JPH101409A - Metal surface-treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject surface-treating agent containing a radical- polymerizable unsaturated bond-containing thiouracil derivative as a main component, excellent in storage stability, adhesive strength to noble metals, water resistance, durability, etc., and useful in a dental field, etc. SOLUTION: This metal surface-treating agent comprises a thiouracil derivative containing at least one radical-polymerizable unsaturated bond preferably expressed by formula I or II (R<1> , R<2> are each H, an alkyl wherein at least one of R<1> and R<2> is H; R<3> is H, an alkyl, phenyl; R<4> is a 1-20C divalent organic residue; Z is an organic group having a radical-polymerizable unsaturated bond) in the molecule, and an organic solvent, especially preferably toluene, acetone, etc. The further addition of an acidic group-containing (meth)acrylic monomer to the metal surface-treating agent enables to give high adhesion even to base metals. Thereby, the metal surface-treating agent can be utilized in many fields, such as medical treatments, electronic materials, precision machines, accessories and ornaments, for bonding resins to metals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a metal surface treating agent useful for developing excellent adhesion to metals. INDUSTRIAL APPLICABILITY The present invention can be used in many fields such as medical treatment for bonding a resin to a metal, electronic materials, precision machinery and jewelry, but is particularly useful in the dental field.

[0002]

2. Description of the Related Art As an adhesive for base metals such as iron, nickel, chromium, cobalt, tin, aluminum, copper, and titanium, various functional groups such as a phthalic anhydride group, a phthalic acid group, a malonic acid group and a phosphate group are used. An adhesive containing an acrylic or methacrylic polymerizable monomer having the following formula has been proposed and put to practical use. However, an adhesive having a sufficient adhesive strength to noble metals such as gold, platinum, palladium, and silver has not been developed. Therefore, in order to adhere to the noble metal, the surface of the noble metal has generally been tin-plated or oxidized in advance. These methods are complicated in operation and do not provide a sufficient adhesive force. Therefore, development of an adhesive for a noble metal or a surface treatment agent for a noble metal has been desired.

In response to the above demands, thiophosphate groups (JP-A-1-138282), thiophosphate chloride groups (JP-A-5-117595) and triazinedithione derivatives (JP-A-64-83254) have recently been proposed. Adhesive polymerizable monomers having such functional groups have been proposed. These surface treatment agents containing an adhesive polymerizable monomer are applied to a noble metal surface in advance, and then the polymerizable resin is cured to enable adhesion to the noble metal.

[0004]

However, in the bonding of precious metals using the above-mentioned surface treating agents, the adhesive strength, water resistance and durability are not yet sufficient, and the adhesive polymerizable monomer is unstable. There are problems such as poor storage stability of the surface treatment agent, and the adhesive strength is affected by the amount of application. Further, the effect of the surface treatment agent is exhibited only in the adhesion of a noble metal, and is not exhibited in the adhesion of a base metal. Therefore, an object of the present invention is to provide a metal surface treating agent having a sufficient initial adhesive strength to both base metals and precious metals, and having good adhesion durability, water resistance and storage stability.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, it has been found that a surface treating agent containing a thiouracil derivative having a radical polymerizable unsaturated bond as a main component has storage stability and adhesive strength to precious metals. And a surface treatment agent containing a thiouracil derivative having a radically polymerizable unsaturated bond and an acidic group-containing (meth) acrylate monomer, which is either a base metal or a noble metal. Have sufficient adhesive strength and excellent storage stability, water resistance and durability, and have completed the present invention.

That is, the present invention provides a metal surface treating agent containing a thiouracil derivative containing at least one radically polymerizable unsaturated bond in a molecule and an organic solvent, and a radically polymerizable unsaturated bond in a molecule. A metal surface treatment agent comprising at least one thiouracil derivative, an acidic group-containing (meth) acrylate monomer and an organic solvent.

The thiouracil derivative is not particularly limited as long as it contains a thiouracil group and at least one radically polymerizable unsaturated bond in the molecule, but preferably has the following general formula (1) or (2): The thiouracil derivative represented by is used.

[0008]

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Wherein R ¹ and R ² are each a hydrogen atom or an alkyl group, at least one of R ¹ and R ² is a hydrogen atom, and R ³ is a hydrogen atom, an alkyl group or a phenyl group; R ⁴ is a divalent organic residue having 1 to 20 carbon atoms, and Z is an organic group having a radical polymerizable unsaturated bond.) In the above general formulas (1) and (2), R ¹ and R 2 ² represents a hydrogen atom or an alkyl group, and at least one of R ¹ and R ² is a hydrogen atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

In the general formulas (1) and (2), R ³ represents a hydrogen atom, an alkyl group or a phenyl group. Examples of the alkyl group include the same as those described above for R ¹ and R ² .

Further, in the above general formulas (1) and (2), R ⁴ is not limited as long as it is a divalent organic residue having 1 to 20 carbon atoms. Therefore, not only a divalent chain or branched hydrocarbon group such as an alkylene group, but also an organic group having an ether bond, an ester bond, a siloxane bond, or a phenylene group in the main chain is included.

Specific examples of the group R ⁴ include:

[0013]

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And the like.

In the general formulas (1) and (2), Z represents an organic group having a radical polymerizable unsaturated bond. Z is not particularly limited as long as it is an organic group having a radical polymerizable unsaturated bond, and specific examples include a methacryloyloxy group, an acryloyloxy group, a 4-vinylbenzyloxy group, a styryl group, an allyloxy group and an allyl group. Is done. Among them, a methacryloyloxy group and an acryloyloxy group are preferred in terms of polymerizability, ease of handling, and the like.

Representative thiouracil derivatives represented by the general formula (1) or (2) are represented by the following general formula (3) or (4).

[0017]

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Wherein R ⁵ and R ⁶ are each a hydrogen atom or an alkyl group; at least one of R ⁵ and R ⁶ is a hydrogen atom; R ⁷ is a hydrogen atom, an alkyl group or a phenyl group; R ⁸ is a divalent saturated hydrocarbon group having 2 to 12 carbon _{atoms, -CH 2 -C 6 H 4 -CH} 2 - or - (CH _{2) O} -
Si (CH ₃ ) ₂ OSi (CH ₃ ) _2- (CH ₂ ) _P- (where o and p are each independently an integer of 1 to 5)
In it, Y is, -COO -, - CH ₂ O- or -C ₆ H
₄ -CH ₂ is O-, R ⁹ is a hydrogen atom or a methyl group.チ オ Specific examples of the thiouracil derivative used in the present invention are as follows.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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The method for producing the thiouracil derivative represented by the general formulas (3) and (4) is not particularly limited, and any method may be employed. An example of an industrially suitable method is specifically described below.

First, a method for producing the thiouracil derivative represented by the general formula (3) will be described. That is, the following general formula (5)

[0030]

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Wherein R ⁵ and R ⁶ are each a hydrogen atom or an alkyl group, and at least one of R ⁵ and R ⁶ is a hydrogen atom. )

[0032]

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(Wherein R ⁷ is a hydrogen atom, an alkyl group or a phenyl group), and a malonic acid derivative represented by the following general formula (7):

[0034]

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(Wherein R ⁵ , R ⁶ and R ⁷ have the same meanings as defined in the above general formula) to obtain a carboethoxythiouracil derivative represented by the following general formula (8). )

[0036]

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(Wherein R ⁵ , R ⁶ and R ⁷ have the same meanings as defined in the above general formula), and a carboxythiouracil derivative represented by the following general formula (9) is obtained.

[0038]

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In the formula, R ⁸ represents a divalent saturated hydrocarbon group having 2 to 12 carbon atoms, —CH ₂ —C ₆ H ₄ —CH ₂ — or — (C
_{H 2) O -Si (CH 3} ) 2 OSi (CH 3) 2 - (CH 2) P
- (. However, o and p are each independently an integer of 1 to 5), and, Y is, -COO -, - CH ₂ O- or -C ₆ H ₄ -CH ₂ is O-, R ⁹ is a hydrogen atom or a methyl group. By reacting an alcohol having a polymerizable unsaturated bond represented by 前 記, a thiouracil derivative having a polymerizable unsaturated bond represented by the general formula (3) can be obtained.

