JP4785742B2 - Dental root canal sealing composition - Google Patents

Description

  The present invention relates to a dental root canal sealing composition that can be cured by addition polymerization without a polymerization catalyst. The dental root canal sealing composition of the present invention is provided in the form of a two-component composition.

  Dental root canal sealing compositions are often injected into the root canal through a needle tube. Since the size of the needle tube is small, the viscosity of the composition is required to be low. On the other hand, dental root canal sealing compositions are applied using lentulos or gutta percha chips. Therefore, the viscosity must be low so that a thin film can be formed. Regardless of the application technique, the viscosity of the material must be low enough to allow the composition to enter the dentin tube in the root canal.

  The application of the dental root canal sealing composition is checked using an X-ray procedure. Since radiopacity is required, the composition should contain a substantial amount of radiopaque filler.

  A dental root canal sealing composition is known from International Patent Publication No. WO 02/13767 disclosing a two-component paste / paste system in the application examples. This two component paste / paste system is based on addition polymerization of equimolar low molecular weight diamines and low molecular weight diacrylates, optionally in the presence of a reactive diluent to adjust the viscosity of the composition.

  However, the presence of low molecular weight amines in dental root canal sealing compositions causes serious drawbacks. Cytotoxic effects are often observed by leaching of such amines from the root canal. Furthermore, the cured composition of International Patent Publication No. WO 02/13767 shows considerable solubility, so that the problem of cytotoxicity is exacerbated and the problem of application arises. Finally, the composition of International Patent Publication No. WO 02/13767 is problematic for industrial applications because of the high vapor pressure of low molecular weight amines and the high rate of penetration through plastic packaging.

  The polyamino ester specifically disclosed in International Patent Publication No. WO 02/13767 has a high viscosity, and it is necessary to use a considerable amount of a reactive diluent in order to reduce the viscosity. However, a reactive diluent cannot be polymerized by addition polymerization, and a polymerization initiator needs to be present.

  International Patent Publication No. WO 02/13767 does not disclose difunctional and polyfunctional acrylate compounds and difunctional and polyfunctional maleimide compounds that can undergo polyaddition.

  The subject of the present invention is a dental product that has low viscosity, low cytotoxicity and low solubility, but has excellent mechanical properties such as low shrinkage and flexibility, and does not cause handling problems during production and application. It is to provide a root canal sealing composition.

International Patent Publication WO02 / 13767 J. et al. Klee, H.C. -H. Horhold, J .; Radadtz; Acta Polymerica, 41 (1990) 557-560; “Telechel Prepolymere aus DGEBA undiscountlanden Diaminen. Unvernette Epoxide-Amin-Addition. J. et al. E. Klee; Acta Polym. 45 (1994) 73-82; “Telechelic prepolymers and macromonomers by step growth processes” (39) J. et al. E. Klee, R.A. -E. Grutzner, H.M. -H. Horhold; Macromol. Chem. Phys. 197 (1996) 2305-2323; Linear arylamine / Bis-2,2- [4- (2,3-epoxypropoxy) -phenyl] -propane addition polymeris, synthesis and propylene, uncrosslinked 44. ”

（式中、
Ｘは、窒素原子または酸素原子を表し、
Ｚは、１〜６個の酸素原子を含んでいてもよくかつ１〜６個のＣ_１〜４アルキル基で置換されていてもよい、ｎ価の飽和脂肪族Ｃ_２〜１６炭化水素基または２価の飽和脂環式Ｃ_３〜６炭化水素基を表し、
ｎは２から６の整数を表す）と、
（ｂ）次式（ＩＩ）

