JP2015042695A - Cement for dental implant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress hardening in cement construction component by its invasion into sulcus upon attaching an abutment constituting a dental implant onto an upper structure.SOLUTION: Cement for a dental implant comprises a first component and second component used for attaching an abutment onto an upper structure. Both of the components have hardening function upon being mixed. Attachment of the abutment onto the upper structure is carried out in at least the following process: the first component is pasted on at least one attaching surface selected from attaching surfaces of the abutment and the upper structure; the second component is pasted on at least one attaching surface selected from attaching surfaces of the abutment and the upper structure; after accomplishment of pasting of the first component and the second component onto the attaching surfaces, by attaching the attaching surface of the abutment onto the attaching surface of the upper structure, the first component and the second component are mixed so that the mixture is hardened.

Description

  The present invention relates to a dental implant cement.

  A dental implant is generally composed of a tooth root part called a fixture made of titanium and an abutment part penetrating a gingival edge part called an abutment made of a metal such as titanium or a gold alloy or a ceramic such as zirconia. Is done. Furthermore, when performing dental implant treatment, an upper structure (prosthesis) serving as an inner crown made of gold-silver-palladium alloy or ceramics is mounted on the abutment. Examples of a method for fixing the upper structure to the abutment include a mechanical fixing method in which the upper structure is fixed with a screw and an adhesive fixing method in which the abutment is fixed using dental cement.

  Among the above fixing methods, the adhesive fixing method (cement fixing method) using dental cement is excellent in aesthetics and can firmly bond the abutment and the upper structure. Demand is increasing. Specifically, the cement fixing method includes a technique using a cement that hardens by an acid-base reaction (cement reaction) such as glass ionomer cement, carboxylate cement, zinc phosphate cement, and radical polymerizable monomer. It has been proposed to use a two-component curable cement, such as a technique using a resin cement or the like that is composed of an inorganic or organic filler and is polymerized and cured by a radical polymerization initiator (see, for example, Patent Documents 1 to 4). ). In addition, as a technique mainly intended for adhesion between the abutment and the upper structure, a technique using a one-component curable cement (see Patent Documents 5 and 6) or a paste by mixing two kinds of components immediately before use. A technique (Patent Document 7) using a two-component curable cement used as a shape has also been proposed. However, in order to ensure the working time in the oral cavity and the accuracy of the work, the one-component curable cement lacks practicality. In this respect, it is considered that it is preferable to use a two-component curable cement when bonding the abutment and the upper structure.

  Here, when glass ionomer cement is used, after a mixture of a liquid component composed of polycarboxylic acid and a powder component composed of fluoroaluminosilicate glass is placed between the abutment and the upper structure, The abutment and the upper structure are bonded and fixed. However, when glass ionomer cement is used, operations such as weighing and kneading become complicated. For this reason, it has also been proposed to use a mixture obtained by pasting polycarboxylic acid and glass ionomer powder and mixing them immediately before use for fixing the prosthesis to the teeth (see Patent Documents 2 and 3). When such a cement is used to bond and fix the superstructure of the dental implant and the abutment, usually, a cement component mixture in which polycarboxylic acid and glass ionomer powder are mixed is applied to the joint surface. Adhere. At this time, the excess cement component mixture mixture protruding from the adhesive interface is left as it is for about 5 to 10 minutes, and after semi-curing or curing, it is removed by a probe or the like. The reason for bonding in such a procedure is that when the abutment and the upper structure are bonded, the cement component mixture existing at the bonding interface is cured, and the adhesion between the abutment and the upper structure is ensured. This is because it takes time to maintain the bonding state for about 5 to 10 minutes.

  When resin cement is used, a cement component mixture obtained by kneading a liquid component containing a (meth) acrylate-based polymerizable monomer and a powder component containing polymethyl methacrylate powder is used as an abutment and a superstructure. The abutment and the upper structure are bonded and fixed by press-contacting them together (for example, refer to Patent Document 4), and a cement component mixture kneaded with two types of paste is used. After mounting between the attachment and the upper structure, the abutment and the upper structure are bonded and fixed by pressing the two together (for example, see Patent Document 5). In this case as well, as described above, the upper structure and the abutment are bonded and fixed so that the cement component mixture obtained by mixing two types of components constituting the cement protrudes from the adhesive interface, and protrudes from the adhesive interface. Any excess cement component mixture is removed after semi-curing or curing.

  On the other hand, the tissue around the dental implant has no cementitious or periodontal tissue around the dental implant and no connective tissue attachment between the dental implant and the surrounding soft tissue compared to the tissue around the natural tooth It is very different in that. A minute groove (so-called sarcus) formed at the boundary between the dental implant and the surrounding tissue is wider and deeper than the sarcus formed at the boundary between the natural tooth and the surrounding tissue. For this reason, when the superstructure and the abutment are bonded and fixed using dental cement, the cement component mixture protruding from the bonding interface easily enters the sarcas. When the cement component mixture that has entered the sarcas is hardened to become a hardened material, the hardened material becomes a hotbed where plaque bacteria propagate and easily causes problems such as inflammation of the tissue around the dental implant.

  Moreover, the width of the sarcas is narrow and has a deep structure. For this reason, when the cement component mixture which entered into the sarcas is cured, it is very difficult to remove the cured product from the sarcas. Furthermore, the tissue surrounding the dental implant is inferior in the ability to protect against plaque bacteria compared to the tissue surrounding the natural tooth. For this reason, the penetration | invasion of the cement component mixture into the sarcas mentioned above and its hardening are serious problems. Therefore, in order to solve such a problem, a technique has been proposed in which the abutment and the upper structure are bonded and fixed in a state in which the sarcus is blocked by the exclusion yarn (Non-Patent Document 1).

JP 2002-275017 A JP 2003-183112 A JP 2006-299201 A JP 2009-1536 A Japanese Patent Laying-Open No. 2005-8522 (see paragraph numbers 0001, 0044, etc.) JP 2006-136649 A (see claim 8, paragraph number 0001, paragraph number 0053, etc.) JP 2006-76962 A (see paragraph numbers 0001, 0039, etc.)

Nakajima Yasushi et al., "Separate volume of dental hygienist, understandable illustration: Introduction to implants for staff", published by Quintessence Publishing Co., Ltd., 2007, page 105

  However, the method of adhering and fixing in a state where the sarcus is sealed off using the exclusion thread is not only complicated, but also increases the time required for adhering and fixing the abutment and the upper structure. The burden on the patient increases. In addition to this, even when the above-described method was used, it was not possible to completely prevent the cement component mixture from entering into the sarcas and hardening. For this reason, it has been difficult to sufficiently suppress problems such as inflammation of the surrounding tissue of the dental implant that is secondarily generated by the cement constituent mixture mixture entering into the sarcus and hardening.

  The present invention has been made in view of the above circumstances, and when the abutment constituting the dental implant and the upper structure are bonded using the two-component curable cement, the cement constituent enters the sarcas. It is an object of the present invention to provide a dental implant cement that suppresses hardening.

The above-mentioned subject is achieved by the following present invention. That is,
The cement for dental implants according to the first aspect of the present invention is composed of a first component and a second component used for bonding the abutment constituting the dental implant and the superstructure, and the first component and the second component The abutment and the upper structure are bonded to each other on the at least one joint surface selected from the joint surface of the abutment and the joint surface of the upper structure. And applying the second component to at least one joint surface selected from the joint surface of the abutment and the joint surface of the upper structure, and imparting the first component and the second component to these joint surfaces After finishing, at least a process of mixing the first component and the second component by bonding the bonding surface of the abutment and the bonding surface of the upper structure and curing the mixture. It is implemented by.

  The cement for dental implants of the second aspect of the present invention is composed of a first component and a second component used for bonding the abutment constituting the dental implant and the superstructure, and the first component and the second component After the abutment and the upper structure are bonded, an adhesive layer formed by bonding between the bonded surface of the abutment and the bonded surface of the upper structure At least one component selected from the unreacted component of the first component, the unreacted component of the second component, and the reacted component of the first component and the second component has a concentration gradient. It is characterized by having.

  In one embodiment of the cement for dental implants of the first and second inventions, either one of the first component and the second component is a liquid component, and the other component is a paste-like component. Is preferred.

  In another embodiment of the cement for dental implants according to the first and second inventions, the viscosity at 23 ° C. of any one of the first component and the second component is 0.1 to 10 Pa · s. The viscosity of the other component at 23 ° C. is preferably 10 to 100 Pa · s.

  The cement for dental implants of the third aspect of the present invention is composed of a first component and a second component used for bonding the abutment constituting the dental implant and the superstructure, and the first component and the second component Has a function of curing by mixing, the viscosity at 23 ° C. of either one of the first component and the second component is 0.1 to 10 Pa · s, and the viscosity at 23 ° C. of the other component is It is preferably 10 to 100 Pa · s.

  The treatment method using the dental implant cement of the present invention is based on an abutment fixed to the side opposite to the side where the jawbone of the fixture embedded in the gingiva and fixed to the jawbone is placed in the dental implant treatment. When adhering the superstructure, a dental cement composed of a first component and a second component and having a function of hardening by mixing the first component and the second component is used. A first component applying step for applying one component to at least one of the joint surfaces selected from the joint surface of the abutment and the joint surface of the upper structure; and a second component of the joint surface of the abutment and the upper structure. The second component applying step applied to at least one of the bonding surfaces selected from the bonding surfaces, the first component applying step, and the second component applying step, and then the bonded surface of the abutment By bonding the bonding surface of the upper structure, a first component and a second component are mixed, in which the mixing and curing step of curing the mixture, the is performed by at least going through.

