Two-component curable composition with significantly improved rapid curability at room temperature and adhesive composition obtained therefrom

Abstract

The present invention relates to a two-component curable composition with significantly improved rapid curability at room temperature and an adhesive composition obtained therefrom and, more specifically, to: a two-component curable composition in which radical polymerization occurs by an oxidation-reduction reaction between an oxidizing agent and a radical initiator specifically included in respective two components of the composition, thereby exhibiting significantly improved rapid curability at room temperature and excellent metal adhesion compared to conventional two-component curable compositions, as well as excellent storage stability at room temperature; and an adhesive composition obtained therefrom.

Description

A two-component curable composition with significantly improved room temperature curing properties and an adhesive composition obtained therefrom

[0001] The present invention relates to a two-component curable composition with significantly improved room-temperature fast-curing properties and an adhesive composition obtained therefrom, and more specifically, to a two-component curable composition which exhibits significantly improved room-temperature fast-curing properties and excellent metal adhesion properties compared to existing two-component curable compositions, and also excellent room-temperature storage stability, by causing radical polymerization by an oxidation-reduction reaction of an oxidizing agent and a radical initiator specifically included in each of the two components of the composition.

[0002] Various adhesive compositions have been developed for bonding between metals or between metal materials and non-metal materials (e.g., organic materials such as plastic materials).

[0003] For example, Japanese Patent Application Laid-Open No. 2006-124414 discloses a two-component acrylic adhesive composition comprising Agent X containing an organic peroxide and Agent Y containing a vanadium compound and an acidic phosphoric acid compound (redox polymerization initiator), and Korean Patent Application Laid-Open No. 10-2012-0001817 discloses a room temperature curable resin composition comprising a polymerizable vinyl monomer, an organic peroxide, and a thiourea derivative.

[0004] However, the peroxides used as oxidizers in the above-described prior arts are generally flammable or combustible substances, making them unstable and posing a risk during the process. Furthermore, the disclosed compositions lack room-temperature curing properties.

[0005] Korean Patent Publication No. 10-2021-0110851 discloses an adhesive composition comprising a manganese-containing or iron-containing salt and a 1,3-dioxo compound as a radical polymerizable composition, which enables room temperature curing without using a peroxide having the above-mentioned disadvantages, but this composition also does not have room temperature fast curing properties.

[0006] Accordingly, there is a demand for the development of an adhesive composition that can solve the problems of the above-mentioned conventional technologies, that is, that can be cured at room temperature without using peroxide, and further has improved room temperature rapid curing characteristics.

[0007] The purpose of the present invention is to provide a two-component curable composition which exhibits significantly improved room temperature fast curing properties (e.g., curing within 5 minutes after being left at room temperature) and excellent metal adhesion properties compared to existing two-component curable compositions (e.g., curing within 3 minutes after being left at room temperature), as well as excellent room temperature storage stability, and an adhesive composition obtained therefrom.

[0008] In order to achieve the above-mentioned object, the present invention provides a two-component curable composition comprising (i) agent A comprising a polymerizable compound and an oxidizing agent; and (ii) agent B comprising a polymerizable compound and a radical initiator; wherein the oxidizing agent comprises a manganese compound and the radical initiator comprises a phosphorus compound and a dicarbonyl compound.

[0009] According to another aspect of the present invention, an adhesive composition is provided obtained by mixing agent A and agent B included in the two-component curable composition of the present invention.

[0010] According to another aspect of the present invention, a method for producing an adhesive composition is provided, comprising a step of mixing agent A and agent B, wherein agent A includes a polymerizable compound and an oxidizing agent, agent B includes a polymerizable compound and a radical initiator, the oxidizing agent includes a manganese compound, and the radical initiator includes a phosphorus compound and a dicarbonyl compound.

[0011] According to another aspect of the present invention, an article to which the adhesive composition of the present invention is applied is provided.

[0012] According to the present invention, each of Agent A and Agent B included in a two-component curable composition exhibits excellent storage stability at room temperature, and when they are mixed at room temperature, radical polymerization occurs by an oxidation-reduction reaction of a manganese compound, a phosphorus compound, and a dicarbonyl compound included in each of Agent A and Agent B, thereby obtaining significantly improved room temperature rapid curing properties (e.g., curing within 3 minutes after being left at room temperature) and excellent metal adhesion compared to existing two-component curable compositions (e.g., curing within 5 minutes after being left at room temperature).

[0013] Hereinafter, the present invention will be described in more detail.

[0014] As used herein, the term “(meth)acrylic” includes acrylic, methacrylic or a combination thereof, and the term “(meth)acrylate” includes acrylate, methacrylate or a combination thereof.

[0015] In this specification, the term “room temperature” (also referred to as “room temperature”) has its usual meaning and may be, for example, a temperature within the range of 15°C to 35°C, more specifically 18°C ​​to 33°C, and even more specifically 20°C to 30°C, but is not limited thereto.

[0016] The term “room temperature curing” in this specification means that when a mixture of agents A and B included in a two-component curable composition (which may correspond to the adhesive composition of the present invention) is left at room temperature, the mixture is cured within 3 minutes after leaving.

[0017] Hereinafter, the components included in the two-component curable composition of the present invention will be described in more detail.

[0018] The two-component curable composition of the present invention comprises (i) agent A comprising a polymerizable compound and an oxidizing agent; and (ii) agent B comprising a polymerizable compound and a radical initiator; wherein the oxidizing agent comprises a manganese compound, and the radical initiator comprises a phosphorus compound and a dicarbonyl compound.

[0019] [Manganese compounds]

[0020] The two-component curable composition of the present invention comprises agent A, which includes a polymerizable compound and an oxidizing agent, wherein the oxidizing agent includes a manganese compound.

