JPS58120782A - Activating method for surface of dental alloy - Google Patents

Abstract

PURPOSE:To provide high adhesion to dental resin materials and stable durability of adhesion by activatng the surfaces of cleaned dental alloys with liquid contg. organo functional silanes and/or partial hydrolyzates thereof. CONSTITUTION:After the surfaces of dental alloys are cleaned, the surfaces are coated with liquid contg. at least 1 kind organo functional silanes having the general formula or their partial hydrolyzates (in the formula, R; an alkyl group having 1-4C, R'; bifunctional hydrocarbon having 1-12C or group-CH2CH2CH2 NHCH2CH2-, X; -NH2, -SH, -OH or -Cl groups, (a); 2-3, (b); 0-1 and a+b=3). The above-mentioned cleaning is accomplished preferably by mechanical or chemical means. The above-mentioned organo functional silanes are used as they are or used in the form of an aq. soln. by hydrolyzing part or the whole of alkoxy groups.

Description

Detailed Description of the Invention The present invention provides a surface activation treatment method for dental alloys such as dental base metal alloys represented by Co-Cr alloys and N+-Cr alloys, dental silver and copper alloys, and dental gold alloys. In particular, these dental metals are subjected to mechanical treatment or chemical treatment, mechanical treatment, and further 'fRe conversion treatment by chemical treatment, etc., and then the general formula (RO) asiR'X is grown at least one kind. organofunctional silanes and/or partial hydrolysates thereof (wherein R is an alkyl group having 1 to 4 carbon atoms, R is a difunctional hydrocarbon having 1 to 12 carbon atoms) or the group -CH2CH2C
H2NHCH2CH2-1X is -NH.

-3H, -OH or -CZ group, a has a value of 2 or 3, b has a value of 0 or 1, a + b = 3)
This relates to a method for activating the surface of a dental alloy for resin bonding, which is characterized by coating the metal surface with a liquid containing: The purpose is to provide an excellent dental metal base. In recent years, in the field of prosthodontics, with the rapid development of dental equipment, dentists' and patients' perceptions of dental prostheses are also changing. Particularly in recent years, there has been an increasing demand for prosthetics not only for their functionality but also for their aesthetics, and there is a demand for natural-looking colors. Conventionally, prosthetics were made to be durable and less likely to break.
/), were often made of metal with excellent material properties such as good compatibility and excellent support, but for these reasons, the use of resin has recently become essential. The current situation is that the frequency of its use is increasing.

When metal and resin are used simultaneously as prosthetics in dental prosthodontics, metal floors and floor resins, hard resin crowns, and various metal restorations such as inlays and crowns and resin cements for bonding are used. Numerous cases have been considered, and research into the adhesion between various dental metals and resins continues day and night.

In other words, as a method of bonding and fixing various dental metals and resins, special consideration must be taken for mechanical heel retention devices, such as attaching a nine-bar skeleton, a rope-like structure, retention beads, etc. Although there have been many attempts to develop adhesive materials and adhesive methods for dental metals, none have been found to be durable enough to withstand the harsh conditions of use in the oral cavity. In other words, problems with mechanical retaining devices include the fact that the retaining part protrudes from the metal surface, so it cannot be applied to the metal edges, and the thickness of the resin part decreases, impairing aesthetics. On the other hand, after the device, due to the difference in thermal expansion coefficient between metal and resin, which corresponds to temperature changes caused by ingestion of food and drink in the oral cavity,
It is highly conceivable that peeling will occur at the interface between the two, and that dirt, plaque, etc. will enter the gap, resulting in a site of severe contamination and even chronic inflammation of the marginal gingiva.