（式中、Ａは、１〜６個の酸素原子を含んでいてもよくかつ１〜６個のＣ_１〜４アルキル基で置換されていてもよい、２価の飽和脂肪族Ｃ_２〜１６炭化水素基または２価の飽和脂環式Ｃ_３〜６炭化水素基を表し、
Ｒ_ａおよびＲ_ｂは、同一または異なっており、かつ水素原子、またはＣ_１〜４アルキル基、Ｃ_１〜４アルコキシ基、フェニル基およびヒドロキシ基から選択される基の１つ以上で置換されていてもよいＣ_１〜６アルキルもしくはＣ_３〜１４シクロアルキル基を表す）
または、式（ＩＩ）と式ＲＮＨ_２（式中、ＲはＣ_１〜４アルキル基、Ｃ_１〜４アルコキシ基、フェニル基、およびヒドロキシ基から選択される１つ以上で置換されていてもよいＣ_１〜６アルキル基またはＣ_３〜１４シクロアルキル基を表す）の化合物の１つ以上とを組み合わせたもの、および／または更なるジアミンもしくはポリアミン化合物と組み合わせたもののいずれかの、１つ以上の化合物少なくともｎモルと
を反応させて得ることのできるアミノ終端プレポリマー、
（ｉｉ）前記アミノ終端プレポリマー（ｉ）と重付加することができる化合物、および
（ｉｉｉ）少なくとも３ｍｍ／ｍｍＡｌの最小Ｘ線不透過性をもたらすフィラー４０〜８５重量％、
からなる歯科用根管密封組成物を提供する。 This problem is solved by the claims of the present invention. The present invention is a dental root canal sealing composition curable without a polymerization initiator,
(I) 23 Viscosity at ℃ is an amino terminated Purepori M a of less than 100 Pas,
(A) 1 mol of the compound of the following formula (I)

(Where
X represents a nitrogen atom or an oxygen atom,
Z is an n-valent saturated aliphatic C _2-16 hydrocarbon group which may contain 1-6 oxygen atoms and may be substituted with 1-6 C _1-4 alkyl groups, or Represents a divalent saturated alicyclic C _3-6 hydrocarbon group,
n represents an integer of 2 to 6),
(B) Formula (II)

Wherein A is a divalent saturated aliphatic C _2-16 which may contain 1-6 oxygen atoms and may be substituted with 1-6 C _1-4 alkyl groups. Represents a hydrocarbon group or a divalent saturated alicyclic C _3-6 hydrocarbon group,
R _a and R _b are the same or different and are substituted with a hydrogen atom or one or more groups selected from a C _1-4 alkyl group, a C _1-4 alkoxy group, a phenyl group and a hydroxy group. Represents an _{optionally substituted} C _1-6 alkyl or C _3-14 cycloalkyl group)
Alternatively, Formula (II) and Formula RNH ₂ (wherein R is optionally substituted with one or more selected from a C _1-4 alkyl group, a C _1-4 alkoxy group, a phenyl group, and a hydroxy group). One or more of any of those in combination with one or more of the compounds of _C1-6 alkyl or _C3-14 cycloalkyl) and / or in combination with further diamine or polyamine compounds An amino-terminated prepolymer obtainable by reacting at least n mol of the compound;
(Ii) a compound capable of polyaddition with said amino-terminated prepolymer (i), and (iii) 40-85% by weight filler providing a minimum radiopacity of at least 3 mm / mm Al,
A dental root canal sealing composition is provided.

  In the dental root canal sealing composition, the first component includes the amino-terminated prepolymer (i) and optionally the filler (iii), and the second component performs the polyaddition with the amino-terminated prepolymer (i). In the form of a two-component composition comprising a possible compound (ii) and optionally said filler (iii).

In the above formula, X represents a nitrogen atom or an oxygen atom. In the above formula, Z is an n-valent saturated aliphatic C _2-16 hydrocarbon group or a divalent saturated alicyclic C _3-6 hydrocarbon group, and these groups are preferably 2 to 16 carbon atoms, preferably May be based on a linear or branched alkylene group having 4 to 10 carbon atoms, or a cycloalkylene group having 3 to 6 carbon atoms, preferably 4 to 6 carbon atoms. Z may be divalent (n = 2), trivalent (n = 3), tetravalent (n = 4), pentavalent (n = 5) or hexavalent (n = 6). Preferred Z is divalent or trivalent. The hydrocarbon group may be substituted with one or more C _1-4 alkyl groups. Specific examples of the alkyl group are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or tert-butyl. The hydrocarbon group may contain 1 to 6 oxygen atoms in the carbon chain or side chain connecting n acrylate substituents. The aliphatic or alicyclic C _2-16 hydrocarbon group is preferably highly flexible due to the presence of ether linkages and the absence of bulky groups. In a preferred embodiment, Z is a divalent group based on a linear alkyl group that may contain an ether bond. Specifically, Z may be a _C2-6 alkylene group.

