JPH032396B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to adhesives, and particularly to long-term storage adhesives suitable for adhering human hard tissues such as teeth and bone tissue. [Prior Art] Various compounds have been known for adhesives, but the properties required differ significantly depending on the field of use and the environment in which they are used. In particular, adhesives used for dental treatment must withstand the complexity of forces applied in the oral cavity, the variety of adherends, and highly unpredictable environments such as humid conditions, and must not be toxic. These strict characteristics are required. Cement-based adhesives made of aqueous solutions of phosphoric acid or polyacrylic acid and basic inorganic oxides have long been used as adhesives for dental treatment. However, although such cement-based adhesives adhere to the tooth structure, they lack water resistance and have little adhesion to polymer-based composite restorative materials, which have recently begun to be widely used as dental filling and restorative materials. There is a drawback that there is no Therefore, in order to compensate for the drawbacks of such cement-based adhesives, a room-temperature curing adhesive using radically polymerizable monomers has been developed, and it is particularly useful as an adhesive between tooth structure and polymeric composite restorative materials. It has come into widespread use. However, adhesives using such radically polymerizable monomers themselves have poor adhesion to the tooth structure, and to compensate for this drawback, the surface of the tooth structure is demineralized in advance using, for example, a highly concentrated phosphoric acid aqueous solution. Requires pre-processing such as processing. Similarly, for the purpose of increasing adhesion to tooth structure,
Methods such as introducing a specific functional group into a radically polymerizable monomer or devising a curing agent for the monomer have been used. In particular, regarding the latter curing agent, the adhesion and adhesion to the tooth structure can be improved by using a sulfinate in addition to the commonly used room-temperature-reactive radical initiator consisting of an organic peroxide and an amine. It is known that
56-33363). In such an adhesive, polymerization of radically polymerizable monomers starts by mixing each component. Therefore, when storing, the usual method is to package components that can initiate polymerization upon mixing into two separate packages, and then mix the components in these two packages before use. It has been adopted. For example, in JP-A-53-39331, one package contains a radically polymerizable monomer and an organic peroxide, and the other package contains a radically polymerizable monomer, an amine or its salt, and a sulfinic acid. An adhesive comprising salt is shown. Furthermore, in JP-A No. 54-28339, one package contains an adhesive material containing a radically polymerizable monomer and an organic peroxide, and the other package contains an adhesive material containing an amine or a salt thereof, and a sulfinate. It is shown. As a result of studying such adhesive materials, the present inventors found that the adhesive strength of the former particularly to tooth enamel is higher than that of the latter. Therefore, the former type of adhesive is an adhesive that has excellent margin sealing properties because it can effectively bond the tooth enamel to the filling material, such as a composite restorative material, that is filled into the cavity of the tooth. Can be done. [Problems to be solved by the invention] However, the former adhesive packaged in two parts has poor adhesive strength and edge sealing properties under severe conditions of long-term storage at high temperatures, such as storage in a warehouse during the summer. There are points to be improved, and it is desired to improve long-term storage stability. Although the cause of this is not clear, the present inventors speculate that the radically polymerizable monomer contained in the same package as the sulfinate is modified by the sulfinate. Therefore, the present inventors aimed to develop an adhesive material that has particularly good adhesion to tooth enamel and dentin, and has excellent long-term storage stability.
I have been doing extensive research. As a result, in the adhesive material in the above packaging form, it is possible to use a specific radically polymerizable monomer and a specific amount of a specific polymer as the radically polymerizable monomer in the same package as the sulfinate salt. The inventors have discovered that the desired adhesive can be obtained by this method, and have completed the present invention. [Means for Solving the Problems] That is, the present invention comprises (a) a radically polymerizable monomer, (b) an organic peroxide, (c) an amine or a salt thereof, (d) a sulfinate, and (e ) An adhesive material whose main component is a polymer having a carboxyl group or its anhydride group; one package () contains (a) and (b), and the other package () contains (a) and (b).