  In one embodiment of the treatment method using the dental implant cement of the present invention, it is preferable that one of the first component and the second component is a liquid component, and the other component is a paste-like component. .

  In another embodiment of the treatment method using the dental implant cement of the present invention, one of the first component and the second component has a viscosity at 23 ° C. of 0.1 to 10 Pa · s, The viscosity of the component at 23 ° C. is preferably 10 to 100 Pa · s.

  In another embodiment of the treatment method using the dental implant cement of the present invention, the first component comprises a liquid component, the second component comprises a paste-like component, and the first component application step comprises converting the first component into an abutment. The second component application step is performed after applying the first component application step, and the second component is applied to the abutment connection surface and the upper structure. It is preferable to implement by placing on at least one joint surface selected from the joint surfaces of the body.

  In another embodiment of the treatment method using the dental implant cement of the present invention, the thickness direction of the adhesive layer formed between the joint surface of the abutment and the joint surface of the superstructure after the mixing / curing step On the other hand, it is preferable that at least one component selected from the unreacted component of the first component and the unreacted component of the second component has a concentration gradient.

  ADVANTAGE OF THE INVENTION According to this invention, when the abutment which comprises a dental implant, and an upper structure are adhere | attached using a two-component hardening type cement, it is for dental implants which suppress that a cement structural component penetrate | invades into a sarcas and hardens. Cement can be provided.

  The cement for dental implants according to the first embodiment is composed of a first component and a second component used for bonding the abutment constituting the dental implant and the superstructure, and the first component and the second component. And has a function of curing by mixing. Here, in the adhesion between the abutment and the upper structure, the first component is applied to at least one of the joint surfaces selected from the joint surface of the abutment and the joint surface of the upper structure (first component application step). And applying the second component to at least one joint surface selected from the joint surface of the abutment and the joint surface of the upper structure (second component application step), After the application of the two components, the first component and the second component are mixed by bonding the joint surface of the abutment and the joint surface of the upper structure, and the mixture is cured (mixing / curing) It is carried out by at least going through (step). In dental implant treatment, the abutment is fixed to the side opposite to the side where the jaw bone of the fixture embedded in the gum and fixed to the jaw bone is disposed.

  In the dental implant cement of the first embodiment, two types of cement constituents constituting the dental implant cement; that is, the first component and the second component are used when the abutment and the superstructure are bonded. In addition, they are separately applied to the joint surface of the abutment and the joint surface of the upper structure without being mixed in advance before bonding. These two types of components are mixed only at the joint interface between the abutment and the upper structure when the joint surface of the abutment and the joint surface of the upper structure are joined. Here, the mixing of the first component and the second component at the bonding interface is performed in a direction perpendicular to the bonding interface when the abutment and the upper structure are bonded to perform fine alignment or fitting. It is promoted by the acting pressing force (first physical mixing force) and the minute slide motion (second physical mixing force) in the in-plane direction of the bonding interface. For this reason, since the first component and the second component which are in a separated state until immediately before joining are mixed immediately after joining, the mixture in which these components are mixed hardens quickly, and the abutment and the upper structure And are bonded.

  On the other hand, in order to sufficiently secure the adhesive strength between the abutment and the upper structure, it is necessary that the mixture of the first component and the second component exist substantially over the entire bonding interface. For this reason, when the dental implant cement of the first embodiment is used, the abutment is bonded to such an extent that the first component and the second component protrude from the bonding interface when the abutment and the upper structure are bonded. The first component and the second component are excessively applied to the surface and the joint surface of the superstructure. For this reason, when the abutment and the upper structure are joined, the first component and the second component protrude from the joining interface and enter the sarcus.

  However, physical mixing forces such as the first physical mixing force and the second physical mixing force generated at the bonding interface act on the first component and the second component that protrude from the bonding interface. There is little room. In addition, the first component and the second component that have infiltrated into the sarcas are thought to be mixed by a chemical mixing force due to molecular diffusion caused by the concentration gradient of each molecule constituting these components. However, such chemical mixing force is very weak compared to the first physical mixing force and the second physical mixing force. For this reason, the 1st component and 2nd component which penetrate | invaded in the sarcas continue maintaining the state which is not mixed so that a hardening reaction is caused substantially compared with the 1st component and 2nd component which exist in a joining interface. Or even if it is mixed so as to cause a curing reaction, a very long time is required.

  For this reason, even when the first component and the second component existing at the bonding interface are mixed and the curing is finished, the first component and the second component that have entered the sarcas are substantially cured. And the uncured state is maintained. That is, after the abutment and the upper structure have been bonded and fixed, the uncured first and second components present in the sarcus can be easily and reliably removed with a probe or water gun. Can be removed. For this reason, compared with the case where the abutment and the upper structure are bonded and fixed using the conventional two-component curing type dental cement, the dental implant cement according to the first embodiment is similar. In the case of performing adhesive fixation, it is possible to suppress the occurrence of secondary problems such as inflammation of the tissue around the dental implant due to the hardening of the cement component in the sarcas.

  If the first component or the second component can be easily applied to the joint surface of the abutment or the upper structure, for example, it can take the form of a liquid component or a paste-like component. Further, these liquid components and paste-like components may contain a powdery substance dispersed therein. However, as a possible form of the first component and the second component, it is excluded that it is a powdery component composed only of a powdery substance. This is because, if the powdery component is not used in combination with a solvent, a binder, a thickener, a dispersant, or the like, it tends to fall off even when applied to the bonding surface, and it is difficult to ensure adhesive strength. In addition, the first component and the second component may be composed only of a substance that is cured by reaction with the other component (a curable substance), and the curable substance and curable properties such as a solvent, a binder, and an additive. You may be comprised from other substances other than a substance. When the first component or the second component is composed of a curable material and other materials, the first component or the second component is a liquid component in which microcapsules containing the curable material are dispersed. Or a paste-like component. In this case, when the abutment and the upper structure are bonded, the microcapsule is mechanically broken by using a pressing force applied to the bonding interface, so that the first component and the second component are substantially separated. Can cause a slow mixing and curing reaction.

  Here, the first component and the second component may both be a combination of liquid components (first combination), or may be a combination of both paste components (second combination). A combination (third combination) in which one of them is a liquid component and the other is a paste-like component may be used. Even if the curable material contained in the first component and the curable material contained in the second component are the same, the abutment and the superstructure can be bonded by properly using the third combination from the first combination. It becomes easy to control the strength. This is because the thickness of the layer (adhesive layer) composed of the mixture of the first component and the second component at the bonding interface and the mixing degree of the first component and the second component differ depending on which combination is selected. Because.

  In the first combination in which the first component and the second component are composed of liquid components, both components have high fluidity and are excellent in mixing at the bonding interface, but it is somewhat difficult to apply a thick coating on the bonding surface. For this reason, the adhesive layer formed at the bonding interface tends to be thin although the homogeneity is high. On the other hand, in the second combination in which the first component and the second component are composed of paste-like components, both components have low fluidity, so the mixing at the bonding interface is slightly inferior, but thickly put on the bonding surface. Is easy. For this reason, it is easy to increase the thickness of the adhesive layer formed at the bonding interface, but the homogeneity tends to be low. In contrast, in the third combination of the first component and the second component consisting of the liquid component and the paste-like component, intermediate characteristics between the first combination and the second combination can be obtained, From the viewpoint of securing the adhesive strength, it is easier to achieve a balance between the homogeneity of the adhesive layer and the thickness of the adhesive layer. Considering these points, the third combination is most preferable among the first to third combinations.

  The viscosity of the first component and the second component at 23 ° C. (hereinafter sometimes simply referred to as “viscosity”) is not particularly limited, but ensures the ease of application of the first component and the second component to the joint surface. In view of the above, the range of about 0.1 to 100 Pa · s is preferable. Further, the viscosity of the first component and the viscosity of the second component may be approximately the same, but are preferably different. In the latter case, the viscosity of one component (low viscosity component) is preferably in the range of 0.1 to 10 Pa · s, more preferably in the range of 1 to 5 Pa · s, and the other component ( The viscosity of the high viscosity component) is more preferably within the range of 10 to 100 Pa · s, and more preferably within the range of 20 to 70 Pa · s. When the viscosity of the low-viscosity component and the viscosity of the high-viscosity component are within the above-described ranges, the application of the first component and the second component to the bonding surface can be facilitated, and at the time of bonding Mixing of the first component and the second component in the bonding interface can be made more reliable. In addition, when the combination of the first component and the second component is a combination of the low viscosity component and the high viscosity component described above, the order of application to the bonding surface first applies the low viscosity component to the bonding surface, It is preferable to apply a high-viscosity component to the bonding surface thereafter.

  Moreover, when the viscosity of both the first component and the second component is less than 0.1 Pa · s, which is a low viscosity region, the fluidity of these components becomes extremely high. Therefore, regardless of the presence or degree of the first physical mixing force or the second physical mixing force, only the chemical mixing force resulting from the mutual molecular diffusion between the first component and the second component can be used. , Mixing of both components is facilitated sufficiently. That is, in such a case, the first component and the second component that have entered the sarcas may be mixed quickly to form a cured body. Therefore, when the viscosity of both the first component and the second component is within a relatively low viscosity range of about 10 Pa · s or less, the lower limit of both viscosities is 0.1 Pa · s or more. Is preferable, and it is more preferably 1 Pa · s or more.