[0021] In the present invention, the manganese compound content in the agent A is more than 0.009 parts by weight and less than 5.5 parts by weight based on 100 parts by weight of the total agent A.

[0022] In the present invention, when the manganese compound content in Agent A is greater than 0.009 parts by weight and less than 5.5 parts by weight based on 100 parts by weight of Agent A, the room temperature curing speed, room temperature storage stability, and metal adhesion can be further improved.

[0023] In one specific example, the manganese compound content in the total 100 parts by weight of the A agent may be, for example, 0.0091 parts by weight or more, 0.0095 parts by weight or more, or 0.01 parts by weight or more, and may also be 5.4 parts by weight or less, 5.3 parts by weight or less, 5.2 parts by weight or less, 5.1 parts by weight or less, 5 parts by weight or less, 4.5 parts by weight or less, 4 parts by weight or less, 3.5 parts by weight or less, or 3 parts by weight or less, but is not limited thereto.

[0024] In one specific example, the manganese compound is, for example, manganese(III) acetate (Mn(OAc)3), manganese(II) acetate (Mn(OAc)2), manganese(III) acetylacetonate (Mn(acac)3), manganese(II) acetylacetonate (Mn(acac)2), manganese dioxide (MnO2), manganese trioxide (Mn2O3), manganese chloride (MnCl2), manganese carbonate (MnCO3), manganese(II) sulfate (MnSO4), manganese 2-ethylhexanoate, potassium manganese salt (KMnO₄), manganese calcium oxide (CaMnO₃), sodium manganese salt (NaMnO₄), ammonium manganese salt ((NH₄)MnO₄), manganese acid, manganese ferrocyanate, manganese(II) phthalocyanine or any of these. Includes, but is not particularly limited to, one or more selected from a group consisting of combinations.

[0025] [Person compound]

[0026] The two-component curable composition of the present invention comprises a B agent including a polymerizable compound and a radical initiator, wherein the radical initiator comprises a phosphorus compound.

[0027] In the present invention, the content of the phosphorus compound in the B agent is more than 0.04 parts by weight and less than 20.5 parts by weight based on 100 parts by weight of the total B agent.

[0028] In the present invention, when the content of the phosphorus compound in Agent B is greater than 0.04 parts by weight and less than 20.5 parts by weight based on 100 parts by weight of the total Agent B, the room temperature curing speed, room temperature storage stability, and metal adhesion can be further improved.

[0029] In one specific example, the content of the phosphorus compound in the total 100 parts by weight of the B agent may be, for example, 0.041 parts by weight or more, 0.042 parts by weight or more, 0.043 parts by weight or more, 0.044 parts by weight or more, 0.045 parts by weight or more, 0.046 parts by weight or more, 0.047 parts by weight or more, 0.048 parts by weight or more, 0.049 parts by weight or more, or 0.05 parts by weight or more, and may also be 20.4 parts by weight or less, 20.3 parts by weight or less, 20.2 parts by weight or less, 20.1 parts by weight or less, or 20 parts by weight or less, but is not limited thereto.

[0030] In one specific embodiment, the phosphorus compound includes, but is not particularly limited to, one or more selected from the group consisting of dibutyl phosphate, diphenyl phosphate, phenyl phosphate, mono(meth)acryloyloxyethyl phosphate, di(meth)acryloyloxyethyl phosphate, ethylene diphosphate, aminotrimethylene phosphate, phenylphosphonic dichloride, isopropyl acid phosphate, diisopropyl acid phosphate, isopropylphenyl phosphate, ortho phosphoric acid, polyphosphoric acid, butyl pyrophosphate, pyrophosphoric acid, or a combination thereof.

[0031] [Dicarbonyl compound]

[0032] The two-component curable composition of the present invention comprises a B agent including a polymerizable compound and a radical initiator, wherein the radical initiator further comprises a dicarbonyl compound in addition to a phosphorus compound.

[0033] In the present invention, the content of the dicarbonyl compound in the B agent is more than 0.005 parts by weight and less than 11 parts by weight based on 100 parts by weight of the total of B agent.

[0034] In the present invention, when the dicarbonyl compound content in Agent B is greater than 0.005 parts by weight and less than 11 parts by weight based on 100 parts by weight of the total Agent B, the room temperature curing speed and metal adhesion can be further improved.

[0035] In one specific example, the content of the dicarbonyl compound in the total 100 parts by weight of the B agent may be, for example, 0.0051 parts by weight or more, 0.006 parts by weight or more, 0.007 parts by weight or more, 0.008 parts by weight or more, 0.009 parts by weight or more, or 0.01 parts by weight or more, and may also be 10.9 parts by weight or less, 10.8 parts by weight or less, 10.7 parts by weight or less, 10.6 parts by weight or less, 10.5 parts by weight or less, 10.4 parts by weight or less, 10.3 parts by weight or less, 10.2 parts by weight or less, 10.1 parts by weight or less, or 10 parts by weight or less, but is not limited thereto.

[0036] In one specific example, the dicarbonyl compound may be at least one selected from the group consisting of a 1,2-dicarbonyl compound, a 1,3-dicarbonyl compound, a 1,4-dicarbonyl compound, or a combination thereof, and preferably a 1,3-dicarbonyl compound.

