KR20170033085A

KR20170033085A - Catechol derivative-based adhesive composition and method for preparing the same

Info

Publication number: KR20170033085A
Application number: KR1020150130958A
Authority: KR
Inventors: 황동수; 오명환; 서덕규; 이도훈
Original assignee: 포항공과대학교 산학협력단
Priority date: 2015-09-16
Filing date: 2015-09-16
Publication date: 2017-03-24
Also published as: KR101799003B1; WO2017047886A1

Abstract

The present invention relates to a catechol derivative-based adhesive composition, and to a production method thereof. More specifically, the present invention relates to an adhesive composition based on catechol derivative which includes a hydroxyl protection group and various functional groups, and to a production method thereof. According to the present invention, the adhesive composition is based on the catechol derivative compound which includes the hydroxyl protection group and the various functional groups, and shows excellent biocompatibility, economic feasibility, and superior adhesiveness even under a wet condition, thereby being able to be used as dental or surgical adhesive.

Description

TECHNICAL FIELD The present invention relates to a catechol derivative-based adhesive composition and a method for preparing the same,

The present invention relates to a catechol derivative-based adhesive composition and a process for its preparation, and more particularly to a catechol derivative-based adhesive composition comprising a hydroxyl protecting group and various functional groups and to a process for preparing the same.

A variety of restorative materials are used in relation to the treatment of dental caries and the aesthetic function of the oral cavity. Composite resins, metal alloys, ceramics, ceramics, and glass are mainly used. These materials have no adhesiveness to hemorrhoids. Therefore, compositions for adhering restoration materials to teeth have been developed.

In general, tooth adhesion is largely divided into enamel and dentin bonding. Enamel is a very hard tissue composed of 95% inorganic, 1% organic and 4% water. Enamel adhesion is generally achieved by dissolving hydroxyapatite crystals by acid etching to expose enamel rods to the surface, causing the adhesive to penetrate, cure, and micro-mechanically bond. The tooth dentin consists of 70% inorganic, 20% organic and 10% water. It is characterized by organic matter and moisture in comparison with enamel. Adhesive composition also needs different composition than enamel. Early dentin adhesives were close to hydrophobic and did not penetrate well into the smear layer of the dentin. Resulting in very low adhesive strength. To overcome this problem, hydrophilic monomers such as 2-hydroxy methacrylate (HEMA) have begun to be added, which allows the adhesive to penetrate well into the dentin layer and withstand wet conditions . However, HEMA has a disadvantage of low strength after polymerization.

A mussel attached to the surface of rocks and so on produces and secretes an adhesive protein, which contains 3,4-dihydroxyphenyl-L-alanine (DOPA), which has mostly catechol functionality. DOPA is a derivative of tyrosine, one of the amino acids that a creature has, and is a precursor of signaling substances, dopamine and norepinephrine. Since DOPA is the most important substance in the adhesive protein of marine mussel, it has excellent adhesion underwater. For this reason, adhesives containing DOPA are considered suitable for use as dental adhesives. However, even if the bonding ability of DOPA itself is excellent, it is easily oxidized into dopa quinone in the air to change the hydroxyl group into a carboxyl group, which causes the DOPA to lose the property of coordinating with the metal. In addition, when it is oxidized, there is a disadvantage that it reacts with other substances to cause an undesired crosslinking reaction and the adhesive ability may be lowered. In order to eliminate these side reactions, it is necessary to carry out the reaction in the absence of oxygen in the production of the catechol derivative, but the production cost is relatively high. In order to develop and commercialize the adhesive using DOPA, It is essential to develop the mechanism.

KR 10-2013-0096424

The inventors of the present invention have found that an adhesive composition based on a catechol derivative containing a hydroxyl protecting group and various functional groups has excellent biocompatibility and is economical and exhibits excellent adhesive strength even in a wet condition , Thereby completing the present invention.

Accordingly, the present invention is intended to provide the adhesive composition and a method for producing the same.

The present invention also provides a bone adhesive comprising the adhesive composition.