As the thiourea derivative represented by the general formula (5), known compounds can be used without any limitation. For example, thiourea, methylthiourea, ethylthiourea, propylthiourea, butylthiourea and the like are preferably used.

The malonic acid derivative represented by the general formula (6) is synthesized by a reaction between diethyl malonate and triethyl orthoate.

Examples of the triethyl orthoate include triethyl orthoformate, triethyl orthoacetate, triethyl orthopropionate, and triethyl orthobenzoate. More specifically, the malonic acid derivative represented by the general formula (6) is prepared by charging 1 mol of diethyl malonate and 2 to 3 mol of sodium ethoxide in the presence of a solvent, and gradually dropping 1 mol of triethyl orthoate. It is obtained by reacting.

As the alcohol having a polymerizable unsaturated bond represented by the general formula (9), when Y is —COO—, an esterification reaction between (meth) acrylic acid and glycol, (meth) acrylic acid chloride And an esterification reaction of glycol. Y is in the case of -CH ₂ O-obtained by reaction of allyl chloride with a glycol. Also, 4 when Y is -C ₆ H ₄ -CH ₂ O- of
-It is obtained by reaction of vinylbenzyl chloride with glycol and the like.

As the glycol, ethylene glycol,
Propylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol,
Decamethylene glycol, dodecamethylene glycol,
Neopentyl glycol, 1,2-propanediol,
Examples thereof include 1,2-butanediol, 1,5-hexanediol, para-xylene glycol, 1,3-bis (hydroxypropyl) tetramethyldisiloxane, and the like.

More specifically, when Y is —COO— in the general formula (9), the corresponding alcohol (9) is
1 mole of (meth) acrylic acid, 1 mole of glycol
It is obtained by charging 4 moles and 0.01 to 0.1 moles of an acid catalyst and reacting them. As the acid catalyst, p-toluenesulfonic acid, benzenesulfonic acid and the like are preferably used.

Alternatively, 1 to 4 moles of glycol and 1 mole of tertiary amine or molecular sieve 3A as a dehydrohalogenating agent are charged in the presence of a solvent, and 1 mole of (meth) acrylic acid chloride is gradually added dropwise to carry out the esterification reaction. You can also get As the tertiary amine, pyridine, triethylamine and the like are preferably used.

In the general formula (9), Y is -CH ₂
In the case of O-, the corresponding alcohol (9) is prepared by charging 1 mol to 4 mol of glycol and 1 to 1.2 mol of the basic catalyst in the presence of a solvent, and gradually dropping 1 mol of allyl chloride to react. can get. Sodium hydride or the like is preferably used as the basic catalyst.

Further, in the general formula (9), Y is -C ₆
In the case of H ₄ —CH ₂ O—, the corresponding alcohol (9) is
It is obtained by charging 1 mol to 2 mol of a glycol and 1 to 1.2 mol of a basic catalyst in the presence of a solvent, and gradually dropping and reacting 1 mol of 4-vinylbenzyl chloride. Sodium hydride or the like is preferably used as the basic catalyst.

In these cases, the mono-substituted product (9) and the di-substituted product are obtained as products. The mono-substituted product (9) can be separated and purified by distillation or column chromatography.

In the condensation reaction between the thiourea derivative of the general formula (5) and the malonic acid derivative of the general formula (6), the reaction of the malonic acid derivative of the general formula (6) with the thiourea derivative of the general formula (5) The molar ratio is preferably from 0.5 to 1.5 mol.

As the reaction catalyst used at this time, known catalysts can be used, and examples thereof include sodium ethoxide and the like, and the amount of the catalyst added is 0.5 to 1. 1 based on the thiourea derivative of the general formula (5). Five-fold moles are preferred.

The solvent used in this reaction includes ethanol and the like. The reaction temperature can be selected from the range of 40 to 80 ° C, and is preferably in the range of 60 to 80 ° C. The reaction time is not particularly limited and can be generally selected from a range of about 1 to 10 hours, but may be determined in relation to the reaction temperature.

After the reaction, the precipitated salt is dissolved in water, and the solution is acidified by adding an acid to obtain a carboethoxythiouracil derivative represented by the general formula (7).

However, in the thiourea of the general formula (5), when either R ⁵ or R ⁶ is an alkyl group, the carboethoxythiouracil derivative of the general formula (7) is substituted on the N atom of the alkyl group. As a mixture of isomers. These can be separated and purified by column chromatography.

In the deesterification reaction of the carboethoxythiouracil derivative of the general formula (7) obtained by reacting the thiourea derivative of the general formula (5) with the malonic acid derivative of the general formula (6), As the esterifying agent, known ones can be used, but it is preferable to use a dimethyl sulfoxide solution of potassium tert-butoxide. The amount of the deesterifying agent to be added is preferably in the range of 6 to 20 times mol, more preferably in the range of 12 to 16 times mol, of the above-mentioned carbethoxythiouracil derivative.

The reaction temperature can be selected from the range of room temperature to 80 ° C., but is preferably in the range of room temperature to 40 ° C. The reaction time is not particularly limited and can be generally selected from a range of about 1 to 24 hours, but may be determined in relation to the reaction temperature.

After the reaction, water is added to the reaction mixture, and the acid is further added to make the solution acidic, whereby a carboxythiouracil derivative represented by the general formula (8) is obtained.

In the reaction of the carboxythiouracil derivative of the general formula (8) with the alcohol having a polymerizable unsaturated bond of the general formula (9), the carboxythiouracil derivative of the general formula (8) The reaction molar ratio of the alcohol having a polymerizable unsaturated bond may be in the range of 1 to 5, but is more preferably in the range of 1 to 3.

Examples of the esterification catalyst used in the esterification reaction include p-toluenesulfonic acid, benzenesulfonic acid, N, N'-dicyclohexylcarbodiimide and the like. The addition amount of these reaction catalysts is preferably in the range of 0.1 to 1 mol per mol of the carboxythiouracil derivative.

The solvent used in this reaction includes tetrahydrofuran, acetone, toluene and the like. It is also preferable to add a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, and butylhydroxytoluene.

The reaction temperature can be selected from the range of room temperature to 80 ° C., but is preferably in the range of room temperature to 70 ° C. The reaction time is not particularly limited and can be generally selected from a range of about 1 to 50 hours, but may be determined within a range where the reactants do not polymerize in relation to the reaction temperature.

After the reaction, the precipitate is filtered, the solvent is distilled off under reduced pressure, and the concentrate is separated and purified by passing through a silica gel column using an inert solvent such as ethyl acetate as a developing solvent to produce a highly pure product. Things are obtained.

Next, a method for producing the thiouracil derivative represented by the general formula (4) will be described.

That is, the following general formula (5)

[0065]

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(Wherein R ⁵ and R ⁶ are as defined above) and a thiourea derivative represented by the following general formula (10):

[0067]

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(Wherein R ⁷ is a hydrogen atom, an alkyl group or a phenyl group) by condensation reaction with a succinic acid derivative represented by the following general formula (11):

[0069]

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(Wherein R ⁵ , R ⁶ and R ⁷ have the same meanings as defined in the above general formula) to obtain a carboethoxythiouracil derivative represented by the following general formula (12). )

[0071]

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(Wherein R ⁵ , R ⁶ and R ⁷ have the same meanings as defined in the above general formula), and a carboxythiouracil derivative represented by the following general formula (9) is obtained.

[0073]

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In the formula, R ⁸ represents a divalent saturated hydrocarbon group having 2 to 12 carbon atoms, —CH ₂ —C ₆ H ₄ —CH ₂ — or — (C
_{H 2) o -Si (CH 3} ) 2 OSi (CH 3) 2 - (CH 2) p
- (. However, o and p are each independently an integer of 1 to 5), and, Y is, -COO -, - CH ₂ O- or -C ₆ H ₄ -CH ₂ is O-, R ⁹ is a hydrogen atom or a methyl group. By reacting the alcohol represented by｝, a thiouracil derivative having a polymerizable unsaturated bond of the general formula (4) can be obtained.

As the thiourea derivative represented by the general formula (5), known ones can be used without limitation as in the case of the production of the general formula (3).

As the succinic acid derivative represented by the general formula (10), known compounds can be used without any limitation. For example, diethyl 2-oxosuccinate, diethyl 2-methyl-2′-oxosuccinate, diethyl 2-ethyl-2′-oxosuccinate, diethyl 2-butyl-2′-oxosuccinate and the like are preferably used.