[0037] In one specific example, the 1,2-dicarbonyl compound comprises at least one selected from the group consisting of diacetyl, glyoxal, 1,2-ketoaldehyde, benzyl, 2,3-pentanedione, ethanedioic acid, formylcarboxylic acid, or a combination thereof, but is not particularly limited thereto, the 1,3-dicarbonyl compound comprises at least one selected from the group consisting of acetylacetone, methyl acetoacetate, dimethylmalonate, ethyl-2-methylacetoacetate, N-methylacetoacetamide, acetoacetamide, 2-acetylbutyrolactone, 2-acetylcyclopentanone, ethyldiacetoacetate, dihydroacetic acid, or a combination thereof, but is not particularly limited thereto, and the 1,4-dicarbonyl compound comprises at least one selected from the group consisting of succinic aldehyde, ethylacetoacetate, phthalaldehyde, Including, but not particularly limited to, one or more selected from the group consisting of 1,4-benzoquinone, acetonylacetone, malic acid, citric acid, adipic acid, glutaric acid or a combination thereof.

[0038] [Polymerizable compound]

[0039] Each of Agent A and Agent B included in the two-component curable composition of the present invention includes a polymerizable compound.

[0040] In one specific example, the content of the polymerizable compound in the agent A may be greater than 94.5 parts by weight and less than 99.991 parts by weight based on 100 parts by weight of the total agent A, and more specifically, the content of the polymerizable compound in the total 100 parts by weight of the agent A may be, for example, 94.6 parts by weight or more, 94.7 parts by weight or more, 94.8 parts by weight or more, 94.9 parts by weight or more, or 95 parts by weight or more, and may also be 99.9909 parts by weight or less, 99.9905 parts by weight or less, or 99.99 parts by weight or less, but is not limited thereto.

[0041] In one specific example, the content of the polymerizable compound in the B agent may be greater than 68.5 parts by weight and less than 99.955 parts by weight based on 100 parts by weight of the total of the B agent, and more specifically, the content of the polymerizable compound in the 100 parts by weight of the total of the B agent may be, for example, 68.6 parts by weight or more, 69 parts by weight or more, 69.5 parts by weight or more, or 70 parts by weight or more, and may also be 99.954 parts by weight or less, 99.95 parts by weight or less, 99.945 parts by weight or less, or 99.94 parts by weight or less, but is not limited thereto.

[0042] In one specific example, independently for each of agent A and agent B, the polymerizable compound may be at least one selected from the group consisting of a polymerizable monomer, a polymerizable oligomer, or a combination thereof.

[0043] In one specific example, the polymerizable monomer or polymerizable oligomer may include one or more (preferably 1 to 4) (meth)acrylic groups in the molecule, for example, the polymerizable monomer may include a (meth)acrylic monomer having one or more (meth)acrylic groups, and any (meth)acrylate known as a (meth)acrylic monomer may be used without any particular limitation.

[0044] In one specific example, the (meth)acrylic monomer having one (meth)acrylic group in the molecule includes, for example, (meth)acrylic acid, lauryl (meth)acrylate, stearyl (meth)acrylate, ethylcarbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, nonylphenoxyethyl (meth)acrylate, nonylphenoxytetraethylene glycol (meth)acrylate, Methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxyethyl (meth)acrylate, butoxytriethylene glycol (meth)acrylate, 2-ethylhexyl polyethylene glycol (meth)acrylate, nonylphenyl polypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, epichlorohydrin (hereinafter abbreviated as ECH)-modified butyl (meth)acrylate, ECH-modified phenoxy (meth)acrylate, ethylene oxide (hereinafter abbreviated as EO)-modified Examples thereof include, but are not limited to, phthalic acid (meth)acrylate, EO-modified succinic acid (meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 3-trimethoxysilylpropyl (meth)acrylate, 3-triethoxysilylpropyl (meth)acrylate, 3-methyldimethoxysilylpropyl (meth)acrylate, (meth)acryloxypropyltriisoproxysilane, or combinations thereof.

[0045] In addition, examples of (meth)acrylic monomers having two or more (e.g., 2 to 4) (meth)acrylic groups in the molecule include 1,6-hexanediol diacrylate (HDDA), butanediol diacrylate (BDDA), diethylene glycol dimethacrylate (DEGDMA), triethylene glycol dimethacrylate (TEGDMA), tripropylene glycol diacrylate (TPGDA), bisphenol A [EO]4~30 diacrylate (BPA[EO]4~30DA, EO is an ethylene oxide unit), and trimethylolpropane triacrylate. triacrylate (TMPTA), trimethylolpropane [EO]3~15 triacrylate (TMP[EO]3~15TA, EO is ethylene oxide unit), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PETTA), ditrimethylolpropane tetraacrylate (DTMPTTA), dipentaerythritol pentaacrylate (DPPA), dipentaerythritol hexaacrylate (DPHA), 1,3-bis-(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane, 1,3-bis-(3-methacryloxypropyl)tetramethyldisiloxane or combinations thereof, but are not limited thereto.

[0046] In one specific embodiment, the polymerizable oligomer may include one or more (preferably 1 to 4) (meth)acrylic groups in the molecule, for example, the polymerizable oligomer may include a (meth)acrylic oligomer having one or more (meth)acrylic groups, and the (meth)acrylic oligomer may be one or more selected from the group consisting of (meth)acrylic-modified polyurethane, (meth)acrylic-modified epoxy, (meth)acrylic-modified silicone-based compound, or a combination thereof.

[0047] In one embodiment, the (meth)acryl-modified polyurethane may include at least one selected from the group consisting of hydrophilic (meth)acryl-modified polyurethane, lipophilic (meth)acryl-modified polyurethane, or a combination thereof.

[0048] In one specific example, the hydrophilic (meth)acryl-modified polyurethane may include polymerized units derived from a hydrophilic polyol; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate.

[0049] In one specific example, the hydrophilic polyol included as a polymerization unit in the hydrophilic (meth)acryl-modified polyurethane may be used without particular limitation as long as it is a polyol having hydrophilicity, and may be, for example, one or more selected from polyethylene glycol, anhydrous sugar alcohol-alkylene oxide adducts, or a combination thereof.