The present invention also provides a dental adhesive comprising the adhesive composition.

The present invention also provides an implant kit comprising the dental adhesive.

In order to achieve the above object,

The present invention

There is provided an adhesive composition comprising a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

P is a hydroxyl protecting group,

L1 or L2 are each independently a hydrogen, hydroxyl group, C ₁ to C ₁₀ straight chain or an alkyl group branched chain, a C ₁ to C ₁₀ alkoxy group, an acrylate group, a methacrylate group, and pentane erythritol tetrakis ( Pentaerythritol tetrakis (3-mercaptopropionate), PETMP).

The present invention also relates to a process for photopolymerizing a mixture of the compound of Formula 1, a methacrylate monomer, a photopolymerization initiator, an aromatic tertiary amine having an electron-withdrawing group, an organic solvent, and a filler And a manufacturing method thereof.

In addition, the present invention provides an osseous adhesive comprising the adhesive composition.

Hereinafter, the present invention will be described in detail.

The present invention provides an adhesive composition comprising a compound of the formula (1).

[Chemical Formula 1]

In Formula 1,

P is a hydroxyl protecting group,

P represents a hydroxyl protecting group, and "hydroxyl protecting group" means a functional group that protects the hydroxyl group from undesired reaction during the synthesis procedure. The hydroxyl protecting group may be a silyl ether, a methyl ether, a C ₁ -C ₆ alkyl ether, a tetrahydropyranyl, or -SiR ₁ R ₂ R ₃ , but is preferably -SiR ₁ R ₂ R ₃ . Specifically, examples of hydroxyl protecting groups include methyl, ethyl, propyl, t-butyl, isopropyl, methoxymethyl (MOM), methylthiomethyl, t- butylthiomethyl, (phenyldimethylsilyl) methoxymethyl, benzyl Methoxyphenoxy) methyl, guaiacol methyl, t-butoxymethyl, 4-pentenyloxymethyl, siloxymethyl, 2-methoxyethoxymethyl Ethoxyethyl, 1- (2, chloroethoxy) methyl and 2- (trimethylsilyl) -ethoxymethyl), 1- Methyl-1-benzyloxyethyl, 1-methyl-1-benzyloxy-2-fluoroethyl, 2,2,2-trichloroethyl, 2- But are not limited to, trimethylsilyl, 2- (phenylselenyl) ethyl, allyl, p-chlorophenyl, p-methoxyphenyl, nitrobenzyl, p-nitrobenzyl, p-halobenzyl, 2,6-dichlorobenzyl, p-cyanobenzyl, And, examples of the -SiR ₁ R ₂ R ₃ is trimethylsilyl, triethylsilyl, tri-isopropyl silyl, dimethyl-isopropyl silyl, diethyl isopropyl silyl, dimethyl silyl teksil, tert- butyldimethylsilyl, di -tert- Butyldimethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl, tri-p-xylylsilyl, triphenylsilyl, diphenylmethylsilyl, tert-butyl (methoxy) diphenylsilyl and the like. The silylation step can be carried out according to standard methodology known to those skilled in the art.

The compound of Formula 1 is preferably a catechol derivative-based compound.

The catechol derivative is a compound containing a dihydroxy group and is capable of coordinating with a metal. Specifically, it is possible to use eugenol, 3,4-dihydroxyphenylalanine (DOPA), Dopa o-quinone, 2,4,5-trihydroxyphenylalanine TOPA or Topa quinone, And so on.

In order to solve the disadvantage that the oxidation stability of catechol is poor in the catechol derivative compound, the compound of the formula (1) may be substituted with the hydroxyl protecting group and various crosslinking agents may be used to improve the compatibility with other polymerizable monomers and oligomers Substituted catechol derivative-based compounds.

Specifically, the compound of Chemical Formula 1 may be a catechol derivative compound protected with -SiR ₁ R ₂ R ₃ represented by Chemical Formula 2, Chemical Formula 3 or Chemical Formula 4.