In which A represents a straight or branched alkylene group having 2 to 16 carbon atoms, preferably 4 to 10 carbon atoms, or 3 to 6 carbon atoms, preferably 4 to 6 carbon atoms. A divalent saturated aliphatic C _2-16 hydrocarbon group or a divalent saturated alicyclic C _3-6 hydrocarbon group, which can be based on a cycloalkylene group. The hydrocarbon group may be substituted with one or more C _1-4 alkyl groups. Specific examples of alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or tert-butyl. The hydrocarbon group may contain 1 to 6 oxygen atoms in the carbon chain or side chain to which the amino group is bonded. Preferably, the divalent saturated aliphatic C _2-16 hydrocarbon group or the divalent saturated alicyclic C _3-6 hydrocarbon group is highly reduced by the presence of an ether bond and the absence of a bulky group. Be flexible. In a preferred embodiment, A is a divalent group based on a linear alkylene group that may contain an ether bond. In a preferred embodiment, A is — (CH ₂ ) ₂ O (CH ₂ ) ₂ O (CH ₂ ) ₂ —.
Ra and Rb may be the same or different and each represents a hydrogen atom, a C _1-6 alkyl or a C _3-14 cycloalkyl group. . Examples of C _1-6 alkyl groups include straight or branched alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl and n -Butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl are included. Examples of C _3-14 cycloalkyl groups include those having 3-14 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The C _1-6 alkyl group and the C _3-14 cycloalkyl group are optionally substituted with one or more groups selected from a C _1-4 alkyl group, a C _1-4 alkoxy group, a phenyl group and a hydroxy group. It may be. Examples of C _1-4 alkyl groups include straight or branched alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert -It can contain butyl. Examples of C _1-4 alkoxy groups include straight or branched alkoxy groups containing 1 to 4 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and Tert-butoxy can be included. Ra and Rb hydrogen are preferable.

In the preparation of the prepolymer, the compound of formula (II), optionally, formula _RNH 2, (wherein R is _{C 1 to 4} alkyl _{groups, C 1 to 4} alkoxy groups, a group selected from a phenyl group and a hydroxy group _May be used in combination with an amine compound of C _1-6 alkyl or C _3-14 cycloalkyl group _optionally substituted with one or more of the above, or a further diamine compound or polyamine compound. The amine of formula RaNH ₂ and / or the further diamine or polyamine compound is not more than n / 1.5 mol, preferably n / 20 to n / 2 mol, of the compound of formula (II) used in the reaction for preparing the prepolymer. Can be used. Here, n is as defined above. The amount of said component used in combination with the diamine of formula (II) must be selected such that the viscosity of the prepolymer does not exceed 100 Pa ^* s, preferably 80 Pa ^* s, more preferably 20 Pa ^* s. .