[0050] In one specific example, the hydrophilic (meth)acryl-modified polyurethane may include polymerized units derived from polyethylene glycol; polymerized units derived from polyisocyanate; and polymerized units derived from hydroxyalkyl (meth)acrylate.

[0051] In one specific example, the hydrophilic (meth)acryl-modified polyurethane may include polymerized units derived from an anhydrous sugar alcohol-alkylene oxide adduct; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate.

[0052] In one specific example, the lipophilic (meth)acryl-modified polyurethane may include polymerized units derived from a lipophilic polyol; polymerized units derived from a polyisocyanate; and polymerized units derived from a hydroxyalkyl (meth)acrylate.

[0053] In one specific example, when the (meth)acryl-modified polyurethane is a combination of a hydrophilic (meth)acryl-modified polyurethane and a lipophilic (meth)acryl-modified polyurethane, it may include 16 to 84 parts by weight of the hydrophilic (meth)acryl-modified polyurethane and 16 to 84 parts by weight of the lipophilic (meth)acryl-modified polyurethane based on 100 parts by weight of the total (meth)acryl-modified polyurethane, and more specifically, within 100 parts by weight of the total (meth)acryl-modified polyurethane, the hydrophilic and lipophilic (meth)acryl-modified polyurethane may be included in an amount of 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, or 20 parts by weight or more, respectively, and also the hydrophilic and lipophilic (Meth)acrylic-modified polyurethane may be included in an amount of 84 parts by weight or less, 83 parts by weight or less, 82 parts by weight or less, 81 parts by weight or less, or 80 parts by weight or less, respectively, but is not limited thereto.

[0054] In one specific example, the anhydrous sugar alcohol-alkylene oxide adduct (also referred to as “anhydrous sugar alcohol-alkylene glycol”) included as a polymerization unit in the hydrophilic (meth)acryl-modified polyurethane is an adduct obtained by reacting hydroxyl groups at both terminals or one terminal (preferably both terminals) of anhydrous sugar alcohol with an alkylene oxide, and means a compound in which hydrogens at both terminals or one terminal (preferably both terminals) of anhydrous sugar alcohol are replaced with hydroxyalkyl groups, which are ring-opened forms of alkylene oxide.

[0055] In one embodiment, the alkylene oxide may be a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, and more specifically, may be ethylene oxide, propylene oxide, or a combination thereof.

[0056] The above anhydrous sugar alcohol can be produced by dehydration of hydrogenated sugars derived from natural products. Hydrogenated sugar (also called “sugar alcohol”) refers to a compound obtained by adding hydrogen to the reducing terminal group of a sugar, and is generally expressed as HOCH2(CHOH). n It has the chemical formula CH2OH (where n is an integer from 2 to 5) and is classified into tetrintol, pentitol, hexitol, and heptitol (having 4, 5, 6, and 7 carbon atoms, respectively) depending on the number of carbon atoms. Among them, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

[0057] The above anhydrous alcohol may be monoanhydrous alcohol, dianhydrous alcohol or a mixture thereof, and although not particularly limited, dianhydrous alcohol may be used.

[0058] Monoanhydrosugar alcohol is an anhydrosugar alcohol formed by removing one water molecule from the interior of a hydrogenated sugar, and has a tetraol form with four hydroxyl groups in the molecule. In the present invention, the type of monoanhydrosugar alcohol is not particularly limited, but preferably, it may be monoanhydrosugar hexitol, and more specifically, it may be 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more thereof.

[0059] Anhydrosugar alcohols are anhydrosugar alcohols formed by the removal of two water molecules from the interior of hydrogenated sugars. They have a diol structure with two hydroxyl groups within the molecule and can be manufactured using hexitols derived from starch. Anhydrosugar alcohols have long been the subject of considerable interest and research into their manufacturing methods, as they are environmentally friendly substances derived from renewable natural resources. Among these dianhydrosugar alcohols, isosorbide, manufactured from sorbitol, currently has the widest range of industrial applications.

[0060] In the present invention, the type of the dianhydrosugar alcohol is not particularly limited, but preferably, it may be a dianhydrosugar hexitol, and more specifically, it may be 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

[0061] In one specific example, the anhydrous alcohol-alkylene oxide adduct may be a compound represented by the following chemical formula 1 or a mixture of two or more thereof.

[0062] [Chemical Formula 1]

[0063]

[0064] In the above chemical formula 1,

[0065] R 1 and R2 Each independently represents a linear or branched alkylene group having 2 to 8 carbon atoms,

[0066] m and n each independently represent an integer from 0 to 15,

[0067] m+n represents an integer from 1 to 30.

[0068] More preferably, in the above chemical formula 1,

[0069] R 1 and R 2 Each independently represents an ethylene group, a propylene group or an isopropylene group, preferably R 1 and R 2 are identical to each other,

[0070] m and n each independently represent an integer from 0 to 14,

[0071] However, m+n is an integer greater than or equal to 1, greater than or equal to 2, or greater than or equal to 3, and also an integer less than or equal to 25, less than or equal to 20, less than or equal to 15, or less than or equal to 12, for example, an integer from 1 to 25, preferably an integer from 2 to 20, and more preferably an integer from 3 to 15.

[0072] In one specific example, the anhydrous alcohol-alkylene oxide adduct may be an anhydrous alcohol-propylene oxide adduct represented by the following chemical formula 1-1, an anhydrous alcohol-ethylene oxide adduct represented by the following chemical formula 1-2, or a mixture thereof.

[0073] [Chemical Formula 1-1]

[0074]

[0075] In the above chemical formula 1-1,

[0076] a and b each independently represent an integer from 0 to 15,

[0077] a+b represents an integer from 1 to 30.