  In the dental implant treatment, when the abutment and the upper structure are bonded and fixed, there are a fixing method called “fitting” and a fixing method called “temporary”. Here, “attachment” is a method of permanently fixing the abutment and the upper structure. On the other hand, “temporary wearing” is a fixing method that assumes that the abutment and the upper structure are temporarily fixed for a few months to several years and then removed for maintenance or the like. . Therefore, when attaching, it is preferable to firmly fix the upper structure and the abutment. However, when temporarily attaching, the upper structure does not come off from the abutment by normal occlusion. When the upper structure is removed from the abutment, it is preferable that the upper structure has a strength that can be easily removed.

  On the other hand, dirt around the dental implant tends to accumulate and inflammation tends to occur. In addition, it is unavoidable that occlusal changes occur due to degeneration of the alveolar bone due to the use of dental implants for many years. Therefore, in recent dental implant treatment, it is considered preferable that the abutment and the upper structure are fixed by temporary attachment and the maintenance is performed periodically. Therefore, the dental cement preferably has an adhesive strength suitable for temporary attachment. Therefore, in view of the above-described circumstances, the adhesive strength suitable for temporary attachment is preferably in the range of 1 to 10 MPa and more preferably in the range of 3 to 7 MPa in terms of tensile adhesive strength. Moreover, it is preferable that the adhesive strength suitable for coalescence exceeds 10 MPa in terms of tensile adhesive strength, and it can be said that the higher the tensile adhesive strength, the better.

  The bond strength between the abutment and the upper structure depends on the dental cement material used for bonding and the bonding conditions. Therefore, in principle, the bond strength is suitable for temporary wear. In some cases, the adhesive strength may be suitable for bonding. However, in the conventional two-component curing type dental cement, it is usually assumed that two types of components are sufficiently mixed before use for bonding. For this reason, when the abutment and the superstructure are bonded using the conventional two-component curable dental cement, the two components are sufficiently mixed to obtain an adhesive strength suitable for bonding. However, it was difficult to obtain an adhesive strength suitable for temporary attachment. However, in the dental implant cement of the first embodiment, the first component and the second component are not mixed well in advance before bonding the abutment and the superstructure, but are mixed at the time of bonding. The For this reason, regarding the mixing condition of the two types of components at the time of bonding that affects the bonding strength, the dental implant cement of the first embodiment is slightly inferior to the conventional two-component curable dental cement. Tend. For this reason, in the cement for dental implants of the first embodiment, it is easy to control the adhesive strength within a range suitable for temporary attachment.

  Next, it demonstrates in detail about a 1st component provision process, a 2nd component provision process, and a mixing and hardening process. When performing these three steps, the first component application step and the second component application step may be performed simultaneously, or one may be performed first and then the other. Moreover, although a 1st component provision process and a 2nd component provision process can be implemented with respect to at least one joining surface among two joining surfaces, you may implement with respect to both joining surfaces. Furthermore, after implementing the 1st component provision process with respect to one joining surface, you may implement a 2nd component provision process further, and can also make the implementation order of these processes reverse. As a specific example in the case of carrying out the first component application step and the second component application step, for example, an embodiment in which the first component is applied to one bonding surface and the second component is applied to the other bonding surface (2 Mode), after applying the first component (or second component) to both bonding surfaces, then applying the second component (or first component) to either one of the bonding surfaces (three-time application method) And a mode in which the first component (or the second component) is applied to both the bonding surfaces, and then the second component (or the first component) is further applied to both the bonding surfaces (four-time application method). It is done. As a modified example of the three-time application method, after the first component (or second component) is applied to both joint surfaces, the second component (or first component) is joined while being sandwiched between these two joint surfaces. In some cases, a mixing / curing step is performed. In this case, the second component (or the first component) is applied to both joint surfaces and simultaneously joined.

  Here, in any of the two-time application method, the three-time application method, and the four-time application method, the combination of the first component and the second component is a combination of the liquid component and the paste-like component, or the viscosity is 0.1. A combination of a low viscosity component in the range of 10 to 10 Pa · s and a high viscosity component in the range of 10 to 100 Pa · s is preferable. In addition, in the case of the three-time application method or the four-time application method, a liquid component (or a low-viscosity component) is added to both joint surfaces from the viewpoint that the curability after mixing two kinds of components can be further increased. After the application, it is preferable to apply a paste-like component (or high viscosity component).

  When the first component (or second component) is applied to the bonding surface, if the first component (or second component) is a liquid component or a low viscosity component, it is applied to the bonding surface with a brush or a cotton swab. When the first component (or the second component) is a paste-like component or a high-viscosity component, it can be placed on the joint surface with a spatula or the like. Moreover, after providing a 1st component (or 2nd component) to a joining surface, when providing a 2nd component (or 1st component) further, the 2nd provision process is the component with the component initially given. It is preferable to carry out so that mixing does not occur. Further, when two kinds of components are sequentially applied to such one joint surface, the first component and the second component are combined with a liquid component and a paste-like component (or a low component). A combination of a viscosity component and a high viscosity component) is preferred. By adopting such a combination, when carrying out the first component application step and the second component application step, mixing of two types of components can be suppressed, and when the abutment and the upper structure are joined together This is because the two components can be appropriately mixed by the physical mixing force acting on the bonding interface.

  The amount of the first component and the second component applied to the bonding surface is not particularly limited, but is usually an amount that can be applied to the entire bonding surface from the viewpoint of ensuring uniform adhesiveness within the bonding interface surface. It is preferable. Further, the total amount of the first component and the second component applied to the bonding surface is such that the thickness of the adhesive layer formed by curing the mixture of the first component and the second component at the bonding interface is about 30 to 50 μm. It is preferable to be selected so that it falls within the range. Thereby, the amount of the first component and the second component protruding from the bonding interface at the time of bonding can be minimized while securing an appropriate adhesive strength.

  In addition, in order to further suppress or delay the curing reaction of the first component and the second component that have protruded from the bonding interface and entered the sarcas, the amount of either component applied to the bonding surface can be reduced. It is preferable that the amount applied to the joint surface of the other component is an excessive amount with respect to the amount applied of one component. The application of the first component and the second component to the joining surface in such a manner is particularly suitable when both the first component and the second component are liquid components. The reason for this is as follows. First, when both the first component and the second component are liquid components having high fluidity, the first component and the second component that have penetrated into the sarcas where the physical mixing force hardly acts are chemically caused by mutual molecular diffusion. Mixing is promoted only by the mixing force. However, if the mixing amount of the first component and the second component is made unbalanced by making the amount of the other component excessive with respect to the amount of the one component, the first in the sarcas This is because even if the component and the second component are mixed, the curing reaction is suppressed or prevented because the mixing ratio is biased.

  In addition, the amount of the first component and the second component that protrude from the bonding interface at the time of bonding, even if the application amount of the first component and the application amount of the second component applied to each bonding surface is unbalanced, The component added excessively preferentially protrudes without being proportional to the applied amount. For this reason, in the bonding interface, the mixing ratio of the first component and the second component is maintained within a range suitable for the curing reaction even if some imbalance occurs, and an adhesive layer can be formed. .

  After finishing the first component application step and the second component application step, a mixing / curing step is performed. In this mixing / curing process, the joint surface of the abutment after the application of each component is joined to the joint surface of the upper structure. And the 1st component and 2nd component which were provided on each joining surface are mixed using the physical mixing force which acts on a joining interface at the time of joining. In this way, the mixture in which the first component and the second component are mixed in the bonding interface forms an adhesive layer as the curing reaction proceeds and cures in the mixture. This completes the adhesion between the abutment and the upper structure.

  As described above, in the bonding work between the abutment and the superstructure using the dental implant cement according to the first embodiment, the first component and the second component are mixed before bonding as in the prior art. There is no need to keep it. On the other hand, the curing reaction of the first component and the second component is started immediately after mixing, and the curing speed is governed by the materials constituting the first component and the second component and the combination thereof. Therefore, when the first component and the second component are mixed before bonding and the abutment and the upper structure are bonded using this mixture as in the conventional case, the mixture of the first component and the second component is used. When the abutment and the upper structure are applied and the crimping operation of the two is completed, the curing reaction is insufficient to some extent in order to ensure workability from mixing to completion of the crimping operation. There must be. This is because when the curing speed is too high, the upper structure is likely to be bonded to the distorted position with respect to the abutment. Therefore, when the abutment and the upper structure are bonded using conventional dental cement, the first component and the second component are configured so as to obtain an appropriate curing rate in order to ensure workability. There are some limitations on the materials and their combinations. However, when the abutment and the upper structure are bonded using the dental implant cement of the first embodiment, the mixing of the first component and the second component and the pressing operation are performed substantially simultaneously. Even if the curing speed is faster than the conventional one, the possibility that the upper structure is bonded to the abutment at a distorted position is very small. Therefore, from the viewpoint of adjusting the curing rate, the degree of freedom of the materials constituting the first component and the second component used in the dental implant cement of the first embodiment and the combination thereof can be made larger than before. it can.