As the alcohol having a polymerizable unsaturated bond represented by the general formula (9), the same alcohol as used in the production of the general formula (3) can be used.

In the condensation reaction between the thiourea derivative of the general formula (5) and the succinic acid derivative of the general formula (10), the reaction of the succinic acid derivative of the general formula (10) with the thiourea derivative of the general formula (5) The molar ratio is preferably from 0.5 to 1.5 mol.

As the reaction catalyst used at this time, known catalysts can be used, and examples thereof include sodium ethoxide and the like, and the addition amount thereof is 0.5 to 1. 1 based on the thiourea derivative of the general formula (5). 0-fold molar is preferred.

The solvent used for this reaction includes ethanol and the like. The reaction temperature can be selected from the range of 40 to 80 ° C, and is preferably in the range of 60 to 80 ° C. The reaction time is not particularly limited and can be generally selected from a range of about 1 to 10 hours, but may be determined in relation to the reaction temperature.

After the reaction, the precipitated salt is dissolved in water, and the solution is acidified by adding an acid to obtain a carboethoxythiouracil derivative represented by the general formula (11).

However, in the thiourea of the general formula (5), when either R ⁵ or R ⁶ is an alkyl group, the carboethoxythiouracil derivative of the general formula (11) is substituted on the N-atom of the alkyl group. As a mixture of isomers. These can be separated and purified by column chromatography.

The deesterification reaction of the carboethoxythiouracil derivative of the general formula (11) obtained by reacting the thiourea derivative of the general formula (5) with the succinic acid derivative of the general formula (10) It can be carried out in the same manner as in the case of the carboethoxythiouracil derivative shown in (7).

The reaction between the carboxythiouracil derivative represented by the general formula (12) and the alcohol having a polymerizable unsaturated bond represented by the general formula (9) is carried out by reacting the carboxythiouracil derivative represented by the general formula (8) with the general formula (8) The reaction can be carried out in the same manner as in the reaction of 9) with an alcohol having a polymerizable unsaturated bond.

In the metal surface treating agent of the present invention, the concentration of the thiouracil derivative is not particularly limited, but is preferably in the range of 0.001 to 20% by weight from the viewpoint of adhesive strength and prevention of excessive use. A more preferred concentration range of the thiouracil derivative concentration is 0.005 to
10% by weight.

As the organic solvent used in the present invention, a general organic solvent or a polymerizable monomer can be used without any limitation as long as it can dissolve the thiouracil derivative.
When a volatile organic solvent is used, good adhesion can be obtained even at a low thiouracil derivative concentration,
It is preferred to use volatile organic solvents.

Specific examples of the above-mentioned organic solvents that can be suitably used in the present invention include alcohols such as methanol, ethanol, isopropyl alcohol and butanol; ketones such as acetone and methyl ethyl ketone; ethyl ether and 1,4-dioxane. Ethers such as ethyl acetate and ethyl formate; aromatic solvents such as toluene, xylene and benzene; hydrocarbon solvents such as pentane, hexane, heptane and octane; methylene chloride, chloroform, 1, Chlorinated solvents such as 2-dichloroethane; and fluorinated solvents such as trifluoroethanol. Among them, acetone, toluene, ethanol and the like are particularly preferably used for reasons such as solubility and storage stability.

The polymerizable monomer which can be suitably used as an organic solvent in the present invention has, for example, a radical polymerizability. Specific examples of polymerizable monomers that can be suitably used include, for example, polymerization of methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and hydroxyethyl (meth) acrylate. Acrylic or methacrylic polymerizable monomers having high properties and styrene are exemplified.

The above organic solvents can be used alone or in combination of two or more.

In the metal surface treating agent of the present invention, an acidic group-containing (meth) acrylate-based monomer may be further blended in order to further enhance the adhesion to the base metal. By using the metal surface treatment agent of such an embodiment, it becomes possible to bond a resin or the like with a base metal such as a cobalt chromium alloy or a nickel chromium alloy. In particular, when the surface treating agent of this embodiment is used for an alloy of a base metal and a noble metal, the adhesive strength of the joined body obtained is determined by using a metal surface treating agent not containing an acidic group-containing (meth) acrylate monomer. Higher than when used. Since an alloy of a base metal and a noble metal is often used for dentistry, the metal surface treatment agent of the above embodiment is particularly effective as a dental metal surface treatment agent.

The acidic group-containing (meth) acrylate monomer has a carboxyl group or an anhydride thereof in the molecule,
There is no particular limitation as long as it is a (meth) acrylate monomer having an acidic group such as a phosphoric acid group, and known compounds can be used. Acrylate monomers are preferred.

[0092]

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(Wherein R ¹⁰ is a hydrogen atom or a methyl group,
R ¹¹ is a divalent to hexavalent organic residue having 1 to 20 carbon atoms which may have an ether bond and / or an ester bond, and X contains a carboxyl group, a carboxyl anhydride group, a phosphate group or a phosphate group. In the above general formula, X is a group containing a carboxyl group, a carboxyl anhydride group, a phosphate group, a phosphate group,
The structure is not particularly limited, but preferred specific examples are as follows.

[0094]

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In the above formula, the structure of R ¹¹ is not particularly limited, and is a known divalent to hexavalent organic residue having 1 to 20 carbon atoms which may have an ether bond and / or an ester bond. Can be adopted, and specific examples are as follows.

[0096]

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An acidic group-containing (meth) compound represented by the above general formula
Preferred specific examples of the acrylate monomer are as follows.

[0098]

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[0099]

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[0100]

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[0101]

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(However, R ¹⁰ is a hydrogen atom or a methyl group.) From the viewpoint of metal adhesion, among the acidic group-containing (meth) acrylate monomers exemplified in the above specific examples, particularly, a carboxyl group and a phosphorus group are preferred. Those having an acid group are preferably used.

The acidic group-containing (meth) acrylate monomers can be used alone or in combination of two or more.

In a metal surface treating agent containing an acidic group-containing (meth) acrylate monomer, a blend of a thiouracil derivative (a), an acidic group-containing (meth) acrylate monomer (b) and an organic solvent (c) The proportion is not particularly limited, but when the total of (a), (b) and (c) is 100 parts by weight, the amount of (a) is 0.001 to 20 parts by weight, and the amount of (b) is When 0.1 to 15 parts by weight and (c) are the balance, good adhesion to both the base metal and the noble metal can be obtained. A more preferable compounding ratio is that (a) is 0.0
05 to 10 parts by weight, (b) 1 to 10 parts by weight, and (c) the remainder.

In the metal surface treating agent of the present invention, it is preferable to use a combination of the thiouracil derivative represented by the general formula (1) or (2) and an organic solvent which dissolves the thiouracil derivative and has volatility. It is suitable in terms of adhesive strength and ease of handling. Further, when it is desired to enhance the adhesion to a base metal, it is preferable to use the metal surface treating agent by blending an acidic group-containing (meth) acrylate monomer represented by the general formula (13). .

Further, a polymerization catalyst can be added to the metal surface treating agent of the present invention, if necessary, as long as the adhesion is not reduced. Examples of the polymerization catalyst that can be added include peroxide-based polymerization catalysts such as diacyl peroxides such as benzoyl peroxide and decanoyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-tert-butyl peroxide; 5-butylbarbi Barbituric acid-based polymerization catalysts such as tool acid and 5-butyl-2-thiobarbituric acid; α-diketones such as camphorquinone and acetylbenzoyl; benzoin alkyl ethers such as benzoin ethyl ether; 2-chlorothioxanthone and methylthio Thioxanthone derivatives such as xanthone; photopolymerization catalysts such as benzophenone derivatives such as benzophenone and P, P'-methoxybenzophenone; and dimethylaminoethyl methacrylate, N, N dimethyl paratoluidine, and P-dimethylbenzoic acid. Amine cocatalyst, etc. and the like. These polymerization catalysts and cocatalysts
One kind or a combination of two or more kinds can be added as required.

If necessary, a polymerization inhibitor such as hydroquinone monomethyl ether, hydroquinone and 4-tert-butylphenol may be added.