Contains (a), (c) and (d), and (e) is packaged in a range of 0.1 to 40 parts by weight based on 100 parts by weight of the total radically polymerizable monomer () and/or or (), and (a) in packaging () contains 80 mol% or more of a radically polymerizable monomer having an OH group, and packaging () and () are stored separately and cannot be used. It is an adhesive characterized in that it is sometimes mixed. One component of the adhesive of the present invention is a radically polymerizable monomer. The monomer is not particularly limited, and known monomers can be used. For example, the most typical ones are acrylates or methacrylates, and specific monovinyl monomers include methyl acrylate, methyl methacrylate,
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, and the like. In addition, polyvinyl monomers include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol,
Diacrylic esters and dimethacrylic esters obtained by reacting dipropylene glycol, butylene glycol, etc. with acrylic acid or methacrylic acid; Acrylic esters and trimethacrylic esters; Tetraacrylic esters and tetramethacrylic esters obtained by the reaction of tetramethylolmethane etc. with acrylic acid or methacrylic acid; Bisphenol-A-diglycidyl methacrylate (hereinafter abbreviated as bisGMA) ) etc. are suitably used alone or in combination. In addition, the radically polymerizable monomer having an OH group that is allowed to coexist with the sulfinate in the packaging () is not particularly limited, but like the radically polymerizable monomer described above, acrylates or Methacrylates are preferred. Specific examples of radically polymerizable monomers having an OH group include:
For example, 2-hydroxyethyl acrylate, 2
-Hydroxy methacrylate; 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate; bis-GMA; reaction of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, butylene glycol, etc. with acrylic acid or methacrylic acid Mono- or di-acrylic esters or mono- or mono-methacrylic esters obtained by reacting trimethylolethane, trimethylolpropane, etc. with acrylic acid or methacrylic acid; Tetramethylolmethane, etc. Mono-, di-, or tri-acrylic esters or mono-, di-, or tri-methacrylic esters obtained by the reaction of acrylic acid or methacrylic acid; mono- or di-acrylic esters or mono- or di-methacrylic esters of glycerin, etc. singly or in combination A mixture of types is preferably used. In addition, organic peroxides, which are components of polymerization curing agents,
As for the amine or its salt, and the sulfinate, those used in conventional adhesives can be used without any restriction. However, as the organic peroxide, diacyl peroxides such as dibenzoyl peroxide, di-p-chlorobenzoyl peroxide, dilauroyl peroxide, etc. are preferably used. Further, as the amine, secondary or tertiary amines are preferable, and those in which an aryl group is bonded to the nitrogen atom of the amine are particularly preferably used from the viewpoint of accelerating curing. For example, N.N'-dimethylaniline, N.N'-dimethyl-p-toluidine,
N-methyl-N'-β-hydroxyethyl-aniline, N,N'-di(β-hydroxyethyl)-aniline, N・N'-di(β-hydroxyethyl)-
Preferred examples include p-toluidine, N-methyl-aniline, and N-methyl-p-toluidine. Furthermore, hydrochlorides, acetates, phosphates, etc. of these amines can also be used. From the viewpoint of the stability of the curing agent, the sulfinates include alkali metal salts of arylsulfinic acids,
Alkaline earth metal salts or amine salts are good. For example, sodium benzenesulfinate, calcium benzenesulfinate, strontium benzenesulfinate, ammonium benzenesulfinate, triethylammonium benzenesulfinate, N of benzenesulfinate,
Examples include N'-dimethyl-p-toluidine salt. Salts of p-toluenesulfinic acid, β-naphthalenesulfinic acid, and styrenesulfinic acid can also be suitably used in the present invention. The blending ratios of (a) the radically polymerizable monomer, (b) the organic peroxide, (c) the amine or its salt, and (d) the sulfinate are as follows. (b)
The organic peroxide is preferably 0.01 to 10% by weight based on the packaging () and the total radically polymerizable monomers (including radically polymerizable monomers having an OH group; the same applies hereinafter) in the packaging () and packaging () described below. is 0.1 to 4% by weight
It is preferable that (c) The amine or its salt is also 0.01% of the total radically polymerizable monomers.