  In addition, the embodiment shown below is also mentioned as a modification of the cement for dental implants of 1st this embodiment demonstrated above. That is, the cement for dental implants of the second embodiment is composed of a first component and a second component used for bonding the abutment constituting the dental implant and the upper structure, and the first component and the first component. It has a function of curing by mixing the two components. In addition to this, after the abutment and the upper structure are bonded, the thickness direction of the adhesive layer formed by bonding between the bonded surface of the abutment and the bonded surface of the upper structure is At least one component selected from one component unreacted component, second component unreacted component, and reaction component between the first component and the second component has a concentration gradient. The concentration gradient need not be formed in all the thickness directions of the adhesive layer, but may be formed only partially.

  Here, “unreacted component” means that when the adhesive layer is formed by the curing reaction accompanying the mixing of the first component and the second component, the curing reaction in the thickness direction of the adhesive layer is non-uniform. In particular, among the substances contained in the first component and / or the second component, there is evidence in the reaction system due to consumption, decomposition, modification, etc. associated with the curing reaction. It means a substance whose abundance decreases (hereinafter referred to as “first evidence substance”). In addition, “reactive component” means that when the adhesive layer is formed by the curing reaction accompanying the mixing of the first component and the second component, the curing reaction in the thickness direction of the adhesive layer is non-uniform. Or it is an indirect evidence substance, specifically, a substance that is newly generated with the curing reaction between the first component and the second component and increases in the abundance in the reaction system (target product) As well as by-products, hereinafter referred to as “second evidence substance”).

  For example, when the dental implant cement is a radical polymerization type cement, which will be described later, specific examples of the first evidence substance described above include a reactive substance that forms a cured body such as a radical polymerizable monomer, and a hardening agent. Various additives (chemical polymerization initiators, amines, etc.) that are added for the purpose of starting or accelerating the reaction may be mentioned. A specific example of the second evidence substance is a polymer formed by polymerization of a radical polymerizable monomer.

  In addition, it is normally expected that multiple types of evidence substances remain in the adhesive layer. Therefore, at least one component selected from the unreacted component of the first component, the unreacted component of the second component, and the reacted component of the first component and the second component is present in the thickness direction of the adhesive layer. In order to determine whether or not there is a concentration gradient, it is only necessary to examine the presence or absence of a concentration gradient with respect to the thickness direction of the adhesive layer for at least any one of the evidence substances, particularly evidence substances that are easy to analyze and detect. Moreover, it does not specifically limit as an analysis / detection method of an evidence substance, A well-known analysis / detection method can be utilized.

  Similarly to the dental implant cement of the first embodiment, the dental implant cement of the second embodiment is also subjected to a first component application step, a second component application step, and a mixing / curing step. The abutment and the upper structure are bonded together. For this reason, the substantially same effect as the cement for dental implants of the first embodiment can be obtained.

  Here, when the abutment and the upper structure are bonded through these three steps, the first component and the second component exist in a separated state until the bonding, and after the bonding, It is mixed by the acting physical mixing force. However, the physical mixing force acting on the bonding interface is very small compared to the physical mixing force acting when mixing two types of components outside the bonding interface before bonding. Therefore, when (a) the viscosity of the first component and / or the second component is high, or (b) when the total amount of the first component and the second component applied to the joining surface is large, (c) upon joining, When the superstructure attached to the abutment is left to stand without much movement for fitting etc., in other words, when the time for applying physical mixing force is short, especially the first component present near the joint surface (Or the second component) is not sufficiently mixed with other components and tends to remain in the adhesive layer unreacted. In such a case, the unreacted component of the first component and the unreacted component of the second component have a concentration gradient in the thickness direction of the adhesive layer. That is, the adhesive layer formed at the bonding interface has an inclined structure. As described above, the cement for dental implants according to the second embodiment is characterized in that the adhesive layer formed by using the cement has an inclined structure with respect to the thickness direction. In consideration of this point, when the adhesive layer has a uniform structure in the thickness direction; that is, when compared with the case where the first component and the second component are completely mixed and cured. In the dental implant cement of this embodiment, it can be said that it is easier to realize an adhesive strength suitable for temporary attachment.

  Furthermore, as another modified example of the cement for dental implants of the first embodiment, the following embodiments may be mentioned. That is, the cement for dental implants of the third embodiment is composed of a first component and a second component used for bonding the abutment constituting the dental implant and the upper structure, and the first component and the first component. It has a function of curing when mixed with two components, and either one of the first component and the second component has a viscosity at 23 ° C. of 0.1 to 10 Pa · s, and the other component has a temperature of 23 ° C. The viscosity is 10 to 100 Pa · s. Here, similarly to the dental implant cement of the first embodiment, the cement for dental implant of the third embodiment is also used in the first component application step, the second component application step, and mixing / curing. Through the process, the abutment and the upper structure are bonded. For this reason, the substantially same effect as the cement for dental implants of the first embodiment can be obtained. However, in the dental implant cement of the third embodiment, a low viscosity component having a viscosity in the range of 0.1 to 10 Pa · s and a high viscosity component in the range of 10 to 100 Pa · s are used in combination. Therefore, as described above, it can be said that it is easy to ensure the adhesive strength of the bonding interface.

  Next, the detail of the 1st component and 2nd component which comprise the cement for dental implants of 1st, 2nd and 3rd this embodiment is demonstrated. As the cement for dental implants of the first, second and third embodiments, a known two-component curable cement can be used. Typically, (1) acid-base curable cement, (2) radical polymerization (3) Mixed cements of (1) and (2) above can be used.

(1) Acid-base curable cement Examples of the acid-base curable cement include zinc phosphate cement, glass ionomer cement, polycarboxylate cement, and zinc oxide Eugenol cement. Details of these cements will be described below.

-Zinc phosphate cement-
The zinc phosphate cement (ZnO—H ₃ PO ₄ -based cement) contains phosphoric acid as a main component, and the content thereof can be, for example, about 45 to 63 mass% with respect to the entire cement. . Moreover, it is preferable that the second component contains zinc oxide as a main component, and further contains magnesium oxide. In addition, metal oxides such as strontium oxide, silicon dioxide, ferric oxide, and yttrium oxide are included. It may be. These metal oxide components used in the second component are generally 700 to 70% by mass of 70 to 90% by mass of zinc oxide and 10 to 30% by mass of other metal oxides such as magnesium oxide. A powdery product obtained by sintering a sintered body obtained by sintering at a high temperature of ℃ or higher with a ball mill or the like is used. Moreover, in addition to the said component, water-soluble solvents, such as water, may be added to a 1st component and a 2nd component, Furthermore, other additives, such as a thickener, may be added as needed.

  Here, the thickener is used for adjusting the viscosity of the first component and the second component and whether the first component and the second component are liquid or paste. As the thickener, both inorganic and organic can be used. For example, inorganic thickeners such as fumed silica having an average particle diameter of 5 to 40 nm, carboxymethylcellulose calcium, carboxymethylcellulose sodium, starch, Sodium starch glycolate, sodium starch phosphate ester, methylcellulose, sodium polyacrylate, alginic acid, sodium alginate, propylene glycol alginate, casein, sodium caseinate, polyethylene glycol, ethylcellulose, hydroxyethylcellulose, gluten, locust bean gum, gelatin, etc. Mention may be made of organic thickeners. Two or more of these thickeners may be mixed and used. In addition, these thickeners are used to adjust the viscosity of the first component and the second component constituting various cements described below, and whether the first component and the second component are liquid or pasty. Can also be used.

-Glass ionomer cement-
The glass ionomer cement has a first component containing polycarboxylic acid as a main component and a second component containing fluoroaluminosilicate glass as a main component. Furthermore, these 1st component and 2nd component contain water-soluble solvents, such as water, You may add other additives, such as a thickener, as needed.

  Here, as the polycarboxylic acid constituting the first component, any polycarboxylic acid used in general dental glass ionomer cement can be used. Typically, α-β unsaturated monocarboxylic acid is used. Examples thereof include polymers of acid or α-β unsaturated dicarboxylic acid. Specifically, this polymer includes acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, etc. It is a copolymer or a homopolymer having a weight average molecular weight of 5000 to 40000.

Further, as the fluoroaluminosilicate glass constituting the second component, fluoroaluminosilicate glass powder or the like generally used for dental glass ionomer cement can be used. The fluoroaluminosilicate glass powder preferably contains Al ³⁺ , Si ⁴⁺ , F ⁻ , O ²⁻ as main components, and further contains Sr ²⁺ and / or Ca ²⁺ . The fluoroaluminosilicate glass powder has, as its main composition, Al ³⁺ : 10 to 25% by weight, Si ⁴⁺ : 5 to 30% by weight, F ⁻ : 1 to 30% by weight, based on the total weight of the glass. Sr ²⁺ : 0 to 20% by weight, Ca ²⁺ : 0 to 20% by weight, alkali metal ions (Na ⁺ , K ⁺ etc.): 0 to 10% by weight. After mixing and melting the raw materials containing these, cooling -It is more preferable to prepare a powder having an average particle size of about 0.02 to 20 μm by pulverization.