(2)

(3)

[Chemical Formula 4]

In Formula 2, Formula 3 or Formula 4,

R 1, R 2 or R 3 are each independently selected from the group consisting of hydrogen, a C ₁ to C ₁₀ linear or branched alkyl group, a C ₁ to C ₁₀ alkoxy, a C ₆ to C ₁₀ aryl group and a C ₆ to C ₁₀ heteroaryl group Lt; / RTI >

The compound of Formula 2 may be prepared as shown in Reaction Scheme 1 below.

[Reaction Scheme 1]

In Scheme 1, silyl-protected catechol (SPC) is prepared by reacting an eugenol and HSiR ₁ R ₂ R ₃ compound under tris pentafluorophenyl borane (TPFPB) (SPC) is reacted with pentane erythritol tetrakis (3-mercaptopropionate) (PETMP) to prepare a compound of formula (2). In addition, since PETMP contains four thiol groups, SPC can bond up to 1 to 4.

The compound of formula (3) or (4) can be prepared according to the following reaction formula (2).

[Reaction Scheme 2]

In Scheme 2, SPC and peroxoic acid are reacted under dichloromethane (DCM) to produce the compound of Formula 3, and the compound of Formula 3 is reacted with methacrylic acid to give the compound of Formula 4 Compounds can be prepared.

The compound of Formula 1 is preferably contained in an amount of 1 to 20% by weight based on the total weight of the adhesive composition.

The adhesive composition may further include a methacrylate-based polymerizable monomer, a photoinitiator, an aromatic tertiary amine having an electron-withdrawing group, an organic solvent, and a filler.

The methacrylate-based polymerizable monomer may be a polymerizable monomer containing a hydrophobic methacrylate functional group and having less volatility and polymerization shrinkage, quick curing, suitable molecular weight and high stability. Specific examples thereof include bis- (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA) Glycol dimethacrylate (EGDMA), ethoxylate bisphenol A dimethacrylate (Bis-EMA), urethane dimethacrylate (UDMA), anhydrous 4-methacryloxyethyl trimellitic acid (4-META) (PENTA), biphenyl dimethacrylate (BPDM), glycerol phosphate dimethacrylate (GPDM), propylene glycol dimethacrylate (PGDMA), and the like.

The methacrylate-based polymerizable monomer may be a polymerizable monomer having low viscosity and excellent hydrophilicity. Specific examples of the monomer include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 1,3-dihydroxypropyl methacrylate Methacrylate, 2-trimethylammonium ethyl methacrylate, polyethylene glycol dimethacrylate, and the like.

The content of the methacrylate monomer is not particularly limited, but is preferably 10 to 99% by weight, more preferably 10 to 90% by weight, based on the total weight of the composition. If the content of the monomer is 10% by weight or less, it is difficult to form a desired polymer and mixing with the filler is not easy. Conversely, if the content of the monomer is 99% by weight or more, the viscosity is not increased.

The initiator of the polymerization reaction may vary depending on the type of catalyst used in the polymerization reaction, such as a cation forming mechanism, an anion forming mechanism, and a radical forming mechanism, and a radical forming mechanism is most commonly used. Depending on the polymerization mechanism, the polymerization reaction may be performed by a photopolymerization reaction, a chemical polymerization reaction, or the like, but is not limited thereto.

The photopolymerization reaction is carried out by a photoinitiator which is activated by visible light or ultraviolet (UV) to initiate polymerization of the monomer, wherein the photoinitiator is selected from the group consisting of camphorquinone, benzyl, 2,3-pentanedione, benzyldimethylketal, Ketal, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, (2-methoxybenzoyl) phosphine oxide, tris (2,4-dimethoxybenzoyl) phosphine oxide, tris (2-methoxybenzoyl) phosphine oxide, dibenzoylphenylphosphine oxide, bis Dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl-bis (2,6-dimethylphenyl) ) Phosphonate, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 3,3'-carbonylbis (7-di No No) coumarin, 3- (4-methoxybenzoyl) and the like coumarin, 3-thenoyl coumarin.