（式中、
Ａは、１〜６個の酸素原子を含んでいてもよくかつ１〜６個のＣ_１〜４アルキル基で置換されていてもよい、２価の飽和脂肪族Ｃ_２〜１６炭化水素基もしくは２価の飽和脂環式Ｃ_３〜６炭化水素基を表し、
Ｘは、酸素原子もしくは窒素原子を表し、
Ｚは、１〜６個の酸素原子を含んでいてもよくかつ１〜６個のＣ_１〜４アルキル基で置換されていてもよい、２価の飽和脂肪族Ｃ_２〜１６炭化水素基もしくは２価の飽和脂環式Ｃ_３〜６炭化水素基を表し、
Ｒ１、Ｒ２、Ｒ３およびＲ４は同一でも異なっていてもよく、水素原子、またはＣ_１〜４アルキル基、Ｃ_１〜４アルコキシ基、フェニル基またはヒドロキシ基で置換されていてもよいＣ_１〜６アルキルもしくはＣ_３〜１４シクロアルキル基を表し、
ｘは１から８の整数である）、
（ｉｉ）前記アミノ終端プレポリマー（ｉ）と重付加することができる化合物、および
（ｉｉｉ）少なくとも３ｍｍ／ｍｍＡｌの最小Ｘ線不透過性をもたらすフィラー４０〜８５重量％
を含む。 In a preferred embodiment, the dental root canal sealing composition comprises:
(I) Prepolymer of formula (III)

(Where
A is a divalent saturated aliphatic C _2-16 hydrocarbon group which may contain 1-6 oxygen atoms and may be substituted with 1-6 C _1-4 alkyl groups, or Represents a divalent saturated alicyclic C _3-6 hydrocarbon group,
X represents an oxygen atom or a nitrogen atom,
Z is a divalent saturated aliphatic C _2-16 hydrocarbon group which may contain 1-6 oxygen atoms and may be substituted with 1-6 C _1-4 alkyl groups, or Represents a divalent saturated alicyclic C _3-6 hydrocarbon group,
R 1, R 2, R 3 and R 4 may be the same or different, and C _1-6 may be substituted with a hydrogen atom, or a C _1-4 alkyl group, a C _1-4 alkoxy group, a phenyl group or a hydroxy group. _Represents an alkyl or C _3-14 cycloalkyl group,
x is an integer from 1 to 8),
(Ii) a compound capable of polyaddition with said amino-terminated prepolymer (i), and (iii) 40-85% by weight filler providing a minimum radiopacity of at least 3 mm / mm Al
including.

The dental root canal sealing composition of the present invention comprises 40-85% by weight filler to provide the minimum radiopacity of the cured composition of at least 3 mm / mm Al. The filler includes La ₂ O ₃ , ZrO ₂ , BiPO ₄ , CaWO ₄ , BaWO ₄ , SrF ₂ , Bi ₂ O ₃ . The radiopacity of the cured composition of the present invention is at least 3 mm / mm Al, preferably at least 5-7 mm / mm Al, and most preferably at least 7 mm / mm Al.

  The dental root canal sealing composition of the present invention preferably does not contain a diluent having a viscosity lower than that of the prepolymer of the present invention, particularly a reactive diluent. Furthermore, the dental root canal sealing composition need not contain a polymerization initiator. In a preferred embodiment, the dental root canal sealing composition consists essentially of components (i) to (iii). The dental root canal sealing composition essentially composed of the components (i) to (iii) is a general additive used in the dental field such as a coloring agent, antibiotic agent, ion releasing agent and the like. The agent may be included in a total amount not exceeding 25% by weight of the composition, preferably not exceeding 10% by weight.

  A preferred embodiment of the dental root canal sealing composition of the present invention comprises 40-85% by weight filler and 15-60% by weight of a compound capable of polyaddition with an amino-terminated prepolymer and an amino-terminated prepolymer. The amino-terminated prepolymer used in the present invention is usually a mixture of oligomers. Thus, the amount of amino-terminated prepolymer and compounds that can be polyadded with amino-terminated prepolymer is calculated based on the oligomer mixture.

  The dental root canal sealing composition of the present invention is a two-component composition that is mixed before use. This two-component composition is preferably a powder / liquid system, a powder / paste system, a paste / paste system or a liquid / paste system. The paste / paste system or liquid / paste system may be injected by an applicator where both components are mixed in a static mixer.