-Polycarboxylate cement-
The polycarboxylate cement contains a polycarboxylic acid as a main component of the first component. Examples of the polycarboxylic acid include a polymer of acrylic acid, and a copolymer of acrylic acid and acrylic acid ester, methacrylic acid ester or unsaturated carboxylic acid (for example, maleic acid, itaconic acid, aconitic acid, etc.). . Moreover, as a 1st component, low molecular carboxylic acid (For example, a citric acid, tartaric acid, a maleic acid, etc.) may be contained with polycarboxylic acid. The second component contains zinc oxide as a main component, and may contain magnesium oxide in addition. Furthermore, the second component may contain other metal oxides such as silicon oxide, aluminum oxide, calcium fluoride, aluminum phosphate, cryolite. Furthermore, these 1st component and 2nd component contain water-soluble solvents, such as water, You may add other additives, such as a thickener, as needed.

-Zinc oxide Eugenol cement-
The zinc oxide eugenol cement contains eugenol (also referred to as eugenol or eugenol), which is an oily liquid with a first component as a main component, and zinc oxide as a main component. In addition, it is also preferable to add acetic acid or zinc acetate to the second component as a curing reaction accelerator. Moreover, a thickener and another additive can be added to a 1st component as needed. The second component contains a water-soluble solvent such as water, and a thickener and other additives can be added as necessary.

  In the various acid-base curable cements described above, the first component and the second component are a combination of a liquid component (or low viscosity component) and a liquid component (or low viscosity component), a liquid component (or low viscosity component). ) And a paste component (or high viscosity component), a paste component (or high viscosity component) and a liquid component (low viscosity component), and a paste component (or high viscosity component) and paste Any of the combination with a component (or high viscosity component) may be sufficient. However, among these combinations, the first component whose main component is an organic component is a liquid component (or low-viscosity component), and the second component whose main component is an inorganic component is a paste-like component (or high-viscosity component). It is preferable that The reason why the second component is a paste-like component (or a high-viscosity component) is that the inorganic component itself is basically in the form of a powder, so that the inorganic powder can be uniformly applied without dropping off the bonding surface. Because.

(2) Radical polymerization type cement (resin cement)
In the radical polymerization type cement, each of the first component and the second component includes a radical polymerizable monomer and one component of a chemical polymerization initiator. In addition, a filler may be added to each component for the purpose of adjusting the viscosity or in a liquid or paste form, and other additives may be added as necessary. Also good. Moreover, as for a 1st component and a 2nd component, from the viewpoint of making adhesive strength and a cure rate balance in balance normally, one component of a chemical polymerization initiator is 0.00 with respect to 100 mass parts of radically polymerizable monomers. It is preferably contained in the range of 05 to 15 parts by mass, and more preferably contained in the range of 0.5 to 8 parts by mass. Furthermore, when using a filler, it is preferable that the filler is contained in the range of 20 to 1000 parts by mass in the first component and the second component with respect to 100 parts by mass of the radical polymerizable monomer. More preferably, it is contained within the range of 70 to 400 parts by mass. This makes it easier to secure sufficient adhesive strength in addition to the appropriate viscosity suitable for the bonding operation. Below, each component, such as the polymerizable monomer used for radical polymerization type cement, a chemical polymerization initiator, and the filler used as needed, is demonstrated.

-Polymerizable monomer-
The polymerizable monomer is not particularly limited as long as it is a known polymerizable monomer capable of radical polymerization, but from the viewpoint of polymerizability and safety to living bodies, a (meth) acrylic acid ester-based radical polymerizable monomer is not limited. A mer is preferably used. Specific examples of the polymerizable monomer include those exemplified below, and these can be used singly or in combination of two or more.

<Monofunctional radical polymerizable monomer>
Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2,3-dihydroxybutyl methacrylate, 2,4-dihydroxybutyl methacrylate 2-hydroxymethyl-3-hydroxypropyl methacrylate, 2,3,4-trihydroxybutyl methacrylate, 2,2-bis (hydroxymethyl) -3-hydroxypropyl methacrylate, 2,3,4,5-tetrahydroxypentyl Methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, tetraethylene glycol Call monomethacrylate, pentaethylene glycol monomethacrylate, N, N-dimethylaminoethyl methacrylate methacrylate, and the like, and corresponding acrylates to these methacrylates.

<Bifunctional radical polymerizable monomer>
(I) an aromatic compound-based bifunctional radically polymerizable monomer;
2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2-bis (4-methacryloyloxyphenyl) propane, 2 , 2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane), 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2, 2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2- (4-methacryloyloxydiethoxyphenyl) -2- (4-methacryloyloxydi) Ethoxyphenyl) propa 2- (4-methacryloyloxydiethoxyphenyl) -2- (4-methacryloyloxyditriethoxyphenyl) propane, 2- (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane, and acrylates corresponding to these methacrylates;

  Addition of diisocyanate compounds having aromatic groups such as diisocyanate methylbenzene and 4,4'-diphenylmethane diisocyanate and methacrylates having hydroxyl groups, methacrylates having amino groups, or acrylates corresponding to these methacrylates Diaducts obtained from

  The hydroxyl group-containing methacrylates described above include 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, diethylene glycol monomethacrylate, and triethylene glycol monoester. There are methacrylate, tetraethylene glycol monomethacrylate, pentaethylene glycol monomethacrylate and the like. Examples of amino group-containing methacrylates include 2-aminoethyl methacrylate, 3-aminopropyl methacrylate, 2-aminopropyl methacrylate, 4-aminobutyl methacrylate, 5-aminopentyl methacrylate, and 3-aminopentyl methacrylate.

(Ii) an aliphatic compound-based bifunctional radically polymerizable monomer;
Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1 , 6-hexanediol dimethacrylate, and acrylates corresponding to these methacrylates;

  Diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), methacrylates having hydroxyl groups, methacrylates having amino groups, or these methacrylates Diaducts obtained from addition with acrylates corresponding to the class. The hydroxyl group-containing methacrylates and amino group-containing methacrylates are as exemplified above.

<Trifunctional radical polymerizable monomer>
Methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates.

<Tetrafunctional radical polymerizable monomer>
Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, diadducts obtained from the addition of a diisocyanate compound and glycidol dimethacrylate, and the like.

  The above diisocyanate compounds include diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 4,4-diphenylmethane diisocyanate, tolylene-2,4. -Diisocyanate and the like

  Among the polymerizable monomers listed above, it is possible to use a bi-, tri- or tetrafunctional radically polymerizable monomer having a plurality of radically polymerizable groups in that the obtained cured product has high mechanical strength. preferable.

<Acid group-containing polymerizable monomer>
The polymerizable monomer described above is a polymerizable monomer that does not contain an acidic group (an acidic group-free polymerizable monomer), but a polymerizable monomer that contains an acidic group (acidic group). Group-containing polymerizable monomer) can also be used. In this case, as the polymerizable monomer, an acidic group-containing polymerizable monomer may be used alone, or an acidic group-containing polymerizable monomer and an acidic group-free polymerizable monomer are used in combination. Also good.

The acidic group-containing polymerizable monomer is a compound having at least one acidic group and at least one radically polymerizable unsaturated group. Here, the acidic group means that an aqueous solution or aqueous suspension of a radical polymerizable monomer having this group exhibits acidity, and is typically a carboxyl group (—COOH), a sulfo group (—SO ₃ ). Examples thereof include those having a hydroxyl group such as H), a phosphinico group {= P (═O) OH}, and a phosphono group {—P (═O) (OH) ₂ }. In addition to such hydroxyl group-containing acidic groups, an acid anhydride group having a structure in which two hydroxyl-containing acidic groups are dehydrated and condensed, an acid halide group in which the hydroxyl group of the hydroxyl group-containing acidic group is substituted with a halogen, etc. Can be mentioned. Also, the radically polymerizable unsaturated group is not particularly limited and may be a known one. Examples thereof include (meth) acryloyl groups such as (meth) acryloyl groups, (meth) acryloyloxy groups, (meth) acryloylamino groups, (meth) acryloylthio groups, vinyl groups, allyl groups, and styryl groups. .

Examples of the acidic group-containing polymerizable monomer include those exemplified in the following (i) to (v).
(I) Radical polymerizable monomer having one carboxyl group in the molecule (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, N- (meth) acryloyl-5 -Acid salicylic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate and acid anhydrides or acid halides of the above radical polymerizable monomers.

(Ii) Radical polymerizable monomer having a plurality of carboxyl groups or acid anhydride groups in the molecule 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane-1 , 1-dicarboxylic acid, 12- (meth) acryloyl oxide decane-1,1-dicarboxylic acid, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid and acid anhydrides of the above radical polymerizable monomers or Acid halide etc.

(Iii) A radically polymerizable monomer having a phosphinicooxy group or phosphonooxy group in the molecule (sometimes referred to as a radically polymerizable acidic phosphate ester)
2- (meth) acryloyloxyethyl dihydrogen phosphate, bis (2- (meth) acryloyloxyethyl) hydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 10- (meth) acryloyl Oxydecyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl 2-bromoethyl hydrogen phosphate, 2- (meth) acrylamidoethyl dihydrogen phosphate Fate, bis (6- (meth) acryloyloxyhexyl) hydrogen phosphate, bis (10- (meth) acryloyloxydecyl) hydrogen phosphate, bis {2- ( Data) acryloyloxy - (1-hydroxymethyl) ethyl} hydrogen phosphate, etc., and acid anhydrides of the radical polymerizable acidic phosphoric acid esters, acid halides and the like.

