KR102189253B1 - Universal Medical Adhesive Composition Containing Photo-polymerized Polymer with Multiple Catechol Groups and Cationic Inorganic Particles and Process for Preparing the Same - Google Patents

Abstract

It relates to a medical universal adhesive composition comprising a photopolymerizable polymer containing multiple catechol groups and surface-modified inorganic particles, and a method for manufacturing the same.According to the adhesive composition according to an aspect, the principle of mussel adhesive protein and inorganic particle technology are simultaneously applied. It has excellent physical and mechanical properties such as light conversion rate, polymerization contraction rate, water absorption rate and solubility, radiation transmittance, adhesion strength, etc., as well as low cytotoxicity and high adhesion properties, so that various medical or dental adhesives, for example , There is an effect that can be used for adhesion of prostheses including teeth or metals, ceramics, polymers, composite materials, or composite resins.

Description

TECHNICAL FIELD [Universal Medical Adhesive Composition Containing Photo-polymerized Polymer with Multiple Catechol Groups and Cationic Inorganic Particles and Process for Preparing the Same}

It relates to a medical universal adhesive composition comprising a photopolymerizable polymer including multiple catechol groups and surface-modified inorganic particles, and a method of manufacturing the same.

In general, adhesion of teeth is largely divided into enamel and dentin adhesion. Enamel is a hard tissue composed of 95% inorganic, 1% organic, and 4% moisture. In enamel adhesion, it is common to dissolve hydroxyapatite crystals by acid corrosion to expose the enamel rod to the surface, so that the adhesive penetrates and hardens, resulting in micromechanical bonding. The dentin of the tooth is composed of 70% inorganic, 20% organic, and 10% moisture. Compared to enamel, it is characterized by high organic material and moisture, and the adhesive composition also needs a different composition from enamel. Early dentin adhesives were close to hydrophobicity and did not penetrate well into the smear layer of dentin, so they showed low adhesive strength. To solve this problem, a hydrophilic monomer such as 2-hydroxyethyl methacrylate (HEMA) has been added, which allows the adhesive to soak into the dentin layer and to withstand wet environments. there was. However, the HEMA polymer has a disadvantage of low strength after polymerization.

On the other hand, recently, many studies using mussels as bioadhesive have been reported. Mussels produce and secrete functionally differentiated adhesives that allow them to adhere to themselves underwater in marine environments characterized by salinity, humidity, algae, turbulence, and waves. They adhere to the surface of the material in water using threads consisting of bundles of fibers secreted from the feet. At the end of each fiber is a plaque composed of a water-resistant adhesive that can adhere to a wet, solid surface. Such a joxa protein includes 3,4-dihydroxyphenyl-L-alanine (dopa), an amino acid obtained by hydration of a tyrosine group using a polyphenol oxidase.

Accordingly, the present inventors have tried to develop medical adhesives having excellent physical and mechanical properties and low cytotoxicity, and as a result, it has been confirmed that medical adhesives including photopolymerizable polymers including catechol groups and cationic inorganic particles have excellent physical and mechanical properties. By doing this, the present invention was completed.

In order to overcome the limitations of the prior art as described above, an aspect is to provide a medical adhesive composition comprising an adhesive monomer having a catechol functional group, which is a component of a mussel adhesive, and surface-modified inorganic particles.

In one aspect, an acrylic monomer containing a catechol group, or a photopolymerizable polymer composition (multifunctional prepolymer mixture) containing an acrylic monomer and a methacrylate monomer containing a catechol group; And it provides a medical adhesive composition comprising a cationic inorganic particles.

The acrylic monomer including the catechol group may be represented by the compound of Formula 1 below.

[Formula 1]

In Formula 1,

또는

이고, A is

or

ego,

Z is a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, a substituted or unsubstituted C ₂ -C ₂₀ alkenylene group, or a substituted or unsubstituted C ₂ -C ₂₀ alkynylene group, and the substitution is a hydroxyl group. , A cyano group, a nitro group, or an amino group,

Y is O or N,

X is H, a C _1-20 alkyl group, a C _2-20 alkenyl group, or a C _2-20 alkynyl group.

In the present specification, the C ₁ -C ₂₀ alkyl group refers to a linear or branched aliphatic hydrocarbon monovalent group having 1 to 20 carbon atoms, and specific examples include methyl group, ethyl group, propyl group, isobutyl group, sec-butyl group , ter-butyl group, pentyl group, iso-amyl group, or hexyl group. In the present specification, the C ₁ -C ₂₀ alkylene group may mean a divalent group having the same structure as the C ₁ -C ₂₀ alkyl group.