[0078] More preferably, in the above chemical formula 1-1,

[0079] a and b each independently represent an integer from 0 to 14,

[0080] However, a+b is an integer greater than or equal to 1, greater than or equal to 2, or greater than or equal to 3, and also an integer less than or equal to 25, less than or equal to 20, less than or equal to 15, or less than or equal to 12, for example, an integer from 1 to 25, preferably an integer from 2 to 20, and more preferably an integer from 3 to 15.

[0081] [Chemical Formula 1-2]

[0082]

[0083] In the above chemical formula 1-2,

[0084] c and d each independently represent an integer from 0 to 15,

[0085] c+d represents an integer from 1 to 30.

[0086] More preferably, in the above chemical formula 1-2,

[0087] c and d each independently represent an integer from 0 to 14,

[0088] However, c+d is an integer greater than or equal to 1, greater than or equal to 2, or greater than or equal to 3, and also an integer less than or equal to 25, less than or equal to 20, less than or equal to 15, or less than or equal to 12, for example, an integer from 1 to 25, preferably an integer from 2 to 20, and more preferably an integer from 3 to 15.

[0089] In one specific example, the anhydrous sugar alcohol-alkylene oxide adduct may be produced by a production method comprising the steps of (1) treating an anhydrous sugar alcohol with an acid component; and (2) performing an addition reaction between the anhydrous sugar alcohol treated with the acid component obtained in step (1) and an alkylene oxide.

[0090] More specifically, the anhydrous sugar alcohol-alkylene oxide adduct may be produced by a production method comprising the steps of (1) treating an anhydrous sugar alcohol with an acid component; (2) performing an addition reaction between the anhydrous sugar alcohol treated with the acid component obtained in step (1) and an alkylene oxide; and (3) performing an addition reaction between the product obtained in step (2) and an alkylene oxide in the presence of a base catalyst.

[0091] The acid component is not particularly limited, and may be selected from the group consisting of phosphoric acid, sulfuric acid, acetic acid, formic acid, heteropolyacid, or a mixture thereof. In one specific example, the heteropolyacid may be phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, or silicomolybdic acid. In addition, a commercially available acid component such as Amberlyst 15 (manufactured by Dow Chemical) may be used.

[0092] In one specific example, the acid treatment may be performed at an elevated temperature (e.g., 80°C to 200°C, or 90°C to 180°C) under a nitrogen atmosphere using 0.1 to 10 moles, preferably 0.1 to 8 moles, and more preferably 0.1 to 5 moles of the acid component per mole of the anhydrous sugar alcohol, and then vacuum depressurization may be performed to remove moisture within the reactor, but is not limited thereto.

[0093] The acid component used in the above acid treatment is intended to facilitate ring opening of the alkylene oxide in the addition reaction of the alkylene oxide described below.

[0094] Typically, the addition reaction of an alkylene oxide to an alcohol proceeds in the presence of a base catalyst. However, in the case of anhydrosugar alcohols, due to their structural characteristics, the rate at which the alkylene oxide is added competes with the rate at which the anhydrosugar alcohol's ring structure is opened and decomposed by the base catalyst. Accordingly, not only the anhydrosugar alcohol but also the decomposition product of the anhydrosugar alcohol reacts with the alkylene oxide, and the reaction product between the decomposition product of the anhydrosugar alcohol decomposed by the base catalyst and the alkylene oxide can act as a factor that reduces product quality and storage stability. However, if the anhydrosugar alcohol is first treated with an acid component and then the alkylene oxide is added, not only does the acid component facilitate the ring opening of the alkylene oxide, but also the decomposition product of the anhydrosugar alcohol by the base catalyst is not generated, so the addition reaction of the anhydrosugar alcohol and the alkylene oxide can easily produce an anhydrosugar alcohol-alkylene oxide adduct. Therefore, when acid-treated anhydrous sugar alcohol and alkylene oxide are subjected to an addition reaction, the conventional problems can be solved.

[0095] In one specific example, the addition reaction of the anhydrous sugar alcohol treated with the acid component and the alkylene oxide may be carried out at an elevated temperature (e.g., 100°C to 180°C, or 120°C to 160°C) while slowly adding the alkylene oxide to the anhydrous sugar alcohol treated with the acid component for, for example, 1 to 8 hours or 2 to 4 hours, but is not limited thereto. The reaction molar ratio of the anhydrous sugar alcohol and the alkylene oxide is, for example, 1 mol or more or 2 mol or more of the alkylene oxide per 1 mol of the anhydrous sugar alcohol, and also 30 mol or less, 20 mol or less, 15 mol or less, or 12 mol or less, and may be, for example, 1 mol to 30 mol, preferably 2 to 20 mol, but is not limited thereto.

[0096] In one specific example, the addition reaction of the product obtained by the addition reaction of the alkylene oxide with an additional alkylene oxide may be performed, for example, in a high-pressure reactor capable of pressurization (for example, a pressure of 3 MPa or more), in the presence of a base catalyst (for example, a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide, or a hydroxide of an alkaline earth metal such as calcium hydroxide), at an elevated temperature (for example, 100°C to 180°C, or 120°C to 160°C), for, for example, 1 hour to 8 hours or 2 hours to 4 hours, but is not limited thereto. The reaction molar ratio of the anhydrous sugar alcohol and the alkylene oxide is, for example, 1 mol or more, 2 mol or more, or 3 mol or more of the alkylene oxide per 1 mol of the anhydrous sugar alcohol, and also 30 mol or less, 20 mol or less, 15 mol or less, or 12 mol or less, and may be, for example, 1 mol to 30 mol, preferably 2 mol to 20 mol, and more preferably 3 mol to 15 mol, but is not limited thereto. Before adding the base catalyst, the acid component used in the treatment can be removed by filtration.