(Iv) Radical polymerizable monomers having a phosphono group in the molecule such as vinylphosphonic acid and p-vinylbenzenephosphonic acid.
(V) A radically polymerizable monomer having a sulfo group in the molecule such as 2- (meth) acrylamide-2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid, vinylsulfonic acid and the like.

  Further, besides the acidic group-containing polymerizable monomers shown in the above (i) to (v), JP-A Nos. 54-11149, 58-140046, 59-15468 JP-A-58-173175, JP-A-61-293951, JP-A-7-179401, JP-A-8-208760, JP-A-8-319209, JP-A-10-236912 An acidic group-containing polymerizable monomer described as a component in a dental adhesive composition disclosed in Japanese Patent Laid-Open No. 10-245525 is also an acidic group-containing polymerizable monomer. It can be suitably used.

-Chemical polymerization initiator-
The chemical polymerization initiator used for the first component and the second component is a combination of two or more compounds, and these are mixed (contacted) to form a redox system to generate radicals. For this reason, at least 1 sort (s) of 2 or more types of compounds is mix | blended with a 1st component, and the remainder is mix | blended with a 2nd component. (1)-(6) in following Table 1 is mentioned as a combination of 2 or more types of each component which comprises a chemical polymerization initiator. In Table 1, the numerical values in parentheses indicate a suitable range of the relative blending ratio, and in the example shown in (1), 1 mol of organic peroxide contained in the second component This means that the amine compound contained in the first component is preferably in a proportion of 0.01 to 4 mol. In addition, the compound shown as a 1st component shown in Table 1 may be contained in the 2nd component, and the compound shown in the 2nd component shown in Table 1 may be contained in the 1st component.

  The chemical polymerization initiator composed of a combination of two or more compounds as exemplified in (1) to (6) of Table 1 can be used alone or two or more chemical polymerization initiators. Can also be used in combination. Among these chemical polymerization initiators, a chemical polymerization initiator composed of the combination shown in the above (1) is preferable because high adhesive strength is obtained and handling is easy. Hereinafter, each component shown in Table 1 constituting the chemical polymerization initiator will be described with specific examples.

<Organic peroxide>
The organic peroxide is not particularly limited, and a known one can be used. Typical organic peroxides include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate, and the like.

  Examples of the ketone peroxide include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide. Examples of the hydroperoxide include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide.

  Diacyl peroxide includes acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. Etc. Dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3- Examples thereof include bis (t-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3.

  Peroxyketals include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t- And butyl peroxy) butane, 2,2-bis (t-butylperoxy) octane, and 4,4-bis (t-butylperoxy) valeric acid-n-butyl ester. As peroxyesters, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, and t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethyl Hexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydrotereph Examples include tartrate, t-butyl peroxy-3,3,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxymaleic acid.

  As peroxydicarbonate, di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, di-n -Propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, diallyl peroxydicarbonate and the like.

<Amines>
The amines are not particularly limited, but secondary or tertiary amines in which an amino group is bonded to an aryl group or a pyridyl group are preferable in terms of acceleration of curing. Specific examples of the amines include secondary amines and tertiary amines represented by the following general formula (1).

Here, in the general formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms in the main chain. In addition, this alkyl group may be substituted with a halogen atom, a hydroxyl group, a phenyl group, or an alkyl group having 1 to 5 carbon atoms. R ² is an alkyl group having 1 to 10 carbon atoms in the main chain. In addition, this alkyl group may be substituted with a halogen atom, a hydroxyl group, a phenyl group, or an alkyl group having 1 to 5 carbon atoms. R ³ is an aryl group having 6 to 14 carbon atoms constituting the ring or a pyridyl group. This aryl group or pyridyl group is a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a formyl group, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 2 carbon atoms. May be substituted with a -5 alkynyl group, a C1-C5 alkoxyl group, a C2-C5 acyl group, a C2-C5 acyloxy group, or a C2-C6 alkoxycarbonyl group. .

In R ¹ and R ² , examples of the alkyl group having 1 to 10 carbon atoms in the main chain include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, and an n-decyl group. Examples of the alkyl group substituted with the substituent include chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, Examples include 6-hydroxyhexyl group, i-propyl group, i-butyl group, t-butyl group, 1-methylpropyl group, 2-ethylhexyl group, benzyl group and the like. Preferred alkyl groups as R ¹ and R ² are those having 1 to 5 carbon atoms in the main chain.

In R ³ , examples of the aryl group having 6 to 14 carbon atoms constituting the ring include a phenyl group, 1- or 2-naphthyl group, 1-, 2- or 9-anthranyl group, and the like. Examples of the aryl group substituted with a group include o-, m- or p-chlorophenyl group, o-, m- or p-bromophenyl group, o-, m- or p-hydroxyphenyl group, 3-hydroxy-2 Naphthyl group, o-, m- or p-nitrophenyl group, o-, m- or p-cyanophenyl group, o-, m- or p-methylphenyl group, o-, m- or p-butylphenyl Group, 3,4-dimethylphenyl group, 2,4-dimethylphenyl group, o-, m- or p-styryl group, o-, m- or p- (2-propynyl) phenyl group, o-, m- Or p-methoxy Phenyl group, o-, m- or p-ethoxyphenyl group, 2-, 3- or 4-acetylphenyl group, 2-, 3- or 4-acetyloxyphenyl group, 4-hydroxy-3-methylphenyl group, Examples include 4-methyl-2-nitrophenyl group. Preferred aryl groups as the group R ⁸ are those having 6 to 10 carbon atoms constituting the ring.

  Among the amine compounds represented by the general formula (1), examples of secondary amines that can be suitably used include N-methylaniline, N- (2-hydroxyethyl) aniline, N-methyl-p-toluidine, and the like. Can be mentioned. Tertiary amines that can be suitably used include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N-methyl- N- (2-hydroxyethyl) aniline, N, N-di (2-hydroxyethyl) aniline, p-bromo-N, N-dimethylaniline, p-chloro-N, N-dimethylaniline, N, N-dimethyl -P-toluidine, N, N-diethyl-p-toluidine, p-tolyldiethanolamine, N-methyl-N- (2-hydroxyethyl) -p-toluidine, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p -Dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N N-dimethylanthranic acid methyl ester, p-dimethylaminophenethyl alcohol, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl -Β-naphthylamine and the like.

<Organic sulfinic acid compound>
Examples of the organic sulfinic acid compound include benzenesulfinic acid, o-toluenesulfinic acid, m-toluenesulfinic acid, p-toluenesulfinic acid, 2.3-dimethylbenzenesulfinic acid, 3,5-dimethylbenzenesulfinic acid, α -Lithium salt, sodium salt, potassium salt, magnesium salt, ammonium salt, pyridinium salt, quinolinium salt and the like of sulfinic acid such as naphthalenesulfinic acid.

<Aryl borate compound>
The aryl borate compound is a borate compound having 1 to 4 boron-aryl bonds in one molecule, and preferably a borate compound having 3 to 4 boron-aryl bonds in one molecule. Specifically, salts of borates having 3 or 4 boron-aryl bonds in one molecule, for example, metal salts such as sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium Salts, ammonium salts such as tetraethylammonium salt, tributylammonium salt, triethanolammonium salt, pyridinium salts such as methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, or methylquinolinium salt, ethylquinolinium salt, butylchi A quinolinium salt such as a norinium salt can be given. Here, as a borate compound having three boron-aryl bonds in one molecule, monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluorophenyl) boron, monoalkyl Tris (3,5-bistrifluoromethyl) phenyl boron, monoalkyltris [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, Monoalkyltris (p-nitrophenyl) boron, monoalkyltris (m-nitrophenyl) boron, monoalkyltris (p-butylphenyl) boron, monoalkyltris (m-butylphenyl) boron, monoalkyltris (p- Butyloxyphenyl) boron, monoalkyltris (m-butyl) Oxy phenyl) boron, monoalkyl tris (p- octyloxyphenyl) boron, a monoalkyl tris (m-octyloxyphenyl) boron can be exemplified. In addition, borate having four boron-aryl bonds in one molecule includes tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl). Phenylboron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m -Nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyloxy) Phenyl) boron, tetrakis (m-octi) It can be exemplified oxyphenyl) boron. In the above borate, alkyl is either n-butyl, n-octyl or n-dodecyl.

<Acid compound>
As the acidic compound, known inorganic acids and organic acids can be used. Specifically, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, maleic acid, citric acid, malonic acid, oxalic acid, propane Examples include organic acids such as sulfonic acid, benzenesulfonic acid, and toluenesulfonic acid. In addition to these acidic compounds, acidic group-containing polymerizable monomers can also be used.

<Barbituric acid derivative>
Examples of the barbituric acid derivative include 5-butyl (thio) barbituric acid, 1,3,5-trimethyl (thio) barbituric acid, 1-benzyl-5-phenyl (thio) barbituric acid, and 1-cyclohexyl. Examples include -5-methyl (thio) barbituric acid, 1-cyclohexyl-5-butyl (thio) barbituric acid and the like.

<Copper compound>
Specific examples of the copper compound include acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like.

