JPH0469313A - Primer for bonding ceramic tooth - Google Patents

Abstract

PURPOSE:To obtain an adhesive primer suitable for the bonding of a dental restoration material and a ceramic tooth by reacting a silane compound having >=3 alkoxy groups with a silane compound having ethylenic unsaturated group, and using the obtained siloxane polymer as a component. CONSTITUTION:The objective primer for the bonding of a ceramic tooth contains a siloxane polymer produced by reacting a silane compound having >=3 alkoxy groups and expressed by formula I (R1 to R3 are 1-5C alkyl; X is H, 1-5C alkyl, 1-5C alkoxy or chloromethyl) with a silane compound having an ethylenic unsaturated group and expressed by formula II [Z is CH2=CH or CH2=C(CH3); R4 to R7 are 1-5C alkyl]. The primer can be used as a one-pack type agent storable stably over a long period and exhibits remarkable bonding performance immediately after application when used as a primer for ceramic tooth.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an adhesive primer for porcelain teeth, and more particularly to an adhesive primer suitable for bonding porcelain teeth with dental restorative materials such as composite lenone. Regarding.

(Prior Art) Conventionally, as an adhesive primer for porcelain teeth, for example, T-
Primers containing as a main component a coupling agent having a (meth)acryloyl group such as methacrylquinopropyl trimetoquinolane are widely used. However, with these existing NRANKANOPRING agents, if they are mixed with a catalyst in advance to form a one-component solution, the activity over time during storage will be significantly reduced. It was necessary to use it. Moreover, it also has drawbacks such as the fact that it takes more than 20 minutes after mixing the silane coupling agent and the catalyst in order for the silane coupling agent to develop sufficient silanol groups to exhibit adhesive performance as a porcelain tooth brimer. have.

(Problems to be Solved by the Invention) The present inventors have completed the present invention as a result of intensive research to solve the above-mentioned problems of existing porcelain tooth bonding brimers. The reason is that it can be used in a one-component type that can be stored stably for a long period of time.
Further, other objects and effects of the present invention will become clear from the following description, which is to provide an adhesive brimer for porcelain teeth which has excellent adhesive performance immediately after application.

(Means for Solving the Problem) The above object is to provide a silane compound having at least three or more alkoxy groups represented by the following formula (1) and the following formula (2).
This is achieved by an adhesive brimer for porcelain teeth characterized by containing a siloxane polymer obtained by reacting with a silane compound having an ethylenically unsaturated group shown in the following.

O (R4),.

Input i -0R6 97 (2) Examples of the compound represented by formula (1) applied to the present invention include 5i(OCzHs)n, 5i(OCRs)a,
H5i (OCRs)z or CCH25z (OCH
i)i, etc., but from the viewpoint of biological safety in the oral cavity, 5i(OCJ, )-5i(OC)li)4 or H5i(OCJ)s is preferred.

Further, as an example of the compound represented by the formula (2), C)+3C)lz=c Co(CHz)lISi(OCLL
.

CHz=CHC-0(CHz), 5i(OCHz)s(
n: I~5) and the like.

The adhesive brimer for porcelain teeth of the present invention has many silanol groups in its molecules, and due to the specific steric hindrance caused by the rigid ladder structure of the molecules, the silanol groups in the molecule are not condensed and are stable for a long period of time. It is.

From the viewpoint of long-term stability, the brimer of the present invention has a constituent molar ratio of the silane compounds represented by the above formulas (1) and (2),
That is, silane compound represented by formula (1): silane compound represented by formula (2) = preferably 0.67 to 99 = (1) 7-rane compound represented by (2): formula (2) When the furan compound shown in is set to 1 to 10, more preferable results can be obtained from the viewpoint of binding to composites and torezin. The noloxane polymer according to the present invention has the formula (1)
It can be easily produced by heating the silane compound represented by formula (2) in an aqueous medium in the presence of a catalyst.

Various types of aqueous media can be used, but a combination system of water and alcohol is preferred. As the alcohol, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, etc. are suitable, but ethyl alcohol is most suitable since it is used in the oral cavity. In these aqueous media, the molar ratio of water to the total amount of the silane compound is preferably 0.5 to 4.0, particularly preferably 1 to 2.
Prepare so that If the amount of water is too small, the reactivity will decrease, making it difficult to generate silanol groups, resulting in poor adhesion to porcelain teeth.On the other hand, if the amount is too large, excessive crosslinking will occur, resulting in gelation, which will cause problems during storage. Stability tends to decrease. When the molar ratio of water to the total amount of silane compounds is 0.5 and alcohol and water are used as the aqueous medium, the ratio of alcohol and water is adjusted to alcohol/water = 2 to 4 by weight. Favorable results are obtained. If the amount of alcohol is too small, the reaction solution tends to become non-uniform, while if it is too large, the reactivity tends to decrease.

Suitable reaction catalysts include acids such as sulfuric acid, phosphoric acid, p-)luenesulfonic acid, and maleic acid, basic compounds such as triethanolamine, and organometallic compounds such as dibutyltin laurate and cobalt naphthenate. In this case, it is preferable to heat to around 80°C.

When using the reaction product produced in this form, it is suitable to dilute the reaction solution with alcohol in order to improve the applicability.
It is preferable to use it after diluting it twice.

The present invention will be specifically explained below with reference to Examples.