In the present specification, the C ₂ -C ₂₀ alkenyl group has a structure including one or more carbon double bonds in the middle or terminal of the C ₂ -C ₂₀ alkyl group, and specific examples thereof include ethenyl group, propenyl group, or butenyl group, etc. Can include. In the present specification, the C ₂ -C ₂₀ alkenylene group may mean a divalent group having the same structure as the C ₂ -C ₂₀ alkenyl group.

In the present specification, the C ₂ -C ₂₀ alkynyl group has a structure including one or more carbon triple bonds in the middle or terminal of the C ₂ -C ₂₀ alkyl group, and specific examples thereof include an ethynyl group or a propynyl group. ), etc. In the present specification, the C ₂ -C ₂₀ alkynylene group may mean a divalent group having the same structure as the C ₂ -C ₂₀ alkynyl group.

In one embodiment, the compound of Formula 1 may be catechol acrylate or catechol methacrylate.

In another embodiment, the compound of Formula 1 may be contained in an amount of 1 to 28% by weight based on the photopolymerizable polymer composition.

In one embodiment, the methacrylate-based monomer may be bisphenol A-glycidyl methacrylate (Bis-GMA).

In another embodiment, the methacrylate-based monomer is an adhesive monomer, (meth)acrylic acid, maleic acid, p-vinylbenzoic acid, 11-(meth)acryloxy-1,1-undecanedicarboxylic acid, 1, 4-di(meth)acryloyloxyethylpyromellitic acid, 6-(meth)acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid, 4-(meth)acryloyloxymethyltrimelli Tic acid and its anhydride, 4-(meth)acryloxyethyltrimellitic acid and its anhydride, 4-(meth)acryloxybutyltrimellitic acid and its anhydride, 4-[2-hydroxy-3-(meth)acrylo Yloxy]butyltrimelitic acid and anhydrides thereof, 2,3-bis(3,4-dicarboxybenzoyloxy)propyl (meth)acrylate, 2-, 3- or 4-(meth)acryloyloxybenzoic acid, NO-di(meth)acryloyloxytyrosine, O-(meth)acryloyloxytyrosine, N-(meth)acryloyloxytyrosine, N-(meth)acryloyloxyphenylalanine, N-(meth) Acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-O-aminobenzoic acid, addition product of glycidyl (meth)acrylate with N-phenylglycine or N-tolylglycine, 4-[(2 -Hydroxy-3-(meth)acryloyloxypropyl)amino]phthalic acid, 3- or 4-[N-methyl-N-2(-hydroxy-3-(meth)acryloyloxyamino]phthalic acid, (Meth)acryloylaminosalicylic acid and (meth)acryloyloxysalicylic acid, 3,3,4,4'-benzophenone tetracarboxylic anhydride (BTDA) or 3,3,4,4-diphenyltetracar (Meth)acrylate of acid dianhydride and 2-(3,4-dicarboxylbezoyloxy)1,3-di(meth)acryloyloxypropane, 2-(meth)acryloyloxyethyl phosphate, 2- and 3-(meth)acryloyloxypropyl phosphate, 4-(meth)acryloyloxybutyl phosphate, 6-(meth)acryloyloxyhexyl phosphate, 8-(meth)acryloyloxyoctyl phosphate , 10-(meth)acryloyloxydecyl phosphate, 12-(meth)acryloyloxydodecyl phosphate, bis{2-(meth)acryloyloxyethyl} phosphate, bis{2-(meth)acrylo Monooxyethylphenyl} phosphate, bis{2-(methyl)acryloyl oxyethyl p-methoxide Cyphenyl} phosphate, 2-sulfoethyl (meth)acrylate, 2- or 1-sulfo-1 or 2-propyl (meth)acrylate, 1- or 3-sulfo-2-butyl (meth)acrylate, 3 -Bromo-2-sulfo-2-propyl (meth)acrylate, 3-methoxy-1-sulfo-2-propyl (meth)acrylate, 1,1-dimethyl-2-sulfoethyl (meth)acrylamide It may be one selected from the group consisting of propanesulfonic acid and 2-methyl-2-(methyl)acrylamide propanesulfonic acid, or a mixture thereof.

In another embodiment, the methacrylate-based monomer is a hydrophilic monomer, and may be hydroxyethyl methacrylate, hydroxypropyl methacrylate, or a mixture thereof.