  The present invention provides a prepolymer that has a low viscosity but at the same time eliminates the problems associated with the presence of low molecular weight amine compounds by Michael addition of specific diamine compounds to specific diacrylate or oligoacrylate compounds. Based on recognition. Surprisingly, the reaction kinetics of Michael addition of diamines and acrylates is different from the reaction kinetics of other addition reactions of amines, and the reaction products do not crosslink or become high molecular weight high viscosity materials. It becomes a low viscosity non-crosslinked prepolymer. The difference in reaction rates between primary and secondary amines for acrylate compounds appears to be the basis for the possibility of obtaining the compositions of the present invention. Due to the unique reaction kinetics of the primary amine in the present invention, the residual primary amine content in the prepolymer of the present invention or in the dental root canal sealing composition is in the primary amine and the secondary amine. Compared to the following systems using functional end groups exhibiting the same reactivity with respect to the following, it is substantially reduced. J. et al. Klee, H.C. -H. Horhold, J .; Acta Polymerica, 41 (1990) 557-560; “Telechel Prepolymere aus DGEBA and diskundaren Diaminen. Unvernette Epoxide-Amin-Addition. J. 29”; E. Klee; Acta Polym. 45 (1994) 73-82; “Telechelic prepolymers and macromonomers by step growth processes” (39); E. Klee, R.A. -E. Grutzner, H.M. -H. Horhold; Macromol. Chem. Phys. 197 (1996) 2305-2323; Linear arylamine / Bis-2,2- [4- (2,3-epoxypropoxy) -phenyl] -propane addition polymerisation-synthesis and propeloidis, Uncrosslinked 44. "Primary amines react much faster than secondary amines, especially in reactions with difunctional or polyfunctional acrylates or acrylamides or bismaleimides or polymaleimides.

The prepolymer contained in the dental root canal sealing composition of the present invention has a viscosity at 23 ° C. of less than 100 Pa ^* s. The viscosity of the prepolymer is preferably in the range of 1~80Pa ^* s, and more preferably in a range of from 1~20Pa ^* s. If the viscosity is too high, it will be difficult to apply the composition through the needle tube. If the viscosity is too low, it becomes difficult to handle the composition.

  The dental root canal sealing composition of the present invention can be cured without a polymerization initiator. The curing mechanism is based on an addition reaction between the amino-terminated prepolymer (i) and a compound that can be polyadded with the amino-terminated prepolymer (i). The compound that can be polyadded with the amino-terminated prepolymer (i) is a difunctional or polyfunctional acylate or a difunctional or polyfunctional maleimide. Bifunctional or polyfunctional acrylates and difunctional or polyfunctional maleimides are preferred in terms of selectivity in the reaction with primary and secondary amino groups. The compound capable of polyaddition with the amino-terminated prepolymer (i) is defined by the formula (I) (wherein X and Z are as defined above and n represents an integer of 2 to 6) It may be the same as or different from the compound.

  The use of certain amino-terminated prepolymers can eliminate or at least greatly reduce the problems associated with low molecular weight amines. Moreover, surprisingly, the use of certain prepolymers provides a low viscosity dental root canal sealing composition. For this purpose, it is essential to avoid hard parts in the prepolymer.

  The composition of the present invention can be applied to the root canal using conventional techniques. Specifically, the composition of the present invention can be applied to the root canal via a syringe tube. Furthermore, the composition of the present invention can also be used for the production of pre-made root canal cones. If a cone made of the composition of the present invention is used in combination with the respective dental root canal sealing composition of the present invention, compatibility between the cone and the sealing composition is ensured, and thus a tight seal is obtained. . The cured product obtained with the composition according to the invention is excellent in terms of mechanical properties, in particular flexibility, and is essential for application as a root canal sealing composition.

（式中、
ＸおよびＺは上に定義したものであり、
ｎは２〜６の整数を表す）と
（ｂ）次式（ＩＩ）

（式中Ａ、ＲａおよびＲｂは上で定義したものである）
または式（ＩＩ）の１つ以上の化合物少なくともｎモル
とを反応させることによって得ることができる。 Here, a general method for the preparation of amino-terminated prepolymers is described. This prepolymer comprises (a) 1 mole of a compound of formula (I)

(Where
X and Z are as defined above,
n represents an integer of 2 to 6) and (b) the following formula (II)

(Wherein A, Ra and Rb are as defined above)
Alternatively, it can be obtained by reacting at least n moles of one or more compounds of formula (II).