The method for preparing the metal surface treating agent by mixing the above components is not particularly limited. For example, the thiouracil derivative, the organic solvent and, if necessary, an acidic group-containing (meth) acrylate monomer, The other optional components may be weighed and weighed in a container at a desired ratio and stirred and mixed until uniform.

The method of using the metal surface treating agent of the present invention is not particularly limited. However, in order to adhere the metal and the resin satisfactorily, the metal surface treating agent of the present invention is applied to the metal surface, A method in which the polymerizable composition is added to the mixture, and the polymerized composition is further cured can be suitably used. Further, by separately bonding a resin, a metal, a ceramic, or the like to the opposite side of the surface of the polymerizable composition which comes into contact with the metal, the metal and these substances can be indirectly bonded.

In the above method, any known polymerizable composition can be used without any limitation as the polymerizable composition to be applied on the metal surface after the treatment. However, considering the polymerizability and ease of handling, the polymerization initiation catalyst Those mainly containing an acrylic or methacrylic polymerizable monomer containing Polymerizable compositions commonly used in dentistry, such as denture base resins, instant polymerization resins, hard resins, composite resins, resin cements, etc., require an acrylic or methacrylic polymerizable monomer and a polymerization initiator. Since it is contained as a component, it can be suitably used.

Specific examples of the acrylic or methacrylic polymerizable monomer include monofunctional polymerizable monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate and methacryloxyethyl propionate. Monomer; triethylene glycol di (meth) acrylate, 2,2-bis (4- (3-methacryloxy-2-hydroxypropoxy) phenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, , 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylhexamethylene diisocyanate,
Polyfunctional polymerizable monomers such as pentaerythritol tri (meth) acrylate; 4-methacryloxyethoxycarbonylphthalic anhydride, 10-methacryloxydecyldihydrodiene phosphate, 10-methacryloxydecamethylenemalonic acid, 2-methacrylic acid Adhesive polymerizable monomers such as roxyethyl 3′-methacryloxy 2 ′ (3,4-dicarboxybenzoyloxy) propyl succinate are exemplified. These are used alone or in combination of two or more.

Specific examples of the polymerization initiation catalyst include benzoyl peroxide / a redox initiator such as N, N-diethanol-P-toluidine; an alkyl metal compound such as a partial oxide of tributylborane; n-butylbarbituric acid / Barbituric acid-based initiators such as copper chloride; and photopolymerization initiation catalysts such as camphorquinone / N, N-dimethylaminoethyl methacrylate.

When the metal surface treating agent of the present invention is used for a pure metal such as gold, palladium, platinum, silver or copper, or a dental gold alloy, a gold-silver palladium alloy or a silver alloy, the effect is obtained. Is particularly remarkable.

[0114]

By using the metal surface treating agent containing a thiouracil derivative having at least one radically polymerizable unsaturated bond in the molecule of the present invention, a metal, in particular, a noble metal and a resin can be bonded with high adhesive strength and high adhesion. Can be bonded with high water resistance and high durability. Further, when a metal surface treating agent further containing an acidic group-containing (meth) acrylate monomer is used, it is possible to exhibit extremely excellent adhesion to any of noble metals and base metals. Especially,
When the metal surface treating agent containing the acidic group-containing (meth) acrylate monomer is applied to an alloy of a base metal and a noble metal, the thiouracil derivative and the acidic group-containing (meth) acrylate monomer may be used alone in an organic solvent. A high bonding strength, which cannot be expected from the metal surface treatment agent blended in the above, can be obtained. Furthermore, these metal surface treating agents of the present invention have high storage stability and are extremely excellent in handling.

The details of the reason why the excellent effects are exhibited as described above are unknown at present, but are presumed as follows. That is, first, when a metal surface treatment agent composed of a thiouracil derivative and an organic solvent is applied to the metal surface, the sulfur atoms in the thiouracil molecule quickly react with the metal atoms or metal oxide on the surface to form a chemical bond with excellent water resistance. It is formed. Next, when the polymerizable composition is applied on the surface, the polymerizable unsaturated bond of the thiouracil derivative reacts with the polymerizable monomer in the polymerizable composition, copolymerizes and cures, forming a strong bond with the metal. It is formed. It is presumed that the reaction at the first stage is particularly likely to occur on the surface of the noble metal, and as a result, good adhesion between the noble metal and the resin or the like can be achieved.

On the other hand, the acidic group-containing (meth) acrylate monomer has a strong tendency to react with the base metal atom or its oxide to form a chemical bond having excellent water resistance. It is believed that the addition of further increases the adhesive strength to the base metal. When a metal surface treatment agent in which an acid group-containing (meth) acrylate monomer is blended with an alloy of a base metal and a noble metal is applied, the above-described reaction and the above-described reaction with a thiouracil derivative occur at the same time. It is estimated that the synergistic effect improved the adhesive strength.

[0117]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Production Example 1 Potassium tert-butoxide (43.7 g, 389)
mmol) and dimethyl sulfoxide (400 ml).
Dissolve in a liter eggplant-shaped flask, and add ethyl 2-thiouracil-5-carboxylate (5.
0 g, 25.0 mmol) was slowly added dropwise and allowed to react at room temperature for 1 hour. After completion of the reaction, methanol (500 ml) was added to the reaction mixture, and the deposited precipitate was filtered.
The obtained precipitate was dissolved in water, and hydrochloric acid was added to the aqueous solution to obtain pale yellow solid 5-carboxy-2-thiouracil (2.54 g).

Under a nitrogen atmosphere, 1,6-hexanediol (47.3 g, 0.40 mol) and molecular sieve 3
A powder (40 g) and acetonitrile (470 ml)
Of methacrylic acid chloride (20.9 g, 0.2 mol) in acetonitrile (30 ml) was slowly added dropwise to a 1-liter three-necked flask at room temperature using a dropping funnel. After the completion of the dropwise addition, the mixture was heated under reflux for 5 hours. Then, the mixture was allowed to cool to room temperature, and molecular sieve 3
The powder A was filtered, and acetonitrile was distilled off from the filtrate under reduced pressure. 300 ml of methylene chloride was added to the residue, and the methylene chloride solution was washed with water. The methylene chloride layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. From the residue, a colorless and transparent liquid 6 was obtained by silica gel column chromatography.
Hydroxyhexyl methacrylate (33.3 g) was separated and purified.

6-hydroxyhexyl methacrylate (5.59 g, 30 mmol), N, N'-dicyclohexylcarbodiimide (2.27 g, 11 mmol),
5-carboxy-2-thiouracil (1.72 g, 10
mmol) and tetrahydrofuran (50 ml).
The mixture was dissolved in a 00 ml three-necked flask and stirred at room temperature for 3 days. As the reaction proceeded, a white precipitate was formed. After completion of the reaction, the white precipitate was filtered. Tetrahydrofuran was distilled off from the obtained filtrate under reduced pressure, and the residue was added to silica gel column chromatography. By using a mixed solvent of ethyl acetate and hexane as a developing solvent, 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate [A] (1.13 g, 3.3 mmol) represented by the following formula 31 is obtained. Was. NMR
The results of (d6DMSO), MASS and elemental analysis are shown below.

[0121]

Embedded image

NMR (δ, ppm); 1.3-1.7 (8H, —COO—CH ₂ (CH ₂ ) _{4
CH 2 -OCO-) 1.87 (3H,} - CH 3) 4.09,4.13 (4H, -COO- CH 2 (CH 2) 4 CH 2 -OCO-) 5.65,6.01 ( _{2H, CH 2 = C-) 7.94} (1H, -N- CH = C-) 12.7 (2H, - NH -) MASS (M + 1) + = 341 elemental _{analysis; C 15 H 20 N 2 O} 5 SCHN calculated value 52.93 5.92 8.23 actual value 52.96 5.92 8.25 Production Example 2 1,10-decanediol (34.9) under a nitrogen atmosphere
g, 0.20 mol) and molecular sieve 3A powder (2
0 g) and tetrahydrofuran (350 ml) were slowly dropped at room temperature using a dropping funnel with a solution of methacrylic acid chloride (10.5 g, 0.1 mol) in tetrahydrofuran (30 ml). After the completion of the dropwise addition, the mixture was heated under reflux for 5 hours. Thereafter, the reaction mixture was allowed to cool to room temperature, and molecular sieve 3A
The powder was filtered, and tetrahydrofuran was distilled off from the filtrate under reduced pressure. 300 ml of methylene chloride was added to the residue, and the methylene chloride solution was washed with water. The methylene chloride layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. From the residue, a colorless transparent liquid 1 was obtained by silica gel column chromatography.
0-hydroxydecyl methacrylate (14.5 g) was separated and purified.