It is suitable that the amount is between 10 and 10% by weight, preferably between 0.1 and 4% by weight. Furthermore, (d) sulfinate is 0.1 to 10% by weight based on the total radically polymerizable monomer,
The content is preferably 0.3 to 5% by weight. The carboxyl group or its anhydride group-containing polymer (polymer) used in the present invention not only increases the adhesive strength of enamel but also provides adhesive strength to dentin. It is an important component in terms of preventing. In particular, the adhesion strength to dentin increases, and more favorable results are obtained in terms of margin sealing properties and prevention of regional harm to the dental pulp. The reason for this is not clear at present, but because the polymer has carboxyl groups or its anhydride groups, it has sufficient adhesive strength even in wet environments such as in the oral cavity and for example against tooth structure. This is thought to be because it has a high temperature and can withstand use. The above polymers are the packaging used in the present invention ()
and 0.1 to 40 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the total radically polymerizable monomer in the packaging ().
Preferably, parts by weight are used. This polymer may be included in either the package () or (), but it is preferably included in the package () from the viewpoint of storage stability or adhesive strength. The above-mentioned polymer having a carboxyl group or its anhydride group preferably has an acid value of 30 to 700, particularly 40 to 600, from the viewpoint of adhesion to teeth. In this specification, the acid value is defined as the number of mg of KOH required to neutralize 1 g of resin.
This acid value represents the concentration of carboxyl groups and their anhydride groups in the polymer. The carboxyl group or its anhydride group that the above-mentioned polymer has is often provided based on the raw material used when producing the polymer. As such a raw material, any known vinyl monomer having a carboxyl group or its anhydride group can be used without particular limitation. Examples of those generally suitably used are as follows. Namely, acrylic acid vinyl monomers such as acrylic acid and methacrylic acid; maleic acid, fumaric acid, itaconic acid, maleic anhydride,
Unsaturated dibasic carboxylic acid monomers such as itaconic anhydride; aromatic unsaturated carboxylic acid monomers such as 4-methacryloxyethyl trimellitic acid;
Alternatively, substituted derivatives obtained by substituting these vinyl monomers with substituents are preferably used. The above-described polymers are particularly preferably those having carboxyl groups bonded to adjacent carbon atoms, or those having anhydride groups bonded to the carbon atoms. It is preferable that the polymer used in the present invention has a hydrophobic group. By using a polymer with hydrophobic groups,
A polymer can have both hydrophilic and hydrophobic properties due to carboxyl groups or its anhydride groups. In this case, the performance can be particularly improved in adhesion of dissimilar materials, such as a material with a hydrophilic surface and a material with a hydrophobic surface. The hydrophobic group bonded to the polymer is not particularly limited, and any known hydrophobic group can be used. Typical examples of the hydrophobic groups that are generally suitably used are as follows. (1) Aryl groups such as phenyl and naphthyl groups (2) Alkyl groups such as methyl, ethyl, propyl and butyl groups (3) Alkoxy groups such as ethoxy, propoxy and butoxy groups (4) Acetyloxy groups Acyloxy groups (5) such as ethoxycarbonyl groups, butoxycarbonyl groups, etc. The polymers used in the present invention generally have a molecular weight of 1000 or less for reasons of ease of availability or ease of handling. ~100000 preferably 2000-50000
It is preferable that the The method for obtaining the above polymer is not particularly limited, but industrially, a vinyl monomer having a hydrophobic group as described above and a vinyl monomer having a carboxyl group or its anhydride group, or their A method of obtaining the resin by copolymerizing with a vinyl monomer in which a functional group is esterified or by subsequent hydrolysis is suitably employed. Therefore, suitable polymers include (A) the following formula: [In the formula, R ¹ is a hydrogen atom or an alkyl group,
R ² is an aryl group, an alkyl group, an alkoxy group,