The above-mentioned chemical polymerization reaction is carried out with a peroxide compound such as benzoyl peroxide (BPO), and is used together with an aromatic tertiary amine cocatalyst having an electron-withdrawing group, whereby radicals are formed by heat to initiate polymerization.

Examples of the aromatic tertiary amine having an electron attractive group include ethyl 4-N, N-dimethylaminobenzoate, methyl 4-N, N-dimethylaminobenzoate, 4-N, N-dimethylaminobenzoate, , 2-butoxyethyl N-dimethylaminobenzoate, 2- (methacryloyloxy) ethyl 4-N, N-dimethylaminobenzoate, and 4-N, N-dimethylaminobenzophenone.

The organic solvent may be methanol, ethanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, It is not.

The filler may be an inorganic filler, an organic filler, a stabilizer, or the like.

The inorganic filler may be, for example, amorphous synthetic silica, crystalline natural silica, barium aluminum silicate, kaolin, talc, strontium aluminum silicate, and the like, but may be other acid reactive fillers, nanosized zirconia fillers, and the like. In general, since the inorganic filler is hydrophilic, the compatibility with the hydrophobic polymerizable monomer is poor, and the inorganic filler can be surface-treated with a silane coupling agent to improve the affinity with the polymerizable monomer.

The organic filler can be prepared by preparing a monolayer constituting a matrix after polymerization in a dental restorative composition and a monomer having compatibility with it by bulk polymerization, emulsion polymerization, suspension polymerization, etc., May be used. In some cases, it is possible to increase the mechanical strength by increasing the curing molecular weight of the monomer without adding an inorganic or organic filler.

The stabilizer may preferably be a phenolic or phosphate stabilizer.

In addition, the adhesive composition may further include known compounds such as polymerization inhibitor, antioxidant, coloring agent, and fluorine additive.

The present invention also relates to a process for photopolymerizing a mixture of the compound of Formula 1, a methacrylate-based polymerizable monomer, a photopolymerization initiator, an aromatic tertiary amine having an electron-withdrawing group, an organic solvent, Of the present invention.

The photopolymerization is preferably performed for 1 to 24 hours under visible light or UV irradiation.

The bone adhesive can maintain the adhesive force even in the presence of water and can be used for underwater bonding.

The dental adhesive may be adhered to at least one substrate selected from the group consisting of biomaterial, plastic, glass, metal, and polymer synthetic resin, and may be used for adhering or fixing the substrate.

The dental adhesive can be used in a variety of formulations and can be used, for example, in the form of a liquid, cementitious, primer or root canal filling sealer.

The dental adhesive may be for the prevention or treatment of periodontal disease.

The dental adhesive according to the present invention is not only excellent in biocompatibility, but also exhibits excellent adhesive strength in teeth and various restorations.

The adhesive composition according to the present invention can be produced by incorporating a hydroxyl protecting group and various functional groups based on catechol derivative compounds, thereby exhibiting excellent biocompatibility, economic performance, and excellent adhesive strength under wet conditions. Therefore, There is an effect that it can be used as a bonding adhesive.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a scanning electron microscope (SEM) image of (a) Example 3-5 and (b) Comparative Example 3 for a dental root canal filling sealer.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.

Example 1. Preparation of functionalized catechol derivatives

1-1. Preparation of Silylated Catechol Derivatives (SPC)

The eugenol used in the examples was purchased from Sigma Aldrich and the triethylsilane and tris (pentafluorophenyl) borane (TPFPB) were purchased from Alpha (Alfa Aesar), and dichloromethane was purchased from JUNSEI and used.

First, 1 g of eugenol and 1.56 g of triethylsilane were mixed at room temperature and then stirred for 5 minutes. Thereafter, 18.7 mg of tris (pentafluorophenyl) borane, which is a reaction catalyst, was added to the mixture to react. After completion of the reaction, the product was dissolved in 10 ml of a dichloromethane solvent, and filtered with a syringe filter containing neutral alumina particles to remove the remaining tris (pentafluorophenyl) borane after the reaction to obtain a silylated catechol derivative (silyl- protected catechol, SPC).