This reaction can be performed without a solvent or in the presence of a suitable solvent. The reaction temperature is preferably in the range of 10 ° C to 150 ° C, more preferably in the range of 20 ° C to 80 ° C. The reaction time depends on the temperature and the reactivity of the reaction system, and usually ranges from several hours to several days. The termination of the reaction can be checked by conventional methods such as in the IR spectrum, in which case the end of the reaction is reached when all the acrylic carbon-carbon double bonds have disappeared. When the reaction is carried out without a solvent, the prepolymer obtained by the reaction of compounds (I) and (II) can be used without further purification of the reaction mixture. In the preparation of the prepolymer, the compound of formula (II) may be used in combination with an amine of formula RaNH ₂ (Ra is as defined above). The amine of formula RaNH ₂ can be used in place of n / 10 to n / 2 mol of the compound of formula (II) used in the reaction to prepare the prepolymer.

  The invention will now be further described with reference to specific examples. Kinematic viscosity was measured at 23 ° C. using a Bohlin CS50 rheometer.

[Example 1]
Homogeneously mix 22.955 g (154.88 mmol) of 2,2- (ethylenedioxy) -diethyleneamine and 15.350 g (77.44 mmol) of butanediol diacrylate in a 250 ml flask equipped with stirrer and condenser And stirred at 20-25 ° C. for 3 days. Thereafter, no double bonds were found at 1609 and 809 cm ⁻¹ in the IR spectrum. Yield: 37.764 g (100% d.Th), η23 ° C. = 5.865 ± 0.148 Pa ^* s (after storage at room temperature for 1 month) 2.036 g (4.197 mmol) of prepolymer prepared was ethoxylated bisphenol The mixture was uniformly mixed with 2.149 g (4.197 mmol) of A diacrylate (SR-601, Sartomer) and reacted at 37 ° C. This mixture had a gel time of 3 hours at 37 ° C.

[Example 2]
Stirrer and condenser 3 in 250ml flask equipped with a, (4), 8, (9) - bis (aminomethyl) - tricyclo -5.2.1.0 ^2,6 decane 15.000 (77. 19 mmol), 2,2- (ethylenedioxy) -diethyleneamine 11.441 g (77.19 mmol) and 15.301 g (77.19 mmol) of butanediol diacrylate were mixed uniformly and stirred at room temperature for 3 days. Thereafter, no double bonds were found at 1609 and 809 cm ⁻¹ in the IR-spectrum. Yield: 41.742 g (100% d.Th), η23 ° C. = 9.815 ± 0.174 Pa ^* s
2.586 g (4.782 mmol) of the prepared prepolymer was uniformly mixed with 2.449 g (4.782 mmol) of ethoxylated bisphenol A diacrylate (SR-601, Sartomer) and reacted at 37 ° C. The gelation time of this mixture is 6-16 hours at 37 ° C. and becomes a solid.

[Application Example 1] (Powder / Liquid)
1.000 g of the amino-terminated prepolymer of Example 1 prepared by addition reaction of 2,2- (ethylenedioxy) diethyleneamine and butanediol diacrylate, cyclohexanedimethanol diacrylate (12.594 wt%), tungsten A powder composed of calcium acid (50.174% by weight) and zirconium oxide (12.544% by weight) (3.050 g) was uniformly mixed and polymerized for 3 hours.