10-hydroxydecyl methacrylate (7.27 g, 30 mmol), N, N'-dicyclohexylcarbodiimide (2.27 g, 11 mmol),
5-carboxy-2-thiouracil (1.72 g, 10
mmol) and tetrahydrofuran (50 ml).
The mixture was dissolved in a 00 ml three-necked flask and stirred at room temperature for 3 days. As the reaction proceeded, a white precipitate was formed. After completion of the reaction, the white precipitate was filtered. Thereafter, by performing the same separation and purification treatment as in Production Example 1, 10-methacryloyloxydecyl 2-thiouracil-5-carboxylate [B] represented by the following Formula 32:
(1.15 g, 2.9 mmol) were obtained. NMR (d6
DMSO), MASS, and elemental analysis are shown below.

[0124]

Embedded image

NMR (δ, ppm); 1.3-1.8 (16H, —COO—CH ₂ (CH ₂ ) ₈ CH ₂ —OCO—) 1.87 (3H, —CH ₃ ), 4.08 _{, 4.13 (4H, -COO- CH 2} (CH 2) 8 CH 2 -OCO-) 5.65,6.01 (2H, CH 2 = C-), 7.93 (1H, -N- CH = C-), 12.8 (2H, - NH -) MASS (M + 1) + = 397 elemental _{analysis; C 19 H 28 N 2 O} 5 S C H N calculated 57.56 7.12 7.07 Found 57.51 7.14 7.08 Production Example 3 1,6-hexanediol (47.3) under a nitrogen atmosphere
g, 0.40 mol) and molecular sieve 3A powder (4
0g) in acetonitrile solution (470 ml)
In a 3-liter three-necked flask, add acrylic acid chloride (1
8.1 g, 0.2 mol) in acetonitrile solution (30
ml) was slowly added dropwise at room temperature using a dropping funnel.
After the completion of the dropwise addition, the mixture was heated under reflux for 5 hours. After the reaction, Production Example 2
Then, a colorless transparent liquid 6-hydroxyhexyl acrylate (28.9 g) was separated and purified.

6-Hydroxyhexyl acrylate (5.17 g, 30.0 mmol), N, N'-dicyclohexylcarbodiimide (2.27 g, 11 mmol)
1), 5-carboxy-2-thiouracil (1.72)
g, 10 mmol) and tetrahydrofuran (50 m
l) was dissolved in a 200 ml three-necked flask, and stirring was continued at room temperature for 3 days. As the reaction proceeded, a white precipitate was formed. After completion of the reaction, the white precipitate was filtered. Thereafter, the same separation and purification treatment as in Production Example 1 was performed to give 6-acryloyloxyhexyl 2-thiouracil-5-carboxylate [C] (1.01 g, 3.1 mmol) represented by the following Formula 33. Obtained. NMR
The results of (d6DMSO), MASS and elemental analysis are shown below.

[0127]

Embedded image

NMR (δ, ppm); 1.3-1.7 (8H, —COO—CH ₂ (CH ₂ ) ₄ CH ₂ —OCO—) 4.09, 4.13 (4H, —COO— CH _{2 (CH 2) 4 CH 2} -OCO-) 5.82,6.12,6.45 (3H, CH 2 = CH -), 7.93 (1H, -N- CH = C-), 12. 7 (2H, - NH -) MASS (M + 1) + = 327 elemental _{analysis; C 14 H 18 N 2 O} 5 S C H N calculated 51.52 5.56 8.58 Found 51.56 5.57 8 .57 Production Example 4 60% sodium hydride (1.92 g,
48 mmol) in tetrahydrofuran (20 ml)
Was added dropwise to a 300 ml three-necked flask containing 1,6-hexanediol (4.72 g, 40 mmol) in tetrahydrofuran (30 ml) at room temperature using a dropping funnel. Subsequently, a solution of chloromethylstyrene (6.1 g, 40 mmol) in tetrahydrofuran (30 ml) was slowly added dropwise. After the completion of the dropwise addition, the mixture was heated under reflux for 4 hours. Thereafter, the reaction mixture was allowed to cool to room temperature, and dilute hydrochloric acid was added to the reaction mixture to stop the reaction. The aqueous layer was extracted with ether, and the combined organic layers were saturated aqueous sodium hydrogen carbonate,
Washed with saturated saline. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and 1-hydroxy-6- (p-vinylbenzyloxy) hexane (7.97 g) was separated and purified by silica gel column chromatography.

1-hydroxy-6- (p-vinylbenzyloxy) hexane (7.03 g, 30 mmol),
N, N'-dicyclohexylcarbodiimide (2.27
g, 11 mmol), 5-carboxy-2-thiouracil (1.72 g, 10 mmol) and tetrahydrofuran (50 ml) were dissolved in a 200 ml three-necked flask, and stirring was continued at room temperature for 3 days. As the reaction proceeded, a white precipitate was formed. After completion of the reaction, the white precipitate was filtered. Thereafter, the same separation and purification treatment as in Production Example 1 is performed to give 6- (p-vinylbenzyloxy) hexyl 2-thiouracil-5-
Carboxylate [D] (1.17 g, 3.0 mmol
1) was obtained. The results of NMR (d6DMSO), MASS and elemental analysis are shown below.

[0130]

Embedded image

NMR (δ, ppm); 1.3-1.7 (8H, —COO—CH ₂ (CH ₂ ) ₄ CH ₂ —OCH ₂ —) 3.49, 4.1 (4H, —COO— CH ₂ (CH ₂ ) ₄ CH ₂ —OCH ₂ —) 4.53 (2H, —O CH ₂ —C ₆ H ₄ ) 5.27, 5.84, 6.71 (3H, CH ₂ = CH— ) _{, 7.3~7.4 (4H, C 6 H} 4) 7.93 (1H, -N- CH = C-), 12.7 (2H, - NH -) MASS (M + 1) + = 389 elemental analysis _{; C 20 H 24 N 2 O} 4 S C H N calculated 61.84 6.23 7.21 Found 61.81 6.27 7.24 preparation example 5 under nitrogen atmosphere, 2,2-dimethyl-1, 3-propanediol (20.8 g, 0.2 mol), molecular sieve 3A powder (20 g) and tetrahydrofuran (350
ml) of methacrylic acid chloride (10.5 g, 0.1 mol) in tetrahydrofuran (30 ml) was slowly dropped at room temperature using a dropping funnel. After the completion of the dropwise addition, the mixture was heated under reflux for 4 hours. After the reaction, the same treatment as in Example 3 was performed, and 3-hydroxy-2,2-dimethylpropyl methacrylate (1
3.1 g) was separated and purified.

3-hydroxy-2,2-dimethylpropyl methacrylate (5.18 g, 30 mmol), N,
N′-dicyclohexylcarbodiimide (2.27 g,
11 mmol), 5-carboxy-2-thiouracil (1.72 g, 10 mmol) and tetrahydrofuran (50 ml) were dissolved in a 200 ml three-necked flask, and stirring was continued at room temperature for 3 days. As the reaction proceeded, a white precipitate was formed. After completion of the reaction, the white precipitate was filtered. Thereafter, by performing the same separation and purification treatment as in Production Example 1, 3-methacryloyloxy-2,2-dimethylpropyl 2-thiouracil-5-carboxylate [E] represented by the following formula 35 (0.91 g) , 2.8
mmol). NMR (d6DMSO), MASS
And the results of elemental analysis are shown below.