In one embodiment, the methacrylate-based monomer may be included in an amount of about 5 to 95% by weight based on the photopolymerizable polymer composition.

In one embodiment, the cationic inorganic particles may be connected with a catechol functional group. In addition, the cationic inorganic particles may have a surface modified with an amine group. Examples of the inorganic particle structure may include barium glass, silica (SiO ₂ ), titanium oxide (TiO ₂ ), zinc oxide (ZnO ₂ ), zirconium oxide (ZnO ₂ ), and the like. In addition, in order to modify the surface of the cationic inorganic particles with imine groups, aminopropyltriethoxysilane ((3-Aminopropyl)triethoxysilane), N-2-aminoethyl)-3-aminodecylaminopropyltrimethoxysilane (N -(2-aminoethyl)-3-aminopropyltrimethoxysilane), 3-trimethoxysilylpropyl diethylenetriamine) and p-(aminoethylaminomethyl)phenethyltrimethoxysilane (p-(aminoethyl-aminomethyl) ) It may be surface-modified with any one selected from the group consisting of) phenethyltrimethoxysilane). Specifically, as disclosed in FIG. 1, it may be surface-modified with a material containing various amine groups according to the four surface-modifying materials mentioned above.

In one embodiment, the cationic inorganic particles may be included in an amount of about 5 to 95% by weight based on the adhesive composition.

In one embodiment, the adhesive composition may include a photoinitiator system and/or a diluting solvent. The photoinitiator system may include a photoinitiator and/or a reducing agent. Specifically, the photoinitiator system may include 0.05 to 5% by weight of a photoinitiator and 0.05 to 5% by weight of a reducing agent. The photoinitiator may be camphorquinone (CQ), and the reducing agent may be N,N-dimethylaminoethyl metagrilate or ethyl p-dimethyl aminobenzoate. The diluting solvent may be selected from the group consisting of water, ethyl alcohol, acetone, and mixtures thereof.

When the photopolymerizable polymer composition of the adhesive composition of the present specification is exposed to a light source in the visible light region that is harmless to the human body, the photoinitiator and the reducing agent form radicals, and the generated radicals initiate polymerization reaction of the monomers to be cured. The polymerization reaction can mainly occur by visible light in a wavelength range of 400 to 500 nm using an α-diketone-based aliphatic and aromatic carbonyl compound photoinitiator and a tertiary amine-based reducing agent. The photoinitiator system referred to herein may include a photoinitiator and a reducing agent. An example of the photoinitiator may be camphorquinone as described above, and may be used in an amount of 0.05 to 5% by weight based on the total weight of the composition. Examples of reducing agents that deprive hydrogen by a photo-excited initiator and actually initiate radical polymerization are N,N-dimethylaminoethyl methacrylate (DMAEMA) and ethyl ρ-dimethyl aminobenzoate. -dimethylaminobenzoate, EDMAB), and the like, and may be used in an amount of 0.05 to 5% by weight based on the total weight of the composition. The photopolymerizable polymer of the present specification and the cationic inorganic particle may be connected through a Schiff base reaction between a catechol group and an amine group of the inorganic particle. Specifically, the adhesive composition of the present specification contains a catechol group, which is a mussel adhesive protein component, so that the amine group on the surface of the cationic inorganic particle and the Schiff base are formed as shown in FIG. It has stronger adhesion and mechanical properties than adhesive or cement.

In one embodiment, the medical adhesive composition may be a dental adhesive composition. The dental adhesive may be used in various formulations, for example, a liquid type, a cement type, a primer, or a formulation of a root canal filling sealer.

In another embodiment, the dental adhesive may be for the prevention or treatment of periodontal disease.

Another aspect provides an implant kit comprising the dental adhesive.

In addition, the adhesive composition may be used for bonding of teeth or prostheses including metals, ceramics, polymers, composite materials, or composite resins.

The adhesive according to an embodiment is not only excellent in biocompatibility, but also exhibits excellent adhesive strength in various restorations including teeth.

According to the adhesive composition according to an aspect, by simultaneously applying the principle of mussel adhesive protein and inorganic particle technology, not only excellent physical and mechanical properties such as light conversion rate, polymerization shrinkage rate, moisture absorption rate and solubility, radiation transmittance, and adhesive strength are excellent, but also Since it exhibits low cytotoxicity and high adhesion properties, there is an effect that can be used for adhesion of various medical or dental adhesives, for example, teeth or prostheses including metals, ceramics, polymers, composite materials, or composite resins. .