In addition, regarding adhesive materials and bonding methods, there were 8 issues of compatibility of the interface between the adhesive material and the metal surface, lack of water resistance, and no effective treatment method for various dental metals was developed.
On the other hand, such a prosthesis is in a special situation where it is constantly moistened by saliva etc. in the oral cavity, and the temperature difference caused by ingestion of food and drink causes internal stress at the adhesive interface, and it is difficult to maintain stable durability over a long period of time. I didn't need it. In order to eliminate these problems, the inventors of the present invention have conducted various studies and found that base metal alloys for @ materials such as Co-Cr alloys and Ni-Cr alloys, dental silver and copper alloys, and dental gold alloys have been developed. After mechanical treatment or chemical treatment and further chemical treatment after mechanical treatment, the general formula (RO
) at least 1M organofunctional silanes having asiR'
an alkyl group having q carbon atoms, R' is 1 to 12
difunctional hydrocarbon or group -CH having 4 carbon atoms
2CH2CH2NHCH2CH2-, X is -NH2, -
5H, -OH or C) group, a has a value of 2 or 3, b has a value of 0 or 1, and the metal surface is coated with a mixture of a + b = 3) for dental use. The present invention was completed by discovering that when a dental resin is applied to the activated surface of metal, it exhibits excellent adhesion and is also highly adhesive and durable. The present invention is a Co-Cr alloy, N
It is applied to the surfaces of dental base metal alloys such as i-Cr alloys, dental silver and copper alloys, dental gold alloys, etc. Mechanical treatments include puff polishing, sandblasting, etc. Treatments include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid,
Typical examples include immersion treatment in various alkaline solutions and aqueous solutions, and electrolytic treatment. By performing this treatment, contaminants such as dirt and oil on the dental metal surface that can hinder adhesion are removed, and many fine irregularities are created on the surface, increasing the effective bonding area by 10 to 100 times or more. This is because a suitable anchoring effect can be obtained, and because a highly active surface is exposed, chemical affinity is increased and wetting to the resin is improved.

General formula (RO) applied after the above surface treatment Old R'
At least 1M organofunctional silanes having X and/or partial hydrolysates thereof, where the formula
an alkyl group having 1 to 12 carbon atoms;
difunctional hydrocarbon or group -CH having 4 carbon atoms
2CR2CH2NHCH2CHll-1X is -NH2,
-SH.

-OH or Cl group, a has a value of 2 or 3, b has a value of 0 or 1, a+b=3) is (CH30)
3 St (CH2)3 NH(CH2) NH, (C
)(,0)3st (CH2)3SH,(CH30)3
st (CH2)3o,, (C city 0)3 St (CJ
(2) 30H, (CH=CH20)3Si CH=CH
It is an organo-functional silane such as No. 2, and its usage is by treating the organo-functional silane as it is or with water to hydrolyze all or part of the alkoxy groups on the molecule and using it in an aqueous solution state, or by using it in an aqueous solution state by treating it with water and hydrolyzing all or part of the alkoxy groups on the molecule. , ethanol, iribrovir alcohol, etc., but preferably the total silane in the mixture is 0.01 digits.
30% by weight is desirable.

The most suitable treatment method is mechanical treatment or chemical treatment, and methods such as dipping, spreading, brush painting, and spraying on the dental metal surface that has been subjected to mechanical treatment and further chemical treatment.

Although organofunctional silanes have been known for many years to be inorganically and organically reactive and useful for improving adhesion between organic and inorganic phases in composites, certain arbitrary silanes It has been criticized that it is not a universal coupling agent that can bond any material to any substrate, and that it is not safe to use in vivo with a physically and chemically stable substrate such as dental metal. When applied to dental resin materials that are limited in terms of The sum
Kusumi was very good.

The present invention will be explained below by giving a number of actual examples.

Example 1 Dental Ni-C produced by casting using a high-frequency centrifugal casting machine
An r-alloy plate (trade name: Narachrome, Regular Tori Giken) IOXIOX 3 mm was subjected to surface conditioning and sandblasting treatment, ultrasonic cleaning and drying, and treatment with an organofunctional silane-containing liquid and drying. The processing conditions are as follows.

The surface to be adhered to the surface adjustment valve was polished to a uniform finish with 1000 grit emery paper.

Sandblasting abrasive grain 50 bare alumina treatment method Paasche Ajrbrush FJA
EC-K Air Eraser loading '1 = JEfE power 3
Distance between KV and nozzle specimen 2 Projection angle of steel abrasive grains 90° Organo-functional silane-containing liquid treatment treatment liquid C1 (2=CH5i (OCH2CH3)3
10 g Distilled water 90 g PH 4.0 (adjusted with acetic acid) Treatment method Brush coating Example 2 The same conditions as in Example 1 were used except that the sandblasting treatment was replaced with a dipping treatment.