1-2. Preparation of Epoxysilylated Catechol Derivatives

10 g of the silylated catechol derivative (SPC) prepared in Example 1-1 and 8.75 g of 3-chlorobenzoperoxoic acid were mixed in a dichloromethane solvent at 0 ° C., Lt; / RTI > Then, the dichloromethane present in the reaction mixture was volatilized, and the reaction mixture was extracted with ethyl acetate, washed twice with saturated sodium bisulfite solution, washed twice with saturated sodium bicarbonate solution, and then washed with ethyl acetate Was volatilized. The primary separated reaction mixture was then subjected to column chromatography using silica / nucleic acid: ethyl acetate (90:10) to separate the pure material to obtain the product, an epoxysilylated catechol derivative.

The results of ¹ H NMR measurement of the product are shown below.

^{_{1 H NMR (CDCl 3) 0.74}} (q, 12H, -Si-CH 2 CH 3) 0.98 (t, 18H, -Si-CH 2 CH 3) 2.52 (q, 1H, -CH 2 CH-O-CH 2 ) 2.69 (q, 1H, -CH 2 CH-O-CH 2) 2.78 (t, 1H, -CH 2 CH-O-CH 2) 2.81 (q, 1H, -CH 2 CH-O-CH 2) 3.11 _{(m, 1H, -CH 2 CH} -O-CH 2) 6.69 (d, 1H, Ar-H) 6.64 (q, 1H, Ar-H) 6.77 (d, 1H, Ar-H).

1-3. Preparation of methacrylated silylated catechol derivatives (Methacrylated SPC)

5 g of the epoxy silylated catechol derivative prepared in Example 1-2, 1.75 g of methacrylic acid and tetraethylammonium bromide as a catalyst were dissolved in 4-methoxyphenol (4 -Methoxyphenol) and reacted for 4 hours. The reaction mixture was then extracted with ethyl acetate, washed twice with saturated sodium bicarbonate solution, and then ethyl acetate was evaporated. The first separated reaction mixture was then subjected to column chromatography using silica / nucleic acid: ethyl acetate (90: 10) to separate the pure material, thereby obtaining a product, methacrylated silylated catechol derivative (Methacrylated SPC) .

The results of ¹ H NMR measurement of the product are shown below.

_{1H NMR (CDCl 3) 0.74 (} q, 12H, -Si-CH 2 CH 3) 0.98 (t, 18H, -Si-CH 2 CH 3) 1.95 (d, 3H, -CH 2 -C (CH 3) = _{CH 2) 2.20 (d, 1H} , -CH 2 CH (OH) CH 2 OOC-) 2.72 (m, 2H, -CH 2 CH (OH) CH 2 OOC-) 4.10 (q, 1H, -CH (OH) _{CH 2 OOC-) 4.22 (q,} 1H, -CH (OH) CH 2 OOC-) 5.58 (d, 1H, -CH 2 C (CH 3) = CH 2) 6.13 (d, 1H, -CH 2 C ( _{CH 3) = CH 2) 6.69} (d, 1H, Ar-H) 6.64 (q, 1H, Ar-H) 6.77 (d, 1H, Ar-H).

1-4. Manufacture of PETMP-SPC

The silylated catechol derivative (SPC) and pentaerythritol tetrakis (3-mercaptopropionate) (PETMP) prepared in Example 1-1 were dissolved in dimethoxy-2-phenylacetate And reacted with an equivalent ratio of 1: 1: 0.05 under a dimethoxy-2-phenylacetophenone catalyst to obtain PETMP-SPC.

Example 2. Preparation of adhesive composition

40% by weight of bisphenol A glycidylmethacrylate, 10% by weight of methacryloyloxyl-decyl-dihydrogen-phosphate (10-MDP) , 10% by weight of methacrylate-SPC and 36.5% by weight of ethanol were mixed. Then, 1% by weight of camphorquinone as a photopolymerization initiator and 2-butoxyethyl-4-dimethylaminobenzoate as a co- , And 2.5 wt%, to prepare a dental adhesive composition.