It is an acyloxy group or an alkoxycarbonyl group. ] At least one unit represented by (B) the following formula [In the formula, R ³ is hydrogen, an alkyl group, or a carboxymethyl group, n and m are zero or 1, and when n is zero, m is 1, R ³ is a hydrogen atom, and n When is 1, m is zero and R ³ is hydrogen,
It is an alkyl group or a carboxymethyl group, and two carboxyl groups may form an anhydride group. ] It consists of at least one type of unit represented by the following. Further, when carrying out the above-mentioned copolymerization, there are no particular limitations, and in general, polymerization carried out using the following polymerization initiator is suitably employed. For example, radical polymerization using an organic peroxide such as benzoyl peroxide or lauroyl peroxide, an azo compound such as azobisisobutyronitrile, an organometallic compound such as tributylboron, or a redox initiator can be suitably used. The unit having a hydrophobic group represented by the above formula (A) is
Considering the water resistance of the resulting adhesive and its affinity with biological hard tissue, it is preferably contained in the polymer having a carboxyl group or its anhydride group in an amount of 40 mol % to 90 mol %. Among the components of the present invention, (e) may be contained in either the package () or () as explained above, and is preferably contained in the package (), but the other four components, namely (a) The four components, radically polymerizable monomer, (b) organic peroxide, (c) amine or its salt, and (d) sulfinate, are divided into two parts and stored separately. One package () contains (a) a radically polymerizable monomer and (b) an organic peroxide, and the other package () contains (a) a radically polymerizable monomer and (c ) amine or its salt and (d) sulfinate. Furthermore, in the packaging (), (a) the radically polymerizable monomer must contain 80 mol% or more, preferably 90 mol% or more of the radically polymerizable monomer having an OH group. The most important point in the present invention is that the radically polymerizable monomer in the same packaging as the sulfinate contains a specific amount of the radically polymerizable monomer having an OH group. This is the point that it includes.
By packaging in this way, the radically polymerizable monomer will not be modified by sulfinate even after long-term storage, and the adhesive will have good adhesive strength and edge-sealing properties. can. As mentioned above, the radically polymerizable monomer having an OH group must be contained in the radically polymerizable monomer of the packaging () in an amount of 80 mol% or more. It may also be included in the monomer. However, packaging() and packaging()
The amount of radically polymerizable monomers having an OH group contained in all radically polymerizable monomers is 10 to 90%, considering the water resistance of the adhesive of the present invention and the ease of wettability with human body hard tissue. It is preferred that the amount is mol %, preferably 20 to 80 mol %. The amount of the radically polymerizable monomer coexisting with the sulfinate in the packaging () is not limited, but is particularly effective for improving adhesive strength to tooth enamel and ensuring rapid hardening speed, etc., as described above. From the point, 1 to 1 part by weight of sulfinate
The range is preferably 150 parts by weight, more preferably 1 to 100 parts by weight. Further, it is preferable that both the packaging () and the packaging () of the adhesive of the present invention be in liquid form, since both packaging can be easily kneaded. Therefore,
If the package () and solid components of the package () are not dissolved in the radically polymerizable monomer, it is preferable to add a low boiling point organic solvent to completely dissolve the solid components. The amount of the low boiling point organic solvent used is in the range of 0.01 to 10 parts by weight, more preferably in the range of 0.01 to 5 parts by weight, based on 1 part by weight of the total radically polymerizable monomer in the packaging () and packaging (). It is preferable. The organic solvent with a low boiling point is not particularly limited, but alcohols such as ethanol and isopropyl alcohol; and esters such as ethyl acetate are preferably used because of their low toxicity. Furthermore, polymers, fillers, stabilizers, etc. can be added to the adhesive of the present invention as appropriate. [Effect] As explained above, the adhesive of the present invention has a radically polymerizable monomer and a sulfinate salt coexisting in the same package, so it has no effect on teeth, especially enamel and dentin. It has excellent adhesive properties. Therefore, since the composite repair material filled in the cavity of the tooth is firmly bonded to the enamel and dentin, the adhesive material has excellent margin sealing properties. Moreover, since the radical polymer monomer coexisting in the same package as the sulfinate contains a radical polymerizable monomer having an OH group,