[0097] The product obtained by the addition reaction of an acid-treated anhydrosugar alcohol and an alkylene oxide (i.e., a compound in which an alkylene oxide is added to an anhydrosugar alcohol) has a very stable structure. Therefore, even in the presence of a base catalyst, the ring structure of the anhydrosugar alcohol does not easily open or decompose at high temperatures. Therefore, it is very advantageous for the additional addition reaction of alkylene oxide. If the acid catalyst continues to be used during the additional addition reaction of alkylene oxide, although the acid catalyst helps promote the ring opening of the alkylene oxide, the reaction rate decreases as the number of moles of alkylene oxide added increases. In other words, the rate of alkylene oxide addition competes with the rate of ring opening of the alkylene oxide itself. At this time, the rate of alkylene oxide addition slows down, and the self-condensation reaction and by-product formation of the ring-opened alkylene oxides can occur, which can cause a deterioration in quality. Therefore, the additional addition reaction of alkylene oxide is carried out in the presence of a base catalyst.

[0098] Afterwards, a step of removing metal ions flowing out from the above-mentioned base catalyst may be additionally performed, and for this purpose, a metal ion adsorbent such as Ambosol MP20 (magnesium silicate component) may be used.

[0099] In one specific example, the lipophilic polyol included as a polymerization unit in the lipophilic (meth)acrylic-modified polyurethane is a polyol having low surface energy properties, and specifically, may be selected from, but is not limited to, polytetrahydrofuran (polytetramethylene ether glycol), polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or a combination thereof.

[0100] In one specific example, the number average molecular weight (Mn) of the lipophilic polyol is not particularly limited, but may be specifically 200 to 3,000 g / mol, more specifically 500 to 2,500 g / mol, even more specifically 700 to 2,300 g / mol, and still more specifically 1,000 to 2,000 g / mol.

[0101] In one specific example, the polyisocyanate included as a polymerization unit in the hydrophilic and lipophilic (meth)acrylic-modified polyurethane is, for example, methylenediphenyl diisocyanate (MDI) (e.g., 2,4- or 4,4'-methylenediphenyl diisocyanate), xylylene diisocyanate (XDI), m- or p-tetramethylxylylene diisocyanate (TMXDI), toluene diisocyanate (TDI), di- or tetra-alkyldiphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate (TODI), phenylene diisocyanate (e.g., 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate), naphthalene diisocyanate (NDI), or Aromatic polyisocyanates such as 4,4'-dibenzyldiisocyanate; Aliphatic such as hydrogenated MDI (H12MDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,12-diisocyanatododecane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, isophorone diisocyanate (IPDI), tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate (HDI) (e.g., 1,6-hexamethylene diisocyanate), dimer fatty acid diisocyanates, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate (e.g., cyclohexane-1,4-diisocyanate), or ethylene diisocyanate polyisocyanate; or a combination thereof, but is not limited thereto.

[0102] In another specific example, the polyisocyanate is methylenediphenyl diisocyanate (MDI), ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene Diisocyanate, toluene diisocyanate mixed with 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (2,4- / 2,6-isomer ratio=80 / 20), diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1,5-diisocyanate or a combination thereof, but is not limited thereto.

[0103] More specifically, the polyisocyanate may be methylenediphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.

[0104] In one specific example, the hydroxyalkyl (meth)acrylate included as a polymerization unit in the hydrophilic and lipophilic (meth)acryl-modified polyurethane may be, for example, a linear or branched alkyl acrylate having a hydroxy group, a linear or branched alkyl methacrylate having a hydroxy group, or a combination thereof, more specifically, hydroxy-C 1-8 Alkyl (meth)acrylate, i.e. linear C having a hydroxy group 1-8 Alkyl acrylate, branched C with hydroxyl group 3-8Alkyl acrylate, linear C with hydroxyl group 1-8 Alkyl methacrylate, branched C with hydroxy group 3-8 It may be an alkyl methacrylate or a combination thereof, and more specifically, it may be, but is not limited to, hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypentyl acrylate, hydroxypentyl methacrylate, 2-hydroxyethylhexyl acrylate, 2-hydroxyethylhexyl methacrylate, 2-hydroxyethylbutyl acrylate, 2-hydroxyethylbutyl methacrylate, hydroxyoctyl acrylate, hydroxyoctyl methacrylate or a combination thereof.

[0105] More specifically, the hydroxyalkyl (meth)acrylate may be 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate or a combination thereof.

[0106] In one specific example, the hydrophilic (meth)acrylic-modified polyurethane may be represented by the following chemical formula 2:

[0107] [Chemical Formula 2]

[0108]

[0109] In the above chemical formula 2,

[0110] R1 is each independently an alkylene group, specifically a C2-C8 linear or C3-C8 branched alkylene group, and more specifically a C2-C6 linear or C3-C6 branched alkylene group,

[0111] R2 is each independently an alkylene group, a cycloalkylene group or an arylene group, specifically a C2-C20 linear or C3-C20 branched alkylene group, a C3-C20 cycloalkylene group or a C6-C20 arylene group,

[0112] R3 is each independently an alkylene group, specifically a C1-C8 linear or C3-C8 branched alkylene group, and more specifically a C2-C6 linear or C3-C6 branched alkylene group,

[0113] R4 is each independently a hydrogen atom or an alkyl group, specifically a hydrogen atom or a C1-C4 linear or C3-C4 branched alkyl group,

[0114] M is a divalent organic group derived from an anhydrous alcohol, specifically a divalent organic group derived from isosorbide, isomannide or isoidide, and more specifically is selected from the following chemical formulas:

[0115]

[0116] m and n each independently represent an integer from 0 to 15,

[0117] m+n represents an integer from 1 to 30, more specifically an integer from 1 to 25, even more specifically an integer from 1 to 20, even more specifically an integer from 3 to 15, even more specifically an integer from 5 to 15.