Example 3. Manufacture of dental adhesive

3-1. Preparation of liquid type dental adhesive 1

A liquid type dental adhesive 1 having the composition shown in the following Table 1, containing methacrylate-SPC (or PETMP-SPC) according to Example 1, was prepared.

Dental adhesive for liquid type 1 ingredient Content (% by weight) ethanol 35 water 2.3 Methacryloyloxypropoxy) phenyl) propane (Bis-GMA), 2,2-bis (4- 44 2-hydroxyethyl methacrylate (HEMA) 10 Methacrylate-SPC (or PETMP-SPC) 7 Campoquinone (CQ) One 4-N, N-dimethylaminobenzoic acid 2-butoxyethyl 0.7 sum 100

3-2. Preparation of liquid type dental adhesive 2

In Example 3-1, the content of methacrylate-SPC (or PETMP-SPC) was reduced to 5% by weight, and methacryloyloxyl-decyl-dihydrogen-phosphate 10-MDP) was added in an amount of 2% by weight, in the same manner as in Example 3-1.

3-3. Manufacture of cement type dental adhesive 1

Cement-type dental adhesive 1 in which the compositions of PETMP-SPC according to Example 1 were mixed with the compositions of the following Table 2 (first paste) and Table 3 (second paste) was prepared.

Cement type dental adhesive - First paste ingredient Content (% by weight) Methacryloyloxypropoxy) phenyl) propane (Bis-GMA), 2,2-bis (4- 30 Triethylene glycol dimethacrylate (TEGDMA) 10 Benzenesulfonic acid sodium salt One Campoquinone (CQ) 0.7 N, N-bis (2-hydroxyethyl) -p-toluidine (DHEPT) 0.3 Calcium aluminofluorosilicate glass 57 Amorphous synthetic silica One sum 100

Cement Type Dental Adhesive - Second Paste ingredient Content (% by weight) Methacryloyloxypropoxy) phenyl) propane (Bis-GMA), 2,2-bis (4- 5 PETMP-SPC 15 2-Hydroxyethyl methacrylate (HEMA) 15 Benzoyl peroxide (BPO) 0.5 Butylate Hydroxytoluene (BHT) 0.5 Barium aluminosilicate 63 Amorphous synthetic silica One sum 100

3-4. Manufacture of cement type dental adhesive 2

In Table 3 of Example 3-3, the content of PETMP-SPC was reduced to 10% by weight and the content of methacryloyloxyl-decyl-dihydrogen-phosphate (10-MDP) A cement-type dental adhesive 2 was prepared in the same manner as in Example 3-3, except that the content was changed to 5 wt%.

3-5. Manufacture of sealer 1 for dental root canal filling

Dental root canal filling sealer 1 containing PETMP-SPC according to Example 1 and having the compositions shown in Table 4 (first paste) and Table 5 (second paste) shown below was prepared.

Dental root canal filling sealer - First paste ingredient Content (% by weight) Bisphenol-A epoxy resin 46.7 PETMP-SPC 15 Calcium tungstate 30 Zirconium oxide 7.9 Amorphous synthetic silica 0.3 Iron oxide pigments 0.1 sum 100

Manufacture of dental cement - second paste ingredient Content (% by weight) Dibenzyldiamine < RTI ID = 0.0 > 11.3 Aminoadamantane 5.2 Tricyclodecane-diamine < RTI ID = 0.0 > 0.6 Calcium tungstate 64.7 Zirconium oxide 16.2 Amorphous synthetic silica 2 sum 100

3-6. Manufacture of sealer 2 for dental root canal filling

In Table 4 of Example 3-5, the content of PETMP-SPC was reduced to 10% by weight, and the content of methacryloyloxyl-decyl-dihydrogen-phosphate (10-MDP) Except that the content was changed to 5% by weight, a sealer 2 for dental root canal filling was prepared in the same manner as in Example 3-5.