1 is a diagram schematically showing a structural formula in which an amine group is introduced into a cationic inorganic particle according to an embodiment.
2 is a diagram schematically showing a cationic inorganic particle according to an embodiment.
3 is a diagram schematically showing an adhesive composition according to an embodiment.
FIG. 4 is a diagram schematically showing that a universal medical adhesive composition including a photopolymerizable polymer including multiple catechol groups and inorganic particles is applied to a tooth according to an embodiment.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.

[Example]

Example 1.

1.1. Preparation of cationic inorganic particles

In order to prepare cationic inorganic particles, the surface of the inorganic particles was modified with inorganic particles.

Specifically, using 1 mL of inorganic particles and inorganic particles (barium glass, silica (SiO ₂ ), titanium oxide (TiO ₂ ), zinc oxide (ZnO ₂ ), and zirconium oxide (ZnO ₂ )) as nuclei, 9 mL of water and It was sufficiently dispersed in a mixed solution of 90 mL of ethanol. Thereafter, 0.1 mL of (3-aminopropyl)triethoxysilane (APTES) and 2.5 mL of aqueous ammonia were added and reacted at room temperature for 24 hours to form cationic inorganic particles.

2 is a diagram schematically showing a cationic inorganic particle according to an embodiment.

As shown in FIG. 2, inorganic particles including amine groups may be synthesized based on inorganic compounds, and the surface is modified with amine groups to constitute a silica layer including a plurality of amine groups.

1.2. Preparation of photopolymerizable polymer adhesive composition in which cationic inorganic particles are bound

10% by weight of the cationic polymer inorganic particles prepared in Example 1.1, 28% by weight of catechol acrylate, 16% by weight of Bis-GMA, and triethylene glycol dimethacrylate (TEGDMA) 4% by weight, distilled water 10% by weight, 10-methacryloyloxydecyldihydrogen phosphate 2% by weight, bis(methacryloyloxy)ethyl phosphate 2% by weight, (2-hydroxyethyl)methacrylate 5 Wt%, polyurethane dimethacrylate 10 wt%, ethyl alcohol 10 wt%, ethyl-4-(dimethylamino)benzoate 1 wt%, camphorquinone 1 wt%, 2,6-di(tersary- 1% by weight of butyl)-4-methylphenol was mixed. Thereafter, a photopolymerization reaction was performed by irradiating a visible light wavelength in a region of 400 to 500 nm for 20 to 40 seconds to prepare a photopolymerization polymer adhesive composition.

3 is a diagram schematically showing an adhesive composition according to an embodiment.

As shown in FIG. 3, the adhesive composition according to an embodiment contains a catechol group, which is a mussel adhesive protein component, so that the conventional photopolymerization dental adhesive through the formation of an amine group on the surface of the cationic inorganic particle and a Schiff base Or, it has stronger adhesion and mechanical properties than cement.

FIG. 4 is a diagram schematically showing that a universal medical adhesive composition including a photopolymerizable polymer including multiple catechol groups and inorganic particles is applied to a tooth according to an embodiment.

As shown in Fig. 4, a mixture of prepolymers (photopolymers) including catechol groups and inorganic particles including amine groups is cured by irradiation with visible light, which provides a medical adhesive and cement. In addition, the catechol group-containing prepolymer is radically polymerized by a photoinitiator under visible light, while the catechol group and the amine group on the surface of the cationic inorganic particles form a Schiff base to form a Schiff base, and conventional photopolymerization in various prosthetics and composite resins or teeth. It has stronger adhesion and mechanical properties than dental adhesives or cements.

Example 2.

An adhesive composition was prepared in the same manner as in Example 1, except that catechol methacrylate was used instead of catechol acrylate in Example 1.2.

Example 3.

An adhesive composition was prepared in the same manner as in Example 1, except that barium glass surface-modified with the type of inorganic particles was used in Example 1.1.

Example 4.

An adhesive composition was prepared in the same manner as in Example 1, except that silica silica (SiO ₂ ) surface-modified as the type of inorganic particles was used in Example 1.1.

Example 5.

Except that the titanium oxide (TiO ₂ ) surface-modified as the type of inorganic particles in Example 1.1. was used, an adhesive composition was prepared in the same manner as in Example 1.

Example 6.

An adhesive composition was prepared in the same manner as in Example 1, except that the zinc oxide (ZnO ₂ ) surface-modified as the type of inorganic particles was used in Example 1.1.

Example 7.