[Application Example 2] (Paste / Paste)
Acrylate paste: 5.000 g (9.77 mmol) of ethoxylated bisphenol A diacrylate (SR-601, Sartomer). 9.917 g of calcium tungstate, 2.479 g of zirconium oxide, 0.050 g of arosil A200 and 0.025 g of iron (III) oxide were uniformly mixed.
Prepolymer paste: 4.830 g (9.77 mmol) of amino-terminated prepolymer according to Example 6, 9.500 g of calcium tungstate, 2.375 g of zirconium oxide and 0.536 g of aerosil A200 were mixed uniformly.
Immediately before use, 1.00 g of acrylate paste and 0.987 g of amino-prepolymer paste were uniformly mixed and polymerized at 37 ° C. for 3 hours.

[Comparative Example]
Stirrer and condenser 3 in 250ml flask equipped with a, (4), 8, (9) - bis (aminomethyl) tricyclo -5.2.1.0 ^2,6 decane 25.000g (128.70mmol ) And 12.755 g (64.35 mmol) of butanediol diacrylate were uniformly mixed and stirred at 20 to 25 ° C. for 3 days. Thereafter, no double bonds were found at 1609 and 809 cm ⁻¹ in the IR spectrum. Yield: 37.764 g (100% d.Th), η23 ° C. = 7157 ± 100 Pa ^* s (after storage at room temperature for 1 month)
2.127 g (3.624 mmol) of the prepolymer was uniformly mixed with 0.716 g (2.416 mmol) of trimethylolpropane triacrylate and reacted at 37 ° C. The mixture has a gel time of 30 minutes at 37 ° C.
This prepolymer has a viscosity that is not suitable for application as a root canal sealing composition. This comparative example shows that a reaction product of 2 moles of diamine and 1 mole of diacrylate disclosed in Application Example 1 of WO 02/13767 can give a prepolymer with too high viscosity. In the case of an equimolar amount of the reaction product of diamine and diacrylate as disclosed in application example 1 of WO 02/13767, the viscosity of the polymer product will be even higher.

Claims (15)

A dental root canal sealing composition that does not contain a polymerization initiator,
(I) an amino-terminated prepolymer having a viscosity at 23 ° C. of less than 100 Pas,
(A) 1 mol of the compound of the following formula (I)

(Where
X represents a nitrogen atom or an oxygen atom,
Z is an n-valent saturated aliphatic C _2-16 hydrocarbon group which may contain 1 to 6 oxygen atoms and may be substituted with 1 to 6 C _1-4 alkyl groups. Or a divalent saturated alicyclic C _3-6 hydrocarbon group,
n represents an integer of 2 to 6),
(B) one or more compounds of formula (II)

(Where
A is a divalent saturated aliphatic C _2-16 hydrocarbon group which may contain 1 to 6 oxygen atoms and may be substituted with _{1 to} 6 C _1-4 alkyl groups. Or a divalent saturated alicyclic C _3-6 hydrocarbon group,
R _a and R _b are the same or different and are substituted with a hydrogen atom or one or more members selected from a C _1-4 alkyl group, a C _1-4 alkoxy group, a phenyl group, and a hydroxy group. It may be a C _1-6 alkyl group or a C _3-14 cycloalkyl group)
Or the formula (II) and the formula RNH ₂ (wherein R may be substituted with one or more groups selected from a C _1-4 alkyl group, a C _1-4 alkoxy group, a phenyl group, and a hydroxy group) One or more compounds, either in combination with one or more compounds of C _1-6 alkyl or C _3-14 cycloalkyl group, and / or in combination with further diamine or polyamine compounds An amino-terminated prepolymer obtained by reacting with at least n moles of
(Ii) a difunctional or polyfunctional acrylate compound or a bifunctional or polyfunctional maleimide compound capable of polyaddition with the amino-terminated prepolymer (i);
(Iii) 40-85 wt% filler that provides a minimum radiopacity of at least 3 mm / mm Al;
Consists of
The composition comprises a first component comprising the amino-terminated prepolymer (i ), a second component comprising the compound (ii ) capable of polyaddition with the amino-terminated prepolymer (i), and A dental root canal sealing composition in the form of a two-component composition in which at least one of the first component and the second component contains the filler (iii) . Prepolymer of formula (III)