Comparative Example 1. Preparation of a liquid type dental adhesive

A liquid type dental adhesive was prepared in the same manner as in Example 3-1, except that 7% by weight of 4-META was used instead of methacrylate-SPC (or PETMP-SPC) in Example 3-1.

Comparative Example 2 Preparation of cement type dental adhesive

A cement-type dental adhesive was prepared in the same manner as in Example 3-3, except that 15% by weight of 4-META was used instead of PETMP-SPC in Table 3 of Example 3-3.

Comparative Example 3: Preparation of dental canal filler sealer

A dental canal filler sealer was prepared in the same manner as in Example 3-5, except that 15% by weight of 4-META was used instead of PETMP-SPC in Table 4 of Example 3-5.

Experimental Example 1. Adhesive strength measurement

The adhesive strength to the dental adhesive according to Examples 3-1 to 3-4 and Comparative Examples 1 and 2 was measured. First, the tooth was polished so that the dentin layer of the tooth was exposed, and the surface of the tooth was corroded by acid treatment for 10 seconds with 35% phosphoric acid gel. Thereafter, water was removed from the surface of the teeth, and a dental adhesive was applied to a predetermined amount of tooth, followed by water repellency and photopolymerization to prepare a test piece. The prepared test pieces were put in distilled water and stored at 35 ° C. for 24 hours, and then the crosshead was moved at a rate of 0.8 mm / min using an universal testing machine to measure the adhesive strength. The results of the adhesion strength measurement are shown in Table 6.

Adhesive strength (MPa) Example 3-1 18.34 Example 3-2 20.30 Example 3-3 10.59 Example 3-4 11.32 Comparative Example 1 6.21 Comparative Example 2 3.85

As shown in Table 6, as a result of the evaluation of the adhesive strength, the dental adhesive according to Examples 3-1 to 3-4 containing methacrylate-SPC (or PETMP-SPC) of the present invention showed 4-META It was found that the adhesive strengths were superior to those of the adhesives according to Comparative Examples 1 and 2, Further, in the case of the liquid type adhesive of Example 3-2 and the cement type adhesive of Examples 3-4, as the addition of methacryloyloxy-decyl-dihydrogenphosphate (10-MDP) Respectively.

FIG. 1 shows Scanning Electron Microscopy (SEM) images of the adhesion between the dental root canal filling sealer of (a) Examples 3-5 and (b) of Comparative Example 3.

As shown in FIG. 1, it can be seen that the sealer for filling a dental root canal according to Example 3-5 exhibits excellent adhesive strength as compared with the sealer according to Comparative Example 3.

Claims

Claims 1. An adhesive composition comprising a compound of formula (1)
[Chemical Formula 1]

In Formula 1,
P is a hydroxyl protecting group,
L1 or L2 are each independently a hydrogen, hydroxyl group, C ₁ to C ₁₀ straight chain or an alkyl group branched chain, a C ₁ to C ₁₀ alkoxy group, an acrylate group, a methacrylate group, and pentane erythritol tetrakis ( Pentaerythritol tetrakis (3-mercaptopropionate), PETMP).

The method according to claim 1,
Wherein the compound of Formula 1 is a compound represented by Formula 2, Formula 3 or Formula 4 below.
(2)

(3)

[Chemical Formula 4]

In Formula 2, Formula 3 or Formula 4,
R 1, R 2 or R 3 are each independently selected from the group consisting of hydrogen, a C ₁ to C ₁₀ linear or branched alkyl group, a C ₁ to C ₁₀ alkoxy, a C ₆ to C ₁₀ aryl group and a C ₆ to C ₁₀ heteroaryl group Lt; / RTI >

The method according to claim 1,
Wherein the compound of Formula 1 is contained in an amount of 1 to 20% by weight based on the total weight of the adhesive composition.