[0133]

Embedded image

NMR (δ, ppm); 0.91 (6H, -CH ₂ C (CH ₃ ) ₂ CH _2- ) 1.87 (3H, CH ₂ = C- CH ₃ ), 4.1, 4. _{18 (4H, -COO- CH 2 C} (CH 3) 2 CH 2 -OCO-) 5.66,6.02 (2H, CH 2 = C-), 7.93 (1H, -N- CH = C -), 12.8 (2H, - NH -) MASS (M + 1) + = 327 elemental _{analysis; C 14 H 18 N 2 O} 5 S C H N calculated 51.52 5.56 8.58 Found 51. 54 5.55 8.57 Production Example 6 Para-xylene glycol (55.2) under a nitrogen atmosphere
g, 0.40 mol) and molecular sieve 3A powder (4
0 g) and acetonitrile (470 ml)
A solution of methacrylic acid chloride (20.9 g, 0.2 mol) in acetonitrile (30 ml) was slowly dropped into a three-neck three-liter flask at room temperature using a dropping funnel. After the completion of the dropwise addition, the mixture was heated under reflux for 5 hours. Thereafter, the mixture was allowed to cool to room temperature, molecular sieve 3A powder was filtered from the reaction mixture, and acetonitrile was distilled off from the filtrate under reduced pressure. 300 ml of methylene chloride was added to the residue, and the methylene chloride solution was washed with water. The methylene chloride layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. From this residue, white solid (4-hydroxymethyl) benzyl methacrylate (34.8 g) was separated and purified by silica gel column chromatography.

4-Hydroxymethylbenzyl methacrylate (6.48 g, 30 mmol), N, N'-dicyclohexylcarbodiimide (2.27 g, 11 mmol)
1), 5-carboxy-2-thiouracil (1.72)
g, 10 mmol) and tetrahydrofuran (50 m
l) was dissolved in a 200 ml three-necked flask, and stirring was continued at room temperature for 3 days. As the reaction proceeded, a white precipitate was formed. After completion of the reaction, the white precipitate was filtered. Thereafter, the same separation and purification treatment as in Production Example 1 was performed to give (4-methacryloyloxymethyl) benzyl 2-thiouracil-5-carboxylate [F] (0.91 g, 2. 5 mmol).
The results of NMR (d6DMSO), MASS and elemental analysis are shown below.

[0136]

Embedded image

NMR (δ, ppm); 1.90 (3H, —CH ₃ ), 5.17, 5.23 (4H, —COO— CH ₂ —C ₆ H ₄ —CH ₂ —OCO—) _{70,6.07 (2H, CH 2 = C-} ), 7.40 (4H, - C 6 H 4 -), 8.00 (1H, -N- CH = C-), 12.8 (2H, ^{- NH -) MASS (M +} 1) + = 361 elemental _{analysis; C 17 H 16 N 2 O} 5 S C H N calculated 56.66 4.47 7.77 Found 56.42 4.31 7.82 preparation 7 1,3-bis (hydroxypropyl) tetramethyldisiloxane (100 g, 0.40 mol) under a nitrogen atmosphere
Methacrylic acid chloride (20.9 g, 0.2 m) was placed in a 1-liter three-necked flask containing powder and molecular sieve 3A powder (40 g) and acetonitrile (470 ml).
ol) in acetonitrile (30 ml) was slowly added dropwise at room temperature using a dropping funnel. After the completion of the dropwise addition, the mixture was heated under reflux for 5 hours. Thereafter, the mixture was allowed to cool to room temperature, molecular sieve 3A powder was filtered from the reaction mixture, and acetonitrile was distilled off from the filtrate under reduced pressure. Methylene chloride 300m for residue
1 was added, and the methylene chloride solution was washed with water. The methylene chloride layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. From this residue, a colorless transparent liquid 1- (methacryloyloxypropyl) -3- (hydroxypropyl) tetramethyldisiloxane (46.2 g) was separated and purified by silica gel column chromatography.

1- (methacryloyloxypropyl)-
3- (hydroxypropyl) tetramethyldisiloxane (9.54, 30 mmol), N, N'-dicyclohexylcarbodiimide (2.27 g, 11 mmol), 5
-Carboxy-2-thiouracil (1.72 g, 10 m
mol) and tetrahydrofuran (50 ml) in 20
The mixture was dissolved in a 0 ml three-necked flask, and stirring was continued at room temperature for 3 days. A white precipitate is formed as the reaction proceeds,
After completion of the reaction, the white precipitate was filtered. Thereafter, the same separation and purification treatment as in Production Example 1 was performed to give a compound [G] (1.13 g, 2.4 mm) represented by the following Formula 37.
ol). The results of NMR (d6DMSO), MASS and elemental analysis are shown below.

[0139]

Embedded image

[0140] NMR (δ, ppm); 0.06 (12H, -Si- CH3), 0.51 (4H, -Si- CH 2 -CH 2 -CH 2 -OCO-), 1.69 (4H, _{-Si-CH 2 - CH 2 -CH} 2 -OCO-), 1.87 (3H, - CH 3), 4.23 (4H, -Si-CH 2 -CH 2 - CH 2 -OCO-), 5 _{.67,6.03 (2H, CH 2 = C-} ), 7.96 (1H, -N- CH = C-), 12.8 (2H, - NH -) MASS (M + 1) + = 473 elemental analysis _{; C 19 H 32 N 2 O} 6 SSi 2 C H N calculated 48.28 6.82 5.93 Found 48.35 6.74 5.73 production example 8 under a nitrogen atmosphere, sodium ethoxide (13.6 g ,
0.2 mol) of ethanol solution (200 ml) in a 1-liter three-necked flask was charged with diethyl malonate (1).
6.0 g (0.1 mol) ethanol solution (50 m
l) was slowly dropped at room temperature using a dropping funnel. After the completion of the dropwise addition, the mixture was heated to reflux. Subsequently, an ethanol solution (100 ml) of triethyl orthopropionate (17.6 g, 0.1 mol) was slowly added dropwise using a dropping funnel. After the completion of the dropwise addition, the mixture was heated and refluxed for 6 hours. After cooling to room temperature, ethanol was distilled off under reduced pressure, and 200 ml of water was added to the residue, followed by ether extraction (3 times). The ether layer was washed with saturated saline, dried over anhydrous magnesium sulfate and concentrated. The residue was distilled under reduced pressure to obtain diethyl 1-ethoxy-1-ethylmethylenemalonate (17.2 g).

In a nitrogen atmosphere, a solution of sodium ethoxide (3.4 g, 0.05 mol) in ethanol (50
ml) in a 500 ml three-necked flask containing diethyl 1-ethoxy-1-ethylmethylenemalonate (12.2).
g, 0.05 mol) of ethanol solution (50 ml) was slowly added dropwise at room temperature using a dropping funnel. After the completion of the dropwise addition, the mixture was heated to reflux. Subsequently, thiourea (3.8 g,
A 0.05 mol) ethanol solution (50 ml) was slowly dropped at room temperature using a dropping funnel. After dropping,
The mixture was refluxed for 3 hours. After allowing to cool to room temperature, the reaction mixture was added to a beaker containing water (200 ml). When concentrated hydrochloric acid was added to the obtained solution, a pale yellow solid precipitated. By filtering the precipitated solid, ethyl 6-
Ethyl-2-thiouracil-5-carboxylate (7.3 g) was obtained.

Potassium tert-butoxide (43.
7 g, 389 mmol) and dimethyl sulfoxide (40
0 ml) in a 2 liter eggplant-shaped flask to dissolve,
Ethyl 6-ethyl-2-thiouracil-5 was added to this solution.
-Carboxylate (5.70 g, 25.0 mmol)
Was slowly added dropwise and reacted for 1 hour at room temperature. After completion of the reaction, methanol (500 ml) was added to the reaction mixture,
The deposited precipitate was filtered. The obtained precipitate was dissolved in water, and hydrochloric acid was added to this aqueous solution to obtain pale yellow solid 5-carboxy-6-ethyl-2-thiouracil (3.10 g).

6-hydroxyhexyl methacrylate (5.59 g, 30 mmol), N, N'-dicyclohexylcarbodiimide (2.27 g, 11 mmol),
5-carboxy-6-ethyl-2-thiouracil (2.
00g, 10 mmol) and tetrahydrofuran (5
0 ml) in a 200 ml three-necked flask to dissolve,
Stirring was continued at room temperature for 3 days. As the reaction proceeded, a white precipitate was formed. After completion of the reaction, the white precipitate was filtered.
Thereafter, the same separation and purification treatment as in Production Example 1 was performed to give 6-methacryloyloxyhexyl 6-ethyl-2-thiouracil-5-carboxylate [H] (1.14 g, 3 .10 mmol)
I got The results of NMR (d6DMSO), MASS and elemental analysis are shown below.