An adhesive composition was prepared in the same manner as in Example 1, except that zirconium oxide (ZnO ₂ ) was used as the type of inorganic particles in Example 1.1.

Comparative Example 1.

In Example 1, except for using 4-methacryloyloxyethy trimellitate anhydride (4-META) instead of catechol acrylate), Example 1 The adhesive composition was prepared in the same manner as described above.

Comparative Example 2.

The same method as in Example 4 except for containing 4-methacryloyloxyethy trimellitate anhydride (4-META) instead of catechol acrylate in Example 2 A photopolymerization type dental adhesive composition was prepared. The dentin adhesive strength of the prepared composition was measured as 25 MPa.

Comparative Example 3.

In Example 1, instead of the cationic inorganic particles, inorganic particles (barium glass, silica (SiO ₂ ), titanium oxide (TiO ₂ ), zinc oxide (ZnO ₂ ), and zirconium oxide (ZnO ₂ )) that do not contain an amine group were used. Except for using only, an adhesive composition was prepared in the same manner as in Example 1.

Comparative Example 4.

In the above Example 2, instead of the cationic inorganic particles, inorganic particles (barium glass, silica (SiO ₂ ), titanium oxide (TiO ₂ ), zinc oxide (ZnO ₂ ), and zirconium oxide (ZnO ₂ )) that do not contain an amine group Except for using only, an adhesive composition was prepared in the same manner as in Example 2.

Experimental example. Measurement of adhesive strength

The adhesive strength of the adhesive composition was measured by Instron.

Specifically, the bovine tooth specimen was polished with 320 grit SiC paper on the occlusal surface with a microtome to expose the dentin. Finally, the surface of each tooth was rinsed with water and lightly air dried. The adhesives of Examples 1 to 7 and Comparative Examples 1 to 4 were filled in a test mold (diameter: 5 mm), fixed directly on the tooth surface, and photocured at 36° C. and 100% relative humidity for 20 seconds. Adhesive strength was measured using an Instron device. The measured values of the adhesive strength are shown in Table 1 below.

Adhesive composition Adhesive strength Example 1 30 MPa Example 2 32 MPa Example 3 32 MPa Example 4 30 MPa Example 5 34 MPa Example 6 32 MPa Example 7 30 MPa Comparative Example 1 21 MPa Comparative Example 2 25 MPa Comparative Example 3 15 MPa Comparative Example 4 15 MPa

As shown in Table 1, it was confirmed that the adhesive composition of the adhesive composition according to the embodiment was significantly increased by about 1.5 to 2.2 times compared to the comparative example.

In addition, the adhesive composition according to an embodiment has excellent physical and mechanical properties such as light conversion rate, polymerization shrinkage rate, moisture absorption rate and solubility, radiation transmittance, adhesive strength, etc., because catechol, which is a hop bonding protein, and inorganic particle technology are simultaneously applied. And showed low cytotoxicity.

Claims (14)

A compound of the following formula 1 containing a catechol functional group, or
A photopolymerizable polymer composition comprising a compound of Formula 1 and a methacrylate-based monomer including a catechol functional group; And
A medical adhesive composition comprising a cationic inorganic particle connected to the catechol functional group, wherein the cationic inorganic particle is modified with an amine group on the surface, and the photopolymerizable polymer and the cationic inorganic particle have a catechol group and an amine group of the inorganic particle The adhesive composition is connected through a Schiff base reaction therebetween;
[Formula 1]