Immersion treatment treatment solution Nitric acid 5Q d Distilled water 100ml Treatment method 80~90'C Immersion 30 minutes actual 2f
T! i Example 3 Dental Ni-C cast using a high-frequency centrifugal casting machine
r alloy plate (product name: Narachrome. Regular Towa Giken) IOX 20X3 Surface conditioning and sandblasting were performed briefly, followed by ultrasonic cleaning followed by immersion treatment and drying, then treatment with organofunctional silane-containing liquid and drying. Ta. Surface conditioning, sandblasting, dipping, and organofunctional silane solution treatment were performed under the same conditions as in Examples 1 and 2, respectively.

Further, as a control, the same dental Ni-Cr alloy plate was prepared, and the one in which only surface conditioning was performed was referred to as Control Example 1, and the one in which surface conditioning was performed and only sandblasting was performed was Control Example 2.
, Comparative example 3 is the one that was subjected to surface conditioning and only immersion treatment.
Comparative Example 4 was prepared by surface conditioning, sandblasting, and dipping treatment, and Control Example 5 was prepared by performing surface m1f- treatment and organofunctional silane-containing liquid treatment.

A hard resin for dental crowns (trade name: Dental Fine Sil, Towa Giken) was applied to the Ni-Cr plywood for @materials prepared according to Examples 1 to 3 and Comparative Examples 1 to 5 of the present invention in accordance with the law. ,,4 (71+± Polymerization under pressure for 15 minutes, opaque thickness 0.4 0.
Table 1 shows the results of measuring the diameter and adhesive strength of test pieces of 2.0-㎜ and 2 mff thick rope dentisi+.

Test method 1) 80°C underwater immersion test The specimens were immersed in 80°C water for 10 minutes.

2) Heat cycling test The samples were subjected to heat cycles up to 300 times by alternately immersing them in water for 1 minute each.

3) Measurement of ff adhesion force Measurement of adhesion force was carried out using an Autograph (IS-2000 Shimadzu Corporation) at a crosshead speed of 2.5 kg/m. Results of 6 tests Table 1 Example 4 Using a high-frequency centrifugal casting machine Dental gold alloy made by casting using
Product name Metaselen Gold 4 Towa Giken) 10X10
X3+++m was subjected to surface conditioning and sandblasting treatment, ultrasonic cleaning diameter drying, organofunctional silane-containing liquid treatment, and drying.

The processing conditions are as follows.

Surface Preparation # The surface to be adhered was polished with emery paper of up to 1000 to give a uniform finish.

Sandblasting abrasive grain 25 Lua Alumina treatment method Paasche Airbrush company mA
EC-K Air Eraser injection pressure 3 to 9 bubbles Distance between nozzle specimens 2 cm Abrasive grain projection angle 90' Organofunctional silane-containing liquid treatment treatment liquid CH2=CH5i (OCH2C, H3)3
0.5gH5CH2CH2CH2Si (
OC! Hs)3 (1+)gNH2
CH2CH2CH2Sj (OCH2CH3)3
0.5g ethanol 98.5g Processing method Brush painting example 5 Dental gold alloy produced by WJa using a high frequency centrifugal casting machine (trade name Metaselen Gold 4. Towa Giken) IOX
The IOX 3+o+ was surface conditioned and sandblasted, ultrasonically cleaned, electrolytically treated and dried, and then treated with an organofunctional silane-containing liquid and dried.

Surface conditioning, sandblasting, and organofunctional silane-containing liquid treatment were performed under the same conditions as in Example 4 for the back piece.

Electrolytic treatment solution Hydrochloric acid (1,19) 15g Sodium chloride 25g Distilled water 60g Treatment method Platinum cathode 3V AC for 1 minute Furthermore, as a control, the same dental gold alloy plate was prepared, and one with only surface conditioning was used as N control example 6 Comparative Example 7 is a sample in which surface conditioning was performed and only sandblasting was carried out; Control Example 8 was a sample in which surface conditioning was carried out and further electrolytic treatment was carried out after sandblasting; This was designated as Control Example 9.