[0118] More specifically, the hydrophilic (meth)acrylic-modified polyurethane may be represented by any one of the following chemical formulas, but is not limited thereto:

[0119]

[0120]

[0121]

[0122]

[0123]

[0124] In the above chemical formulas, m, n and m+n are each independently as defined in the above chemical formula 2, and p represents an integer from 1 to 15.

[0125] The above hydrophilic (meth)acryl-modified polyurethane can be obtained by reacting a hydrophilic polyol with a polyisocyanate and then reacting it with a hydroxyalkyl (meth)acrylate.

[0126] More specifically, the hydrophilic (meth)acryl-modified polyurethane can be produced by a method comprising the steps of: (a) reacting a polyisocyanate with at least one hydrophilic polyol selected from the group consisting of polyethylene glycol, anhydrous sugar alcohol-alkylene oxide adducts, or combinations thereof to produce an intermediate having an isocyanate terminal; and (b) reacting the intermediate obtained from step (a) with a hydroxyalkyl (meth)acrylate.

[0127] According to one specific example, a hydrophilic (meth)acryl-modified polyurethane can be prepared by reacting 1 equivalent of polyethylene glycol with 2 equivalents of diisocyanate to prepare an intermediate having an isocyanate terminal, and then reacting the isocyanate terminal of the intermediate with 2 equivalents of a hydroxyalkyl (meth)acrylate (e.g., 2-hydroxyethyl methacrylate).

[0128] According to one specific example, a hydrophilic (meth)acryl-modified polyurethane can be prepared by reacting 1 equivalent of an anhydrous sugar alcohol (e.g., isosorbide (ISB))-alkylene oxide adduct with 2 equivalents of diisocyanate to produce an intermediate having an isocyanate terminal, and then reacting the isocyanate terminal of the intermediate with 2 equivalents of a hydroxyalkyl (meth)acrylate (e.g., 2-hydroxyethyl methacrylate).

[0129] According to one specific example, the reaction of the hydrophilic polyol (e.g., an anhydrous sugar alcohol-alkylene oxide adduct, polyethylene glycol or a combination thereof) with the polyisocyanate can be carried out, optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)), at room temperature or at an elevated temperature (e.g., 50 to 100° C., preferably 50 to 70° C.) for an appropriate period of time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours).

[0130] According to one specific example, the reaction of the hydrophilic polyol (e.g., an anhydrous alcohol-alkylene oxide adduct, polyethylene glycol or a combination thereof) with a polyisocyanate (i.e., the intermediate obtained from step (a)) with a hydroxyalkyl (meth)acrylate can be carried out, optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)), at an elevated temperature (e.g., at 50 to 100° C., preferably at 50 to 70° C.) for an appropriate period of time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours).

[0131] In one specific example, the lipophilic (meth)acrylic-modified polyurethane may be represented by the following chemical formula 3:

[0132] [Chemical Formula 3]

[0133]

[0134] In the above chemical formula 3,

[0135] R1 is each independently an alkylene group, a cycloalkylene group or an arylene group,

[0136] R2 is each independently an alkylene group,

[0137] R3 is each independently a hydrogen atom or an alkyl group,

[0138] L is a divalent organic group derived from lipophilic polyol,

[0139] The number average molecular weight of the above lipophilic polyol is 200 to 3,000 g / mol.

[0140] More specifically, in the above chemical formula 3,

[0141] R1 is each independently a C2-C20 linear or C3-C20 branched alkylene group, a C3-C20 cycloalkylene group or a C6-C20 arylene group,

[0142] R2 is each independently a C1-C8 linear or C3-C8 branched alkylene group,

[0143] R3 is each independently a hydrogen atom or a C1-C4 linear or C3-C4 branched alkyl group,

[0144] L is a divalent organic group derived from a lipophilic polyol selected from polytetrahydrofuran, polypropylene glycol, polydimethylsiloxane (PDMS) polyol, or a combination thereof,

[0145] The number average molecular weight of the above lipophilic polyol is 500 to 2,500 g / mol.

[0146] More specifically, the lipophilic (meth)acrylic-modified polyurethane may be represented by any one of the following chemical formulas, but is not limited thereto:

[0147]

[0148]

[0149]

[0150]

[0151] In the above chemical formulas, n can independently represent an integer from 1 to 15.

[0152] The above lipophilic (meth)acryl-modified polyurethane can be obtained by reacting a polyisocyanate with a lipophilic polyol and then reacting it with a hydroxyalkyl (meth)acrylate.

[0153] More specifically, the lipophilic (meth)acryl-modified polyurethane can be produced by a method comprising the steps of: (c) reacting a lipophilic polyol with a polyisocyanate to produce an intermediate having an isocyanate terminal; and (d) reacting the intermediate obtained from step (c) with a hydroxyalkyl (meth)acrylate.

[0154] According to one specific example, a lipophilic (meth)acryl-modified polyurethane can be prepared by reacting 1 equivalent of a lipophilic polyol (e.g., polytetrahydrofuran, polypropylene glycol, or polydimethylsiloxane diol having a number average molecular weight of 200 to 3,000 g / mol) with 2 equivalents of a diisocyanate to prepare an intermediate having an isocyanate terminal, and then reacting the isocyanate terminal of the intermediate with 2 equivalents of a hydroxyalkyl (meth)acrylate (e.g., 2-hydroxyethyl methacrylate).