In Formula 1,
A is

or

ego,
Z is a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, a substituted or unsubstituted C ₂ -C ₂₀ alkenylene group, or a substituted or unsubstituted C ₂ -C ₂₀ alkynylene group, and the substitution is a hydroxyl group. , A cyano group, a nitro group, or an amino group,
Y is O or N,
X is H, a C _1-20 alkyl group, a C _2-20 alkenyl group, or a C _2-20 alkynyl group. delete The method of claim 1, wherein the cationic inorganic particles are aminopropyltriethoxysilane ((3-Aminopropyl)triethoxysilane), N-2-aminoethyl)-3-aminodecylaminopropyltrimethoxysilane (N-(2- aminoethyl)-3-aminopropyltrimethoxysilane), 3-trimethoxysilylpropyl diethylenetriamine) and p-(aminoethylaminomethyl)phenethyltrimethoxysilane (p-(aminoethyl-aminomethyl)phenethyltrimethoxysilane) The adhesive composition that is surface-modified with any one selected from the group consisting of. The adhesive of claim 1, wherein the inorganic particles are barium glass, silica (SiO ₂ ), titanium oxide (TiO ₂ ), zinc oxide (ZnO ₂ ), and zirconium oxide (ZnO ₂ ). Composition. The method of claim 1, wherein the methacrylate-based monomer is bisphenol A-glycidyl methacrylate (Bis-GMA), hydroxyethyl methacrylate, hydroxypropyl methacrylate, (meth)acrylic acid, maleic acid, p -Vinylbenzoic acid, 11-(meth)acryloxy-1,1-undecanedicarboxylic acid, 1,4-di(meth)acryloyloxyethylpyromellitic acid, 6-(meth)acryloyloxyethylnaphthalene -1,2,6-tricarboxylic acid, 4-(meth)acryloyloxymethyltrimellitic acid and its anhydrides, 4-(meth)acryloxyethyltrimellitic acid and its anhydrides, 4-(meth)acrylic Roxybutyltrimellitic acid and its anhydride, 4-[2-hydroxy-3-(meth)acryloyloxy]butyltrimellitic acid and its anhydride, 2,3-bis(3,4-dicarboxybenzoyloxy) Propyl (meth)acrylate, 2-, 3- or 4-(meth)acryloyloxybenzoic acid, NO-di(meth)acryloyloxytyrosine, O-(meth)acryloyloxytyrosine, N-( Meth)acryloyloxytyrosine, N-(meth)acryloyloxyphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-O-aminobenzoic acid, glycidyl Adduct product of (meth)acrylate with N-phenylglycine or N-tolylglycine, 4-[(2-hydroxy-3-(meth)acryloyloxypropyl)amino]phthalic acid, 3- or 4-[N -Methyl-N-2(-hydroxy-3-(meth)acryloyloxyamino]phthalic acid, (meth)acryloylaminosalicylic acid and (meth)acryloyloxysalicylic acid, 3,3,4,4' -Benzophenone tetracarboxylic anhydride (BTDA) or (meth)acrylate of 3,3,4,4-diphenyltetracarboxylic dianhydride and 2-(3,4-dicarboxylbezoyloxy)1, 3-di(meth)acryloyloxypropane, 2-(meth)acryloyloxyethyl phosphate, 2- and 3-(meth)acryloyloxypropyl phosphate, 4-(meth)acryloyloxybutyl phosphate , 6-(meth)acryloyloxyhexyl phosphate, 8-(meth)acryloyloxyoctyl phosphate, 10-(meth)acryloyloxydecyl phosphate, 12-(meth)acryloyloxydodecyl phosphate, Bis{2-(meth)acryloyloxyethyl} phosphate, bis{2- (Meth)acryloyloxyethylphenyl} phosphate, bis{2-(methyl)acryloyl oxyethyl p-methoxyphenyl} phosphate, 2-sulfoethyl (meth)acrylate, 2- or 1-sulfo-1 Or 2-propyl (meth)acrylate, 1- or 3-sulfo-2-butyl (meth)acrylate, 3-bromo-2-sulfo-2-propyl (meth)acrylate, 3-methoxy-1 -Sulfo-2-propyl (meth)acrylate, 1,1-dimethyl-2-sulfoethyl (meth)acrylamide propanesulfonic acid and 2-methyl-2- (methyl) acrylamide propanesulfonic acid, or a mixture thereof The adhesive composition is selected from the group. delete The adhesive composition of claim 1, wherein the compound of Formula 1 is catechol acrylate or catechol ethacrylate. The adhesive composition of claim 1, further comprising a photoinitiator system or a diluting solvent. The method of claim 8, wherein the photoinitiator system comprises 0.05 to 5% by weight of a photoinitiator and 0.05 to 5% by weight of a reducing agent based on the total composition, the photoinitiator is camphorquinone, and the reducing agent is N,N-dimethylaminoethyl meta The adhesive composition that is grate or ethyl p-dimethyl aminobenzoate. The adhesive composition of claim 8, wherein the diluting solvent is selected from the group consisting of water, ethyl alcohol, acetone, and mixtures thereof. The adhesive composition of claim 1, comprising 1 to 28% by weight of the compound of Formula 1 based on the photopolymerizable polymer composition. The adhesive composition according to claim 1, comprising 5 to 95% by weight of a methacrylate-based monomer based on the photopolymerizable polymer composition. The adhesive composition according to claim 1, comprising 5 to 95% by weight of cationic inorganic particles based on the adhesive composition. The adhesive composition of claim 1, which is for dental use.

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