The method according to claim 1,
Wherein the adhesive composition further comprises a methacrylate-based polymerizable monomer, a photoinitiator, an aromatic tertiary amine having an electron-withdrawing group, an organic solvent, and a filler.

5. The method of claim 4,
The methacrylate-based polymerizable monomer may be at least one selected from the group consisting of 2,2-bis- (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane (Bis-GMA), triethylene glycol dimethacrylate TEGDMA), ethylene glycol dimethacrylate (EGDMA), ethoxylate bisphenol A dimethacrylate (Bis-EMA), urethane dimethacrylate (UDMA), anhydrous 4-methacryloxyethyl trimellitic acid (PGDMA), dipentaerythrityl pentaacrylate monophosphate (PENTA), biphenyl dimethacrylate (BPDM), and glycerol phosphate dimethacrylate (GPDM), and propylene glycol dimethacrylate &Lt; / RTI > wherein the hydrophobic monomer is at least one hydrophobic monomer selected from the group consisting of acrylic acid and methacrylic acid.

5. The method of claim 4,
The methacrylate-based polymerizable monomer may be at least one selected from the group consisting of 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, Wherein the hydrophilic monomer is at least one hydrophilic monomer selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2-trimethylammonium ethyl methacrylate, and polyethylene glycol dimethacrylate. / RTI >

5. The method of claim 4,
Wherein the methacrylate monomer is contained in an amount of 10 to 99 wt% based on the total weight of the composition.

5. The method of claim 4,
The photopolymerization initiator may be at least one selected from the group consisting of camphorquinone, benzyl, 2,3-pentanedione, benzyldimethylketal, benzyldiethylketal, 2-chlorothioxanthone, (2,4,6-trimethylbenzoyl) phenylphosphine oxide, dibenzoylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, tris 2-methoxybenzoyl) phosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3, Benzyl-bis (2,6-dimethylphenyl) phosphonate, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 3,3'-carbonyl At least one selected from the group consisting of bis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, That is, the adhesive composition.

5. The method of claim 4,
The aromatic tertiary amine having an electron-withdrawing group may be 4-N, N-dimethylaminobenzoate, 4-N, N-dimethylaminobenzoate, 4-N, N- At least one selected from the group consisting of 2-butoxyethyl dimethylaminobenzoate, 2- (methacryloyloxy) ethyl 4-N, N-dimethylaminobenzoate and 4-N, N-dimethylaminobenzophenone By weight.

5. The method of claim 4,
The organic solvent may be at least one selected from the group consisting of methanol, ethanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane and tetrahydrofuran &Lt; / RTI >

5. The method of claim 4,
Wherein the filler is at least one inorganic filler selected from the group consisting of amorphous synthetic silica, crystalline natural silica, barium aluminum silicate, kaolin, talc, and strontium aluminum silicate.

A photopolymerization initiator, a photopolymerization initiator, a mixture of an aromatic tertiary amine having an electron-withdrawing group, an organic solvent, and a filler.
[Chemical Formula 1]

In Formula 1,
P is a hydroxyl protecting group,
L1 or L2 are each independently a hydrogen, hydroxyl group, C ₁ to C ₁₀ straight chain or an alkyl group branched chain, a C ₁ to C ₁₀ alkoxy group, an acrylate group, a methacrylate group, and pentane erythritol tetrakis ( Pentaerythritol tetrakis (3-mercaptopropionate). PETMP).

13. The method of claim 12,
Wherein said photopolymerization is carried out for from 1 to 24 hours under visible light or UV irradiation.

A bone adhesive comprising the adhesive composition of any one of claims 1 to 11.

15. The method of claim 14,
Characterized in that the bone adhesive is for bonding in water.

A dental adhesive comprising the adhesive composition of any one of claims 1 to 11.

17. The method of claim 16,
Wherein the dental adhesive is a formulation of a liquid type, a cement type, a primer or a root canal filling sealer.

17. The method of claim 16,
Wherein the dental adhesive is for prevention or treatment of periodontal disease.

An implant kit comprising the dental adhesive of claim 16.