[0144]

Embedded image

NMR (δ, ppm); 1.02 (3H, —CH ₂ CH ₃ ) 1.3 to 1.7 (8H, —COO—CH ₂ (CH ₂ ) ₄ CH ₂ —OCO—) 87 (3H, C = C- CH 3) 2.05 (2H, - CH 2 CH 3) 4.09,4.13 (4H, -COO- CH 2 (CH 2) 4 CH 2 -OCO-) 5 _{.65,6.01 (2H, CH 2 = C-} ) 12.5 (2H, - NH -) MASS (M + 1) + = 369 elemental _{analysis; C 17 H 24 N 2 O} 5 S C H N calculated 55 .42 6.57 7.60 Found 55.42 6.59 7.63 Production Example 9 Sodium ethoxide (13.6 g,
0.20 mol) in a 1 liter three-necked flask containing an ethanol solution (200 ml).
Diethyl succinate (40.4 g, 0.2 mol)
Ethanol solution (100 ml) was slowly dropped at room temperature using a dropping funnel. After the completion of the dropwise addition, the mixture was heated to reflux. Subsequently, methylthiourea (18.0 g, 0.2 m
ol) in ethanol (100 ml) was slowly added dropwise using a dropping funnel. After the completion of the dropwise addition, the mixture was heated under reflux for 3 hours. The mixture was allowed to cool to room temperature, and the reaction mixture was washed with water (500 m
1) was added to the beaker. When concentrated hydrochloric acid was added to the obtained solution, a pale yellow solid precipitated. The precipitated solid was filtered and separated and purified using column chromatography to obtain ethyl 3,5-dimethyl-2-thiouracil-6-carboxylate (16.2 g).

Potassium tert-butoxide (43.
7 g, 389 mmol) and dimethyl sulfoxide (40
0 ml) in a 2 liter eggplant-shaped flask to dissolve,
To this solution was added ethyl 3,5-dimethyl-2-thiouracil-6-carboxylate (5.70 g, 25.0 mm).
ol) was slowly added dropwise and reacted for 1 hour at room temperature. After completion of the reaction, methanol (500 ml) was added to the reaction mixture, and the deposited precipitate was filtered. The obtained precipitate was dissolved in water, and hydrochloric acid was added to this aqueous solution to give a pale yellow solid 6-.
Carboxy-3,5-dimethyl-2-thiouracil (2.88 g) was obtained.

6-hydroxyhexyl methacrylate (5.59 g, 30 mmol), N, N'-dicyclohexylcarbodiimide (2.27 g, 11 mmol),
6-carboxy-3,5-dimethyl-2-thiouracil (2.00 g, 10 mmol) and tetrahydrofuran (50 ml) were dissolved in a 200 ml three-necked flask, and stirring was continued at room temperature for 3 days. As the reaction proceeded, a white precipitate was formed. After completion of the reaction, the white precipitate was filtered. Thereafter, the same separation and purification treatment as in Production Example 1 was performed to give 6-methacryloyloxyhexyl 3,5-dimethyl-2-thiouracil-6-carboxylate [I] (1.13 g) represented by the following Formula 39. , 3.07
mmol). NMR (d6DMSO), MASS
And the results of elemental analysis are shown below.

[0148]

Embedded image

NMR (δ, ppm); 1.3-1.7 (8H, —COO—CH ₂ (CH ₂ ) ₄ CH ₂ —OCO—) 1.87 (3H, CH ₂ CC— CH ₃ ) 2.36 (3H, C = C- CH 3) 3.68 (3H, N-CH 3) 4.09,4.13 (4H, -COO- CH 2 (CH 2) 4 CH 2 -OCO-) _{5.65,6.01 (2H, CH 2 = C-} ) 12.3 (1H, - NH -) MASS (M + 1) + = 369 elemental _{analysis; C 17 H 24 N 2 O} 5 S C H N calculated 55.42 6.57 7.60 Actual value 55.48 6.54 7.61 Examples 1 to 9 and Comparative Examples 1 to 9 Nine kinds of thiouracil derivatives (A to I) shown in Table 1 and the following publicly known compounds 11-methacryloxy-1,1-undecanedicarboxylic acid [J], 10-methacryloyloxydecyldihydrodiene phosphate [K], 4-methacryloyloxyethyl trimellitate Anhydride [L]
Each was used to examine the adhesive effect on dental precious metals. The structure and abbreviation of the thiouracil derivative are as described above.

[0150]

Embedded image

Each of these compounds was made into a 0.5% by weight acetone solution to prepare a metal surface treating agent. Dental gold-silver-palladium alloy “Gold Para 12” (10 × 10 × 3 mm manufactured by Towa Giken Co., Ltd.), a pure gold plate (10 × 10
× 3 mm) was polished with # 1500 water-resistant abrasive paper, and then subjected to sandblasting, and an adhesive tape having a hole of 4 mmφ was attached to the treated surface to fix the adhesive area. The previously prepared metal surface treatment agent was applied to each surface with a brush, and acetone was air-dried. One minute later, a kneaded paste of the dental adhesive “Bistite Resin Cement” (manufactured by Tokuyama) was raised on the surface treated with the metal surface treatment agent. Next, a sandblast treatment was performed in advance 8
A round bar made of SUS304 having a size of φ18 mm was pressed against the bonding surface to perform bonding. Remove excess resin cement,
One hour later, the adhesive test piece was immersed in water at 37 ° C. Twenty-four hours later, the tensile adhesive strength was measured using an autograph manufactured by Shimadzu Corporation (crosshead speed: 10 mm / min). The measurement values of six test pieces were averaged, and the measurement results are shown in Table 1.

[0152]

[Table 1]

Examples 10 to 18 Using the compound (A) shown in Example 1 of Table 1, the concentration effect of the adhesive component contained in the metal surface treating agent was examined. That is, the compound (A) is dissolved in acetone,
20, 10, 5, 1, 0.5, 0.1, 0.01, respectively
Dental gold-silver-palladium alloy "Gold Para 12" was prepared in the same manner as in Examples 1 to 9 except that acetone solutions having a concentration of 0.005 and 0.001% by weight were prepared, and this solution was used as a metal surface treatment agent. The effect of adhesion to a pure gold plate was examined. Table 2 shows the results.

[0154]

[Table 2]

Example 19 and Comparative Example 5 A 0.5% methyl methacrylate solution of the compound (A) used in Example 1 was prepared, and “gold” as a dental noble metal alloy was prepared according to the methods of Examples 1 to 9. The coated surface was washed with pure acetone after 1 minute, and then a stainless steel rod was bonded with "Bistite resin cement" (manufactured by Tokuyama) to obtain an adhesive test piece (Example 19). On the other hand, as a comparative example,
A test piece coated with methyl methacrylate alone (Comparative Example 5) was also prepared. As in Examples 1 to 9, these test pieces were immersed in water at 37 ° C. for one day, and then the tensile adhesive strength was measured. The average adhesive strength was 23 MPa, whereas the average adhesive strength was 10 MPa in the comparative example. Examples 20 to 28 and Comparative Example 6 A 0.5% acetone solution of Compound A used in Example 1 was prepared, and “gold para 12” which is a dental precious metal alloy according to the method of Examples 1 to 9, And applied to a “pure gold plate”, air-dried, and a stainless steel rod was bonded using “Bistite Resin Cement” (manufactured by Tokuyama), and an adhesive test piece (Example 20)
And Similarly, adhesion test pieces (Examples 21 to 28) were prepared using Compounds B to I. On the other hand, as a comparative object, a test piece (Comparative Example 6) in which pure acetone solution alone was applied and “gold 12” and “pure gold plate” and a stainless steel rod were adhered with a bistit resin cement was also prepared. These test pieces were immersed in water at 37 ° C. one hour after bonding for the purpose of evaluating the bonding durability, and then placed in a constant temperature water bath at 4 ° C. and 60 ° C. after 24 hours.
A thermal cycle test of alternately immersing for minutes was performed 5000 times, and the tensile adhesive strength was measured. Table 3 shows the results.

[0156]

[Table 3]

In each case where any of the metal surface treating agents was used (Examples 20 to 28), the adhesive strength of various metals after the heat cycle test was the initial adhesive strength {the numerical value in parentheses in Table 3}. There was no significant decrease. On the other hand, in Comparative Example 6, a large decrease in the adhesive strength was observed.