  The compounding amount of the chemical polymerization initiator is in the range of 0.1 to 15 parts by mass per 100 parts by mass of the total polymerizable monomer (the total of the acidic group-containing polymerizable monomer and the non-acidic polymerizable monomer). The inside is preferable and the inside of the range of 0.5-8 mass parts is more preferable. By setting the blending amount to 15 parts by mass or less, it is possible to suppress the curing rate from becoming higher than necessary, and to improve the workability at the time of joining. In addition to this, discoloration of the cured product can be reliably suppressed. Moreover, by making a compounding quantity into 0.1 mass part or more, it can suppress that a cure rate becomes remarkably slow, and can ensure appropriate physical properties (for example, mechanical strength etc.) as a hardened | cured material easily. In addition, since the chemical polymerization initiator is composed of a combination of two or more types of compounds, the compounding amount of the chemical polymerization initiator is the total amount of each compound. Since the functional monomer also functions as an acidic compound, the amount of aryl borates is the amount of the chemical polymerization initiator.

-Filler-
As the filler, an organic filler and an inorganic filler can be used. Examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, ethylene-vinyl acetate copolymer, Examples thereof include styrene-butadiene copolymers, acrylonitrile-styrene copolymers, acrylonitrile-styrene-butadiene copolymers, and the like can be used alone or as a mixture of two or more. Examples of the inorganic filler include quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, strontium glass, and fluoroaluminosilicate glass. These are also used alone or in admixture of two or more.

  As the filler, an inorganic filler is preferably used, and among the inorganic fillers, fluoroaluminosilicate glass is more preferably used for the purpose of imparting a sustained release of fluorine. Such fluoroaluminosilicate glass is not particularly limited as long as it is a filler of oxyfluoride glass of aluminum and silicon, and those commonly used as acid-reactive fillers and ion-eluting fillers in dental cements and the like. Can be used. The preferred composition of the fluoroaluminosilicate glass is 10% to 33% by weight of silicon; 4 to 30% by weight of aluminum; 5 to 36% by weight of alkaline earth metal; 0 to 10% by weight of alkali metal; 2-16% by mass; fluorine 2-40% by mass; the remaining amount is oxygen. The alkaline earth metal is preferably calcium, magnesium, strontium, or barium. Moreover, as said alkali metal, sodium, lithium, and potassium are suitable, and sodium is especially suitable especially. Furthermore, if necessary, a material in which a part of the aluminum is replaced with titanium, yttrium, zirconium, hafnium, tantalum, lanthanum, or the like can be used.

  Such a fluoroaluminosilicate glass is, for example, a method of mixing metal compounds such as silica, alumina, fluorite, cryolite, aluminum fluoride, sintering at 1100 to 1300 ° C., and then pulverizing, or a sol-gel method, etc. Can be manufactured. The inorganic filler can be used after being surface-treated by a known method using a surface treatment agent such as a silane coupling agent. Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinylethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-chloropropyltrimethylsilane. Methoxysilane, hexamethyldisilazane and the like are preferably used. When fluoroaluminosilicate glass is used as the inorganic filler, the fluoraluminosilicate glass may be coated with a polymer compound or the like for the purpose of improving kneadability with other components.

  The shape of the filler is not particularly limited, and the filler may have an irregular particle shape as obtained by ordinary pulverization, or may be a spherical particle. The particle size of the filler is not particularly limited, but the larger the particle size, the lower the viscosity at the same filling amount. For this reason, the viscosity of the first component and the second component to which the filler is added can be controlled to a desired viscosity by selecting the particle size in addition to the addition amount of the filler. In addition, it is preferable that the average particle diameter of a filler is 0.01-100 micrometers, especially 0.1-50 micrometers from a viewpoint that the viscosity suitable for joining operation | work of an abutment and an upper structure is easy to be obtained.

(3) Mixed cement of acid-base curing cement and radical polymerization cement As the mixing cement, there is no particular limitation as long as it is a cement that utilizes the polymerization mechanism of both acid-base curing reaction and radical polymerization reaction. In radical polymerization type cement, a copper compound and a halogen compound are used as one component of the chemical polymerization initiator used as the first component, and barbituric acid is used as one component of the chemical polymerization initiator used as the second component. Can be mentioned. Here, as the halogen compound, dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like are preferably used. Moreover, it is preferable to use a copper compound within the range of 0.000001-0.01 mol with respect to 1 mol of barbituric acid, and it is preferable to use a halogen compound within the range of 0.0001-1 mol.

  Other mixed cements include resin reinforced glass ionomer cements. In this cement, the first component contains an acidic group-containing polymerizable monomer and one component of a chemical polymerization initiator, the second component contains fluoroaluminosilicate glass and / or zinc oxide, and one of the chemical polymerization initiators. Ingredients included. In addition, a water-soluble solvent such as water or a thickener can be added to the first component and the second component, if necessary, for adjusting the viscosity and liquid / paste. In addition, as a combination of 2 or more types of each component which comprises a chemical polymerization initiator, (1)-(6) illustrated in Table 1 is mentioned, for example.

  Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the present invention is not limited to these examples and the like.

First, the abbreviations of the compounds used in Examples and Comparative Examples described below are shown below.
<Polymerizable monomer>
D-2.6E: 2,2-bis (4- (methacryloyloxyethoxy) phenyl) propane UDMA: 1,6-bis (methacrylethyloxycarbonylamino) 2,2,4-trimethylhexane PM: 2 -Methacryloyloxyethyl dihydrogen phosphate (PM1) and bis (2-methacryloyloxyethyl) hydrogen phosphate (PM2) in a mass ratio of 2: 1-3G: triethylene glycol dimethacrylate- HEMA: 2-hydroxyethyl methacrylate

<Filler>
F-1: Spherical silica-zirconia γ-methacryloyloxypropyltrimethoxysilane surface-treated product; average particle size 0.4 μm
F-2: γ-methacryloyloxypropyltrimethoxysilane surface-treated product of spherical silica-titania; average particle size 0.07 μm
F-3: fumed silica; average particle size 0.01 μm
F-4: Powder obtained by pulverizing fluoroaluminosilicate glass powder (Tokuso Ionomer, manufactured by Tokuyama Dental Co., Ltd.) to a mean particle size of 0.5 μm using a wet continuous ball mill (New My Mill, manufactured by Mitsui Mining Co., Ltd.)

<One component of polymerization initiator>
BPO: benzoyl peroxide PBTEOA: triethanolammonium salt of tetraphenyl boron DEPT: N, N-bis (2-hydroxyethyl) amino-p-toluidine

<Thickener>
・ CPC: Carboxymethylcellulose

<Acid polymer>
PA: polyacrylic acid (polymerization degree 1000)

Example 1
Mix 20 parts by weight of PM, 80 parts by weight of UDMA, 0.6 parts by weight of DEPT, 8 parts by weight of F-1 and 5 parts by weight of F-2, and stir until uniform to prepare the first component did. 50 parts by mass of D-2.6E, 50 parts by mass of UDMA, 1.4 parts by mass of PBTEOA, 7.0 parts by mass of BPO, 100 parts by mass of F-1, and 60 parts by mass of F-2 were mixed. It knead | mixed until it became uniform and adjusted the 2nd component (Table 2).

  And when producing the adhesion sample of a 2cm square pure titanium flat plate and a 2cm square dental gold-silver-palladium alloy plate using the cement which consists of these 1st components and the 2nd component, two plates are joined. Until just before, the first component and the second component were substantially separated, and the first component and the second component were mixed at the time of joining.

  In addition, preparation of the adhesion sample was specifically performed in the following procedure. First, the surface of 2 cm square plate dental pure titanium (Morita Co., Ltd. dental pure titanium) and 2 cm square plate dental gold-silver-palladium alloy (GC cast well MC12) were coated with # 600 silicon carbide paper (Sankyo). After polishing with Riken (manufactured by Riken Corporation), dental alumina sandblasting was performed, and the remaining alumina particles were washed and left in an environment of temperature 37 ° C. and humidity 100%. Next, the first component was placed on the entire surface of one surface of a pure titanium flat plate and a dental gold-silver-palladium alloy plate, and then dried with compressed air for 10 seconds. Subsequently, 0.2 g of the second component is further deposited on the surface of the pure titanium flat plate on which the first component is arranged, and then bonded to the surface on which the first component of the dental gold-silver-palladium alloy plate is arranged. And pressed with a load of 200 g. In this state, an adhesive sample was obtained by leaving it in an environment of a temperature of 37 ° C. and a humidity of 100% for 10 minutes. At this time, the application amount of the first component to the bonding surface was sufficient to allow the excess first component to protrude from the bonding interface during bonding. The reason why the application amount of the second component is 0.2 g is also the same reason. The pure titanium flat plate imitates an abutment, and the dental gold-silver-palladium alloy plate imitates the upper structure.

(Examples 2 to 16)
In the same manner as in Example 1, the first component and the second component were prepared according to the composition table shown in Table 2, and an adhesive sample was prepared in the same manner as in Example 1.

(Comparative Examples 1-5)
Similarly to Example 1, a first component and a second component were prepared according to the composition table shown in Table 1. And when producing the adhesion sample of a 2cm square pure titanium flat plate and a 2cm square dental gold-silver-palladium alloy board using the cement which consists of these 1st components and 2nd components, the 1st component and 2nd The components were mixed in advance on kneaded paper, and the mixture was bonded by sandwiching it between two plates. In addition, an adhesive sample was produced in the same manner as in Example 1 under the other conditions. In addition, the usage-amount of the 1st component and the 2nd component which were used in the case of joining was made into sufficient quantity so that the mixture of an excess 1st component and a 2nd component may protrude from a bonding interface.