Modification of the radically polymerizable monomer coexisting with the sulfinate can be prevented. Therefore, the above-mentioned adhesion to teeth and margin sealing properties do not deteriorate even when the adhesive of the present invention is stored for a long period of time, and the adhesive strength before storage is maintained. The adhesive also has excellent storage stability. The adhesive of the present invention exhibits a suitable adhesive effect particularly when used in a humid environment. Therefore, the adhesive of the present invention is not limited to dental adhesives, but is also useful as an adhesive for human hard tissue such as bone tissue. EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. Example 1 The composition shown in Table 1 as the adhesive () liquid was
In addition, an adhesive () having the composition shown in Table A below was prepared, and immediately after preparation and after being stored at 37°C for 2 months, the adhesive strength to enamel and untreated dentin was measured by the following method. Measurement of adhesive strength with enamel First, paste (A) and paste (B) were prepared according to the following formulations. (A)Bis-GMA Triethylene glycol dimethacrylate (hereinafter abbreviated as TEGDMA) Dihydroxyethyl-p-toluidine (hereinafter abbreviated as DEPT) Silanized quartz powder (particle size 80 μm or less) 2,6-di-t-butyl-p - Cresol (hereinafter abbreviated as BHT) 11.0 parts by weight 10.5 〃 0.5 〃 78.0 〃 0.01 〃 (B)Bis-GMA TEDMA BPO Silanized quartz powder (particle size 80μm or less) BHT 11.0 parts by weight 10.5 〃 1.0 〃 78.0 〃 0.01 Next The labial surface of a freshly extracted bovine tooth was polished with emery paper (#320) to expose the smooth enamel, and the polished surface was treated with a 37% orthophosphoric acid aqueous solution for 1 minute, rinsed with water for 30 seconds, and then flushed with nitrogen gas. I sprayed it to dry the surface. Then, a 2 mm thick plate of wax with holes of 4 mm in diameter was attached to the dry surface using double-sided tape. Next, the adhesive solution () and solution () were mixed at a ratio of 1:1, applied to the enamel surface surrounded by the plate-shaped wax, and nitrogen gas was blown to remove the ethanol and excess adhesive. . The pastes (A) and (B) were mixed at a ratio of 1:1 and filled thereon. After leaving it for one hour, remove the wax plate and soak it in water at 37℃ for a day and night.
℃ and 60℃ water for 1 minute alternately 500 times,
The tensile strength was then measured. For the measurement, Tensilon manufactured by Toyo Baldwin was used, and the tensile speed was
The speed was set at 10 mm/min. The results obtained are shown in Table 2. Example 2 TEGDMA 56.3 parts by weight bis GMA 43.2 〃 BPO 0.5 〃 BHT 0.01 〃 were used as the adhesive () liquid, and the composition shown in Table 3 was prepared as the adhesive () liquid. In the same manner, the adhesive strength to enamel was measured immediately after preparation and after storage at 37°C for 2 months. The results are shown in Table 4. Example 3 Using TEGDMA 47.7 parts by weight HEMA 21.6 〃 bis GMA 30.2 〃 BPO 0.5 〃 BHT 0.01 〃 as the adhesive () liquid, the composition shown in Table 5 was prepared as the adhesive () liquid, and immediately after preparation After storage at 37° C. for 2 months, the adhesive strength with enamel was measured in the same manner as in Example 1 as follows. The results are shown in Table 6. Measurement of bond strength with untreated dentin The labial surface of a freshly extracted bovine tooth was polished with emery paper (#320) to expose the smooth dentin, the polished surface was rinsed with water for 30 seconds, and then nitrogen gas was blown. and dried the surface. Then, a 2 mm thick plate of wax with holes of 4 mm in diameter was attached to the dry surface using double-sided tape. Next, the adhesive solution () and solution () are mixed at a ratio of 1:1, applied to the dentin surface surrounded by plate-shaped wax, and nitrogen gas is blown to remove the ethanol and excess adhesive. Ta.