Examples 29 to 37 After preparing a 0.5% acetone solution of the compound A used in Example 1, the solution was evaluated in order to evaluate the storage stability of the primer.
It was stored for 2 months in a constant temperature room at 7 ° C. The primer after storage is applied to “gold para 12” and “pure metal plate” which are dental precious metal alloys according to the methods of Examples 1 to 9, and after air-drying, using “Bistite resin cement” (manufactured by Tokuyama). A stainless steel rod was adhered to obtain an adhesion test piece (Example 29). Similarly, after preparing a 0.5% acetone solution of Compounds B to I, they were stored at 37 ° C. for 2 months, and they were adhered to each other to obtain adhesion test pieces (Examples 30 to 37). One hour after bonding, these test pieces were immersed in water at 37 ° C., and after 24 hours, the tensile bond strength was measured. Table 4 shows the results.

[0159]

[Table 4]

Even when the metal surface treatment agent stored at 37 ° C. for 2 months was used (Examples 29 to 37), the adhesive strength to various metals was the initial adhesive strength {the numerical value in () in Table 4}. There was no significant decrease compared to.

Example 38 0.001 g of 10-methacryloyloxydecyl 2-thiouracil-5-carboxylate [B], 1.4 g of 11-methacryloyloxy-1,1-undecanedicarboxylic acid [J], and 18.599 g of acetone After mixing, a homogeneous solution was obtained. This was used as a metal surface treatment agent. Dental gold-silver-palladium alloy "Gold Para 12" (g)
10 × 10 × 3 mm manufactured by Wagiken Co., Ltd., dental cobalt-chrome alloy “Wachrome” (10 × 10 × manufactured by Towagiken)
3mm), pure gold plate (10 × 10 × 3mm), pure copper plate (1
(0 × 10 × 3 mm) was polished with # 1500 water-resistant abrasive paper, and then subjected to sandblasting, and an adhesive tape having a 4 mmφ hole was attached to the treated surface to fix the adhesive area. The previously prepared metal surface treatment agent was applied to each surface with a brush, and acetone was air-dried. After one minute,
On the surface treated with the metal surface treatment agent, a kneading paste of a dental adhesive "Bistite resin cement" (manufactured by Tokuyama) was raised. Then, a SUS304 round bar of 8 mmφ × 18 mm, which had been previously sandblasted, was pressed against the bonding surface to perform bonding. Excess resin cement was removed, and one hour later, the adhesive test piece was immersed in water at 37 ° C.
Twenty-four hours later, the tensile adhesive strength was measured using an autograph manufactured by Shimadzu Corporation (crosshead speed: 10 mm / min). The measured values of six test pieces were averaged, and Table 6 shows the measured results.

Examples 39 to 52 In accordance with the method of Example 38, metal surface treating agents having the compositions shown in Table 5 were prepared, and the adhesive strength to various metals was measured in the same manner. Table 6 shows the measurement results. The structure and the abbreviation of the acidic group-containing (meth) acrylate monomer used are shown below.

[0163]

Embedded image

[0164]

[Table 5]

[0165]

[Table 6]

Examples 40, 41, 43, 46 and 49
Represent the results when different acidic group-containing (meth) acrylate monomers are used, and are shown in Examples 39, 41, 42, and 4
4, 45, 47, 48, 50 and 51 represent the results using different thiouracil derivatives, and Examples 43, 46, 49 and 52 represent the results using different solvents. Examples 38 and 52 show the range tested for the content of the thiouracil derivative, and Examples 39 and 47 show the range tested for the content of the acidic group-containing (meth) acrylate monomer. Example 47 is an example using a plurality of organic solvents, and Example 44 is an example using a plurality of acidic group-containing (meth) acrylate monomers. In all the examples described above, the adhesive strength to “gold para 12”, “wachrome”, a pure gold plate, and a pure copper plate all showed good results.

Further, Embodiment 46, Embodiment 2 and Embodiment 4
8 and Example 1, the adhesive strength to “gold para 12” which is an alloy of a base metal and a noble metal is as follows:
In each case, it is higher than the case where the acidic group-containing (meth) acrylate monomer is not blended.

Examples 53 to 54 and Comparative Examples 7 to 8 Metal surface treating agents having the compositions shown in Table 7 were prepared and evaluated in the same manner as in Example 38. Table 8 shows the results.

[0169]

[Table 7]

[0170]

[Table 8]

Comparative Example 7 was an example containing no thiouracil derivative, and caused a problem in the bonding strength to “gold para 12” and a pure gold plate. Examples 53 and 54 contain acidic groups (meta)
Since the content of the acrylate monomer is out of the range, the adhesive strength to “wachrome” and a pure copper plate is reduced. Comparative Example 8 did not contain an organic solvent, the thiouracil derivative was not dissolved in the acidic group-containing (meth) acrylate monomer, and a uniform solution was not obtained.

Examples 55 to 61 and Comparative Example 9 The metal surface treating agent used in Example 48 was used in accordance with the method of Example 38 as a dental alloy such as “Gold Para 12”, “Wachrome” and a pure metal plate, pure copper Each was applied to a plate, and after air-drying, a stainless steel rod was adhered using “Bistite Resin Cement” (manufactured by Tokuyama) to obtain an adhesion test piece (Example 55). Similarly, adhesion test pieces (Examples 56 to 61) were prepared using the metal surface treatment agents used in Examples 41, 42, 43, 44, 45, and 46. On the other hand, as a comparative object, an adhesion test piece (Comparative Example 9) in which pure acetone solution alone was applied was also prepared. These test pieces were immersed in water at 37 ° C. one hour after bonding for the purpose of evaluating the bonding durability.
After a lapse of time, a thermal cycle test of alternately immersing in a constant temperature water bath at 4 ° C. and 60 ° C. for 1 minute was performed 5000 times, and the tensile adhesive strength was measured. Table 9 shows the results.

[0173]

[Table 9]

In all cases (Examples 55 to 61) using any of the metal surface treating agents, the adhesive strength of various metals after the heat cycle test was the initial adhesive strength {the numerical value in parentheses in Table 9}. There was no significant decrease. On the other hand, in Comparative Example 9, a large decrease in the adhesive strength was observed.

Examples 62 to 68 The metal surface treating agents used in Example 48 were stored in a constant temperature room at 37 ° C. for 2 months, followed by “Gold Para 12”, “Wachrome” and It was applied to a pure gold plate or a pure copper plate, air-dried, and a stainless steel bar was bonded using “Bistite Resin Cement” (manufactured by Tokuyama) to obtain an adhesion test piece (Example 62). Similarly, Examples 41, 42 and 4
The metal surface treating agents used in 3, 44, 45 and 46 were stored at 37 ° C. for 2 months and bonded to obtain adhesive test pieces (Examples 63 to 68). One hour after bonding, these test pieces were immersed in water at 37 ° C., and after 24 hours, the tensile bond strength was measured. Table 10 shows the results.

[0176]

[Table 10]

Even when the metal surface treating agent stored at 37 ° C. for 2 months was used (Examples 62 to 68), the adhesive strength to various metals was the initial adhesive strength {the numerical value in () in Table 10}. There was no significant decrease compared to.

Claims (3)

[Claims] 1. A metal surface treating agent comprising a thiouracil derivative containing at least one radically polymerizable unsaturated bond in a molecule and an organic solvent. 2. A metal surface treatment comprising a thiouracil derivative containing at least one radically polymerizable unsaturated bond in a molecule, an acidic group-containing (meth) acrylate monomer and an organic solvent. Agent. 3. The thiouracil derivative according to claim 1, wherein the thiouracil derivative containing at least one radically polymerizable unsaturated bond in a molecule is a thiouracil derivative represented by the following general formula (1) or (2). Metal surface treatment agent. Embedded image (Wherein, R ¹ and R ² are each a hydrogen atom or an alkyl group, and at least one of R ¹ and R ² is a hydrogen atom;
R ³ is a hydrogen atom, an alkyl group or a phenyl group;
R ⁴ is a divalent organic residue having 1 to 20 carbon atoms, and Z is an organic group having a radical polymerizable unsaturated bond. )