(In the formula, A may contain 1 to 6 oxygen atoms and may be substituted with 1 to 6 C _1-4 alkyl groups, which is a divalent saturated aliphatic C ₂ Represents a ₁₆ hydrocarbon group or a divalent saturated alicyclic C _3-6 hydrocarbon group,
X represents an oxygen atom or a nitrogen atom,
Z is a divalent saturated aliphatic C _2-16 hydrocarbon group which may contain 1 to 6 oxygen atoms and may be substituted with _{1 to} 6 C _1-4 alkyl groups. Or a divalent saturated alicyclic C _3-6 hydrocarbon group,
R 1, R 2, R 3 and R 4 may be the same or different, and may be substituted with a hydrogen atom, or a C _1-4 alkyl group, a C _1-4 alkoxy group, a phenyl group or a hydroxy group _{. Represents a 4} alkyl or C _3-14 cycloalkyl group,
x is an integer from 1 to 8),
(Ii) a difunctional or polyfunctional acrylate compound or a difunctional or polyfunctional maleimide compound capable of polyaddition with said amino-terminated prepolymer (i), and (iii) a minimum x-ray of at least 3 mm / mm Al 40-85% by weight filler, which provides impermeability,
The dental root canal sealing composition according to claim 1, comprising: A divalent saturated aliphatic C _2-10 hydrocarbon chain in which A may contain 2 to 4 oxygen atoms and may be substituted with _{1 to} 6 C _1-4 alkyl groups The dental root canal sealing composition according to claim 2, wherein A is _{- (CH 2) 2 O (} CH 2) 2 O (CH 2) 2 - represents a root canal sealing composition according to claim 1. Z is representative of a 1-6 _{C 1-4} alkyl group substituted by 2 may be divalent saturated aliphatic _{C 2 to 10} hydrocarbon chains, according to any one of claims 1 to 4 Dental root canal sealing composition. The dental root canal sealing composition according to any one of claims 1 to 5 , wherein Z represents a _C2-6 alkylene group. The dental root canal sealing composition according to any one of claims 1 to 6 , wherein X represents an oxygen atom. The dental root canal sealing composition according to any one of claims 1 to 7 , wherein X represents a nitrogen atom. R1, R2, R3 and R4 is the same root canal sealing composition according to any one of claims 2-8. R1, R2, R3 and R4 is a hydrogen atom or a phenyl group, substituted by a hydroxy group or an amino group selected from optionally _{C 1 to 4} alkyl groups, in any one of claims 2 to 9 The dental root canal sealing composition as described. _{Filler, La 2 O 3, ZrO 2} , BiPO 4, CaWO 4, BaWO 4, includes a SrF 2, _Bi 2 _{O 3,} the dental root canal sealing according to any one of claims 1 to 10 Composition. The dental root canal sealing composition according to any one of claims 1 to 11 , wherein the two-component composition is a powder / liquid system or a paste / paste system. Prepolymer of the following formula

( Wherein x is as defined in claim 2 )
Dental root canal sealing composition according to any one of claims 1 to 12 comprising. The amino-terminated prepolymer is
(I) 1 mol of the compound of the following formula (IV)

(Wherein X and Z are as defined in claim 2), and (ii) at least 2 moles of one or more compounds of formula (III)

(In the formula, A is as defined in claim 2, and Ra and Rb are the same or different and may be substituted with a hydrogen atom, or a C _1-4 alkyl group, a phenyl group or a hydroxy group. _{Represents a 1-4} alkyl group or a C _3-14 cycloalkyl group),
Which can be obtained by reacting
The dental root canal sealing composition according to any one of claims 1 to 13 . Said amino-terminated prepolymer further comprises the formula RNH ₂ (Wherein R is C _1-4 Alkyl group, C _1-4 C which may be substituted with one or more groups selected from an alkoxy group, a phenyl group and a hydroxy group _1-6 Alkyl or C _3-14 15. A dental root canal sealing composition according to claim 14, which is obtainable by reacting a cycloalkyl group) or a further diamine or polyamine compound.