Pastes (A) and (B) prepared in the measurement of adhesive strength with the enamel were mixed at a ratio of 1:1 and filled thereon. After leaving it for one hour, remove the wax plate and immerse it in water at 37°C for a day and night, then immerse it in water at 4°C and 60°C for 1 minute alternately 500 times, and then proceed in the same manner as above for measuring the adhesive strength with enamel. The tensile strength was measured using the method described below. The results are also listed in Table 2. Table A - Sodium toluenesulfinate 1.3% by weight HEMA 13.0 〃 DEPT 0.7 〃 BHT 0.01 〃 Ethanol 85.0 〃

【table】

[Table] Example 2 The adhesive () solution and the adhesive () solution shown in Example 1 were prepared and stored at 37°C for 2 months. Next, a cavity with a diameter of 3 mm and a depth of 2 mm was created on the labial surface of the extracted human tooth, and 40% of the enamel was removed.
After etching with phosphoric acid for 60 seconds, a mixture of the above adhesives () and () was applied thinly to the cavity wall and filled with the same paste used in Example 1. After 1 hour of filling, it was stored in water at 37°C, and after 1 day and 1 month, a barcoration test was performed in which it was immersed in fuchsin aqueous solutions at 4°C and 60°C for 500 times for 1 minute alternately, and the margin sealing properties were tested. did. The evaluation method was to cut the extracted tooth down the center and examine whether there was any dye (fuchsin) intruding between the cavity wall and the filling. As a result, no dye invasion was observed in any of the samples. Comparative Example 1 Using TEGDMA 47.7 parts by weight HEMA 21.6 〃 bis GMA 30.2 〃 BPO 0.5 〃 BHT 0.01 〃 as the adhesive () liquid, the composition shown in Table 3 was prepared as the adhesive () liquid. Immediately after storage and after storage at 37°C for 2 months, adhesive strength to enamel was tested in the same manner as in Example 1, and margin sealability tests were conducted in the same manner as in Example 2. The results are shown in Table 4.

【table】

[Table] Comparative Example 2 The adhesion force to untreated dentin of bovine teeth was measured in the same manner as in Example 1 using the adhesives () and () shown below and found to be 0 kg/cm ² . Ta. Adhesive () liquid () liquid () liquid () Half part HEMA 21.6 〃 BIS GMA 30.2 〃 BPO 0.5 〃 BHT 0.01 〃 Adhesive () Sodium p -truins sulfate 1.3 Heavy part HEMA 13.0 〃 DEPT 0.7 〃 BHT 0.1 〃 Ethanol 85.0 〃 Ethanol 85.0 〃

Claims (1)

[Claims] 1 (a) radically polymerizable monomer, (b) organic peroxide,
(c) An amine or its salt, (d) a sulfinate, and (e) a polymer having a carboxyl group or its anhydride group as its main component.
(a) and (b), but the other package () contains (a), (c) and (d)
Contains (e) all radically polymerizable monomers
It is contained in packaging () and/or () in a range of 0.1 to 40 parts by weight per 100 parts by weight, and (a) in packaging () contains a radically polymerizable monomer having an OH group. An adhesive containing 80 mol% or more and characterized in that the packaging () and () are stored separately and mixed at the time of use.