<Evaluation>
Table 2 shows the composition, viscosity, form, and presence / absence of mixing of the first component and the second component before joining in the preparation of the adhesive samples of the examples and comparative examples in Table 2. Show. Table 3 shows the results of evaluating the adhesive strength of the adhesive samples of each of the examples and the comparative examples, the removability of excess cement generated when the adhesive samples were produced, and the excess cement removal rate.

  As shown in Table 3, in Examples 1 to 16, adhesive strength suitable for temporary attachment was obtained, whereas in Comparative Examples 1 to 3, adhesive strength suitable for fusion was obtained. Moreover, in Examples 1-16, although an excess component did not harden | cure for a long time after joining, removal is easy, but in Comparative Examples 1-5, the excess component hardened early and it became difficult to remove.

  In addition, the measuring method of viscosity shown in Table 3, and the evaluation method and evaluation criteria of adhesive strength, excess cement removal property and excess cement removal rate shown in Table 3 are as follows.

<Viscosity measurement>
A 0.1 g sample prepared on a viscosity measuring apparatus (CS rheometer CVO120HR manufactured by BOHLIN) was placed, and the viscosity measurement was started while maintaining at 23 ° C. The viscosity 60 seconds after the start of the measurement was taken as the viscosity of the sample. The measurement conditions of the viscosity measuring apparatus were a cone diameter of 2 cm, a cone inclination angle of 1 °, and a shore rate of 10 s- ¹ .

<Adhesive strength>
Apply an instantaneous adhesive (Toagosei Co., Ltd., Aron Alpha, Jelly) on the outer surface of the dental gold-silver-palladium alloy plate that constitutes the adhesion sample, and press the stainless steel attachment (adhesion test piece) with a diameter of 8 mm from above. A sample for adhesion test evaluation was prepared. Next, after this sample for adhesion test evaluation was allowed to stand for 24 hours in an environment of 37 ° C. and 100% humidity, adhesion was performed at a crosshead speed of 2 mm / min using a tensile tester (manufactured by Shimadzu Corporation). The adhesive strength of the sample was measured. In addition, about 4 test pieces per test, the tensile strength was measured by the said method and the average value was evaluated as adhesive strength.

<Removability of excess components>
At the time of preparation of the adhesive sample, the surplus component that protrudes from the joint interface between the dental pure titanium plate and the dental gold-silver-palladium alloy plate is allowed to stand in an environment of a temperature of 37 ° C. and a humidity of 100%, immediately after joining (0 minutes). During the period from the first to the tenth minute, the removal of the excess component was evaluated by scratching the excess component with a probe every minute. The evaluation criteria are as follows.
○: The surplus component is not hardened, and the surplus component can be easily removed from the portion scratched by the probe.
Δ: Although the surplus component was slightly cured, the surplus component can be removed as a lump when scratched with a probe.
X: The surplus component is hardened, and the surplus component cannot be removed even when scratched with a probe.

<Excess component removal rate>
Separately from the dental pure titanium plate and dental gold-silver-palladium alloy plate used for bonding when preparing an adhesive sample, another dental gold-silver-palladium alloy plate is prepared, and this plate is used for bonding Arranged side by side with the alloy plate. At this time, the two dental gold-silver-palladium alloy plates were arranged so that the end faces face each other, and the gap between the end faces was set to 100 μm. By joining in this state, the surplus component that protruded from the joining interface flowed into the gap. The surplus component that flowed into the gap was left in an environment of temperature 37 ° C. and humidity 100% for 5 minutes after joining. Thereafter, the gap was sufficiently washed with a water gun, and the removal rate of excess cement remaining in the gap after washing was evaluated by visual observation with a magnifier. The evaluation criteria are as follows.
○: No surplus component remains in all the gap portions (length: 2 cm, width: 100 μm).
Δ: Some surplus component remains in a part of the gap (area ratio to the total area of the gap part is approximately 10% or less).
X: It is easily confirmed that surplus components remain in the gap (remaining at a ratio exceeding about 10% in terms of the area ratio to the total area of the gap).

<Quantitative analysis in the thickness direction of the adhesive layer using an electron beam microanalyzer>
About the cement used in Examples 1-11 and Comparative Examples 1-3, about the thickness direction of the contact bonding layer formed using this cement, the quantitative analysis by an electron beam microanalyzer (EPMA) was implemented in the following procedures. .

  First, after placing a Teflon (registered trademark) mold having a hole of 100 μm thickness and a diameter of 20 mm on one side of a flat polyester film of 3 cm in length and width, a first component is applied to the inside of the hole and compressed. It was dried with air for 10 seconds. Subsequently, after adding 0.2 g of the second component to one side of the other polyester film, the first component and the second component applied to the surface of each polyester film are in contact with each other and mixed. Two polyester films were pressed. And after press-contacting, it was left to stand in the environment of temperature 37 degreeC and humidity 100% until a junction part fully hardened | cured. Note that the amount of the first component applied to the bonding surface was sufficient to allow the excess first component to protrude from the bonding interface during bonding. The reason why the application amount of the second component is 0.2 g is also the same reason. In addition, about the cement of Comparative Examples 1-3, after mixing a 1st component and a 2nd component previously, the mixed composition which mixed these two components inside the hole is provided, Then, two polyester films are attached. Welded.

  Next, the hardened cement body (adhesive layer) formed between the two polyester films was taken out by manually peeling each polyester film. Then, 5.4 ml of an epoxy resin (EPON812RESIN) and 6.0 ml of a curing agent (EpoxyHardner MNA) are weighed and put into a resin composition obtained by stirring for 5 minutes with a spatula. Stir further. Thereafter, 8 drops of a polymerization catalyst (DMP-30) was added to the resin composition containing the hardened cement and stirred until it was uniformly mixed. Thereafter, the resin composition containing the hardened cement was filled with a spatula so as not to entrap large bubbles in the microtome mold and cured at a temperature of 60 ° C. for 2 days. In this way, a cured resin product in which a hardened cement body was embedded in the matrix was obtained.

  Next, a diamond knife is attached to the ultra microtome “MT-XL” (RMC), and the cross section of the cured resin produced by the above method is taken out, so that the cross section of the cured cement embedded in the cured resin is obtained. The exposure process was performed. In addition, although this cross-section was performed with respect to the resin hardened material which embedded the hardened cement body (adhesive layer) formed and taken out between the polyester films, the artificial prosthesis made of an abutment and a metal or ceramic member Even if it is a hardened cement body formed between these, this joined body can be cut directly by the above method, and the cross section of the adhesive layer can be similarly obtained.

  Subsequently, using a sputter coater (CC-40F, manufactured by Meiwa Forsys), carbon was vapor-deposited on the cross section of the hardened cement body to prepare an observation sample. About the observation sample, EPMA JAX-8800 (manufactured by JEOL Ltd.) is used, and the qualitative multipoint (5 points) analysis is performed with respect to the thickness direction of the adhesive layer so as to cross the section of the hardened cement body by the WDS method. went. The measurement was performed at five points so as to be equidistant from the surface provided with the first component toward the surface provided with the second component, and the phosphorus element content at each point was determined. The results are shown in Table 4. In Table 4, “Measurement point 1” means the measurement point closest to the surface to which the first component is applied, and as the number of measurement points increases, the measurement point is changed to the surface to which the second component is applied. It means approaching. Of the five measurement points, the measurement point with the highest phosphorus element content was taken as 100%.

Claims (5)

Consists of a first component and a second component used to bond the abutment constituting the dental implant and the superstructure,
The first component and the second component have a function of curing by mixing,
Adhesion between the abutment and the superstructure is
Applying the first component to at least one joining surface selected from the joining surface of the abutment and the joining surface of the upper structure; and
The second component is applied to at least one joint surface selected from the joint surface of the abutment and the joint surface of the upper structure,
After the application of the first component and the second component to these joint surfaces, the first component and the second component are joined by joining the joint surface of the abutment and the joint surface of the upper structure. Cement for dental implants, characterized in that it is carried out through at least a process of mixing the components and curing the mixture. Consists of a first component and a second component used to bond the abutment constituting the dental implant and the superstructure,
The first component and the second component have a function of curing by mixing,
After adhering the abutment and the upper structure, the thickness direction of the adhesive layer formed by the adhesion between the joint surface of the abutment and the joint surface of the upper structure, At least one component selected from the unreacted component of the first component, the unreacted component of the second component, and the reacted component of the first component and the second component has a concentration gradient. The dental implant cement according to claim 1.   The dental implant cement according to claim 1 or 2, wherein one of the first component and the second component is a liquid component, and the other component is a paste-like component.   The viscosity at 23 ° C. of one of the first component and the second component is 0.1 to 10 Pa · s, and the viscosity at 23 ° C. of the other component is 10 to 100 Pa · s. The cement for dental implants according to any one of claims 1 to 3. Consists of a first component and a second component used to bond the abutment constituting the dental implant and the superstructure,
The first component and the second component have a function of curing by mixing,
The viscosity at 23 ° C. of any one of the first component and the second component is 0.1 to 10 Pa · s, and the viscosity at 23 ° C. of the other component is 10 to 100 Pa · s. Cement for dental implants.