where R is a saturated aliphatic hydrocarbon residue having 2 to 5 carbon atoms, R' is an unsaturated aliphatic hydrocarbon residue having 2 to 4 carbon atoms, and n is 1 (11) a methacrylate polymer; A resin for the outer layer of the veneer layer or jacket crown made of a mixture. 4 Unsaturated carbonate is diethylene glycol bis(
The resin for the outer layer of a front cover layer or jacket crown according to claim 3, which is made of triethylene glycol bis(allyl carbonate) or triethylene glycol bis(allyl carbonate). 5. The front according to claim 3, wherein the methacrylate polymer is at least one polymer selected from the group consisting of alkyl methacrylate polymers, glycol dimethacrylate polymers, and bisphenol A dimethacrylate polymers. Resin for outer layer of cladding or jacket crown.