Dental gold alloy plates prepared according to Kienro's Examples 4 to 5 and Control Examples 6 to 9 had a thickness of 404 mm and had 5 holes in diameter.
UA zk bath-resistant film was attached, dental adhesive material (trade name: Orthomite US Ttden Pharmaceutical) was applied to it according to the legal method, and an acrylic goblet was glued on top of it using the butt-butt method, and the adhesive strength was measured. 1 9 35
2? '10 20 Procedural Amendment (Voluntary) March 11, 1980 Commissioner of the Japan Patent Office '9 Shima 1) Haruki Tono1, Indication of Case Patent Application No. 003491, 19882
, Name of the invention S Activation treatment method for dental alloy surfaces 3, Relationship with the case of the person making the amendment Patent applicant address 6-1-38 Nishiawaji, Higashiyodoyo-ku, Ohkori City Name Towa Giken Co., Ltd. Taka Hashi Toshugyu Representative Director and President Toshiyuki Takahashi 4, Agent Address: 50 Sumiyoshi-cho, Shinjuku-ku, Tokyo "Scope of Claims, Paragraphs 1 J and 1, Part 1 of the Claims of the Patent in the Specification" Correct the first term as follows.

1. After cleaning the dental alloy surface, the surface is cleaned with at least one organofunctional silane having the general formula (RO) aSiRX and a partial hydrolyzate of bamboo shoots (wherein the formula R is an alkyl group having 1 to 4 FA atoms, R" is a difunctional carbonized 7kH polymer having 1 to 12 carbon atoms;
M CfhCH2CFhNHCHsCHx -, X
A method for activating the surface of a dental alloy for resin bonding, characterized in that the surface of a dental alloy for resin bonding is coated with a solution containing a and b"3), which is developed to a value of 4t-NHZ or 1.

Toru no r (RO) aSiR'XJ
Le.

b 3, Beams in the specification, page 2, line 14 and page 5, line 15 “・
The phrase ``1 group, α is'' is corrected to ``...the group a is''.

4. On page 4, line 7 of the specification, the phrase ``・eye・endurable river・'' is corrected to ``...-endurable...''.

5. In the specification, page 6, line 8, ``...alkaline solution/use'' should be corrected to ``...alkali solution...J.''

6. Page 7, line 4 of the B item specification [change t...a to 2 or...j to ``...a to 2 or...
” he corrected.

7. In the specification, on page 7, line 11, "...isopropyl alcohol..." is corrected to "...isopropyl alcohol...".

8. Mei #8, page 11, line 12, ``...It turned out. The results are shown in Table 1. is circular and its diameter is 5
, 0, and its area is approximately 20 mTrL2. The results are shown in Table 1. ” he corrected.

9. In the specification, page 11, line 15, "...in 80'C water for 1o..." replaces "...in 80°C water for 1o..."
8 minutes...'' and corrected it.

10. In the specification, page 15, line 8, ``...'s PUA...-
"..." is corrected to "PVA of...".

that's all

Claims (1)

[Claims] 1. p,,'+ After surface cleaning treatment of the white alloy,
The surface is covered with an organofunctional silane of the general formula (RO) asiR'X and or a partial hydrolyzate thereof (wherein R is 1 to 4
an alkyl group having 1 to 12 carbon atoms;
Difunctional hydrocarbon or group -CH containing carbon atoms
2CH2CH2NHCH2CH2. X bar NHw SH-OH ma1c + knee C4 group,
a:i2ma1cc30) What is the value, b has a value of 0 or 1, and a+b=3) Resin bonding method characterized by coating with a liquid containing 2. A method for activating an alloy surface for resin bonding according to claim 1, item t, in which the cleaning treatment is performed by mechanical means. 3. A patent in which the cleaning treatment is performed by chemical means. 41. A method for activating a dental alloy surface for resin bonding according to claim 1. 41. A method for activating a dental alloy surface for resin bonding according to claim 1, wherein the cleaning treatment is performed by a combination of mechanical treatment and chemical means. Activation treatment method for dental alloy surfaces.