In addition, the adhesion test in Examples was conducted by the following method.

(Adhesion test method) Dental porcelain "Obtenocll5P System" (manufactured by Generic/Pentron, USA) was 8 mm in diameter x 3 in height.
It was fired into a mm-thick disk and embedded in an acrylic resin square rod.

After that, it was polished with #600 SiC abrasive paper, and then etched with [Belfeel 7 etching material] for about 20 seconds. An adhesive tape with a hole of 5 mm in diameter was pasted on the treated surface. After that, a primer was applied to the open porcelain surface and a light blow of air was applied.

Next, prepare the other acrylic resin square rod, apply the bonding material "Helfeel Bonding Material (for chemical polymerization)" manufactured by Kanebo Co., Ltd. to the acrylic square rod, and then apply the bonding material "Helfeel Ateria" manufactured by Kanebo Co., Ltd. The kneaded paste was raised and pressed against the primer-coated porcelain surface for butt adhesion. One hour after butt adhesion, it was immersed in water at 37°C, and about 24 hours later, the bow-stripe adhesive strength was measured using a universal testing machine (manufactured by Instron).

Example 1 Tetranidoxinlan (manufactured by Shin-Etsu Chemical Co., Ltd.) 53 g,
3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 g, ethanol 27 g, o,
Put 9g of t 5mo 1/l hydrochloric acid aqueous solution into a flask,
The mixture was refluxed at 80° C. for 15 hours to perform a polycondensation reaction.

This reaction solution was diluted 3 times with ethanol and used as a primer for bonding porcelain teeth, and the adhesive strength between porcelain teeth and composite resin was evaluated.

As a result, the average adhesive strength of the 10 samples was 210 kg/
cm'', the fracture condition was only cohesive failure of the porcelain or composite resin, and there was no interfacial peeling between the porcelain and the composite resin.

Comparative Example 1 An adhesion test between a porcelain tooth and a composite resin was conducted without using the primer prepared in Example. As a result, the average adhesive strength of the 10 samples was 60 kg/cm'', and all of them peeled off at the porcelain-composite resin interface.

Examples 2 to 5 Tetramethquine 25F50 (manufactured by Co., Ltd.) 10g. 25g of X-ri/-le and 0. 1 m o
Pour 1 og of a 1/1 triethanolamine aqueous solution into a flask and reflux at 80°C for the prescribed time listed in Table 1 below. This reaction solution was diluted 4 times with ethanol and used as an adhesive primer. Adhesion between the porcelain, the composite, and the resin was evaluated in the same manner as in Example 1.

The results are shown in Table 1.

From the table above in Table 1, when the reflux time was 10-15 hours, the adhesive strength was as high as approximately 200 kg/cm, but when the reflux time was 5 or 20 hours, the adhesive strength decreased slightly. Recognize.

Examples 6 to 8 50 g of tetramethoxysilane, 10 g of 3-methacryloxypropyltrimethoxysilane, 25 g of ethanol, and a 0.12 m o 1/1 aqueous sulfuric acid solution were placed in a flask in the predetermined amounts listed in Table 2, and heated to 80°C. The mixture was refluxed for 13 hours, and this reaction solution was diluted 3 times with ethanol, used as an adhesive primer, and evaluated for adhesion between porcelain and composite resin in the same manner as in Example 1. From the results in Table 2, the molar ratio of water/silane compound is 0.
When it was smaller than 5, the adhesive force became slightly low. Furthermore, it can be seen that when the molar ratio is 4.0 or more, the adhesive strength is high, but the stability during storage is somewhat poor.

Examples 9 to 1O Tests were carried out in the same manner as in Example 1 except that chloromethyltrimethoxysilane or trimethoxysilane was used in place of the tetraethoxysilane in Example 1. The results are shown in Table 3.

Table 3: Tetraethquinsolan. 3-Methacryloquinopropyltrimethoquinolane was added to a predetermined molar ratio (listed in Table 4), 27 g of ethanol, 5 mol/1 hydrochloride acid aqueous solution, 8 liquids, and 9 flasks, and the mixture was heated at 80°C for 15 hours. The mixture was refluxed to perform a polycondensation reaction.

This reaction solution was diluted 3 times with ethanol and used as a primer for bonding porcelain teeth, and the adhesive strength between porcelain teeth, composite, and Trenone was evaluated.

The adhesion test was carried out immediately after the primer was prepared and held at 37°C.High adhesion was obtained with chloromethyltrimethoxysilane and trimethoxysilane as well as with trimethoxysilane.

Examples 11-15

Claims (1)

[Claims] A product obtained by reacting a silane compound having at least three alkoxy groups represented by the following formula (1) with a silane compound having an ethylenically unsaturated group represented by the following formula (2). An adhesive primer for porcelain teeth characterized by containing a siloxane polymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) [However, R_1, R_2 and R_3 are alkyl groups with 1 to 5 carbon atoms, X is hydrogen, alkyl groups with 1 to 5 carbon atoms, carbon Represents 1 to 5 alkoxy groups or chloromethyl groups. ]▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(
2) [However, Z is CH_2=CH-, or ▲There is a mathematical formula, chemical formula, table, etc.▼ group, R_4, R_5
, R_6 and R_7 represent an alkyl group having 1 to 5 carbon atoms. ]