[0155] According to one specific example, the reaction of the lipophilic polyol and the polyisocyanate can be carried out, optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)), at room temperature or at an elevated temperature (e.g., 50 to 100° C., preferably 50 to 70° C.) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours).

[0156] According to one specific example, the reaction product of the lipophilic polyol and polyisocyanate (i.e., the intermediate obtained from step (c)) with a hydroxyalkyl (meth)acrylate can be carried out, optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)), at an elevated temperature (e.g., 50 to 100°C, preferably 50 to 70°C) for an appropriate period of time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours).

[0157] In one specific example, when the (meth)acryl-modified polyurethane is a hydrophilic (meth)acryl-modified polyurethane alone, it can be produced by a method (first production method) comprising: (1) reacting a polyol component comprising at least one hydrophilic polyol selected from the group consisting of anhydrous sugar alcohol-alkylene oxide adducts, polyethylene glycol, or combinations thereof with a polyisocyanate to produce an intermediate having an isocyanate terminal; and (2) reacting the intermediate obtained from step (1) with a hydroxyalkyl (meth)acrylate.

[0158] In another specific example, when the (meth)acryl-modified polyurethane is a lipophilic (meth)acryl-modified polyurethane alone, it can be produced by a method (second production method) comprising the steps of (1) reacting a polyol component including a lipophilic polyol with a polyisocyanate to produce an intermediate having an isocyanate terminal; and (2) reacting the intermediate obtained from step (1) with a hydroxyalkyl (meth)acrylate.

[0159] In another specific example, when the (meth)acryl-modified polyurethane is a combination of a hydrophilic (meth)acryl-modified polyurethane and a lipophilic (meth)acryl-modified polyurethane, it can be produced by a method (third production method) comprising (1) a step of reacting a polyol component including a hydrophilic polyol and a lipophilic polyol with a polyisocyanate to produce an intermediate having an isocyanate terminal; and (2) a step of reacting the intermediate obtained from step (1) with a hydroxyalkyl (meth)acrylate.

[0160] In another specific example, when the (meth)acryl-modified polyurethane is a combination of a hydrophilic (meth)acryl-modified polyurethane and a lipophilic (meth)acryl-modified polyurethane, it can be produced by a method (a fourth production method) comprising a step of mixing the hydrophilic (meth)acryl-modified polyurethane and the lipophilic (meth)acryl-modified polyurethane, and more specifically, a hydrophilic (meth)acryl-modified polyurethane comprising (i) polymerized units derived from one or more hydrophilic polyols selected from the group consisting of anhydrous sugar alcohol-alkylene oxide adducts, polyethylene glycol, or combinations thereof; polymerized units derived from polyisocyanates; and polymerized units derived from hydroxyalkyl (meth)acrylates; and (ii) polymerized units derived from a lipophilic polyol; polymerized units derived from a polyisocyanate; and a step of mixing a lipophilic (meth)acrylic-modified polyurethane comprising polymerized units derived from hydroxyalkyl (meth)acrylate.

[0161] In the above methods for producing (meth)acryl-modified polyurethane, the hydrophilic polyol, the anhydrous sugar alcohol-alkylene oxide adduct, the lipophilic polyol, the polyisocyanate, and the hydroxyalkyl (meth)acrylate are as described above.

[0162] According to one specific example, in the above methods for producing (meth)acryl-modified polyurethane, the reaction of the polyol component and the polyisocyanate may be carried out, optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)), at room temperature or at an elevated temperature (e.g., at 50 to 100°C, preferably at 50 to 70°C) for an appropriate time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours), and the reaction of the reaction product of the polyol component and the polyisocyanate (i.e., the intermediate obtained from step (1)) with the hydroxyalkyl (meth)acrylate may be carried out, optionally in the presence of a catalyst (e.g., a tin-based catalyst such as dibutyltin dilaurate (DBTDL)), at an elevated temperature (e.g., at 50 to 100°C, preferably at 50 to 70°C) for an appropriate time. It can be performed for a period of time (e.g., 0.1 to 5 hours, preferably 0.5 to 2 hours).

[0163] In one specific example, the (meth)acryl-modified epoxy may be an epoxy compound having one or more (preferably 1 to 4) (meth)acryl groups in the molecule.

[0164] In one specific example, the (meth)acryl-modified epoxy may include at least one selected from the group consisting of a petroleum-based (meth)acryl-modified epoxy resin, a (meth)acryl-modified epoxy compound derived from anhydrous sugar alcohol, a (meth)acryl-modified epoxy compound derived from anhydrous sugar alcohol-alkylene oxide adduct, or a combination thereof.

[0165] In one specific example, the (meth)acryl-modified epoxy may be a (meth)acryl-modified epoxy compound derived from an anhydrous sugar alcohol, a (meth)acryl-modified epoxy compound derived from an anhydrous sugar alcohol-alkylene oxide adduct, or a mixture thereof.

[0166] The above anhydrous alcohols and anhydrous alcohol-alkylene oxide adducts are as described above.

[0167] More specifically, the (meth)acryl-modified epoxy compound derived from the anhydrous sugar alcohol or anhydrous sugar alcohol-alkylene oxide adduct may be represented by any one of the following chemical formulas, but is not limited thereto:

[0168]

[0169]

[0170] Here, m and n each independently represent an integer from 0 to 15, and m+n represents an integer from 1 to 30, more specifically an integer from 1 to 25, even more specifically an integer from 1 to 20, even more specifically an integer from 3 to 15, and even more specifically an integer from 5 to 15.

[0171] In one specific example, the petroleum-based (meth)acryl-modified epoxy resin may be at least one selected from the group consisting of a (meth)acryl-modified epoxy resin derived from bisphenol, a (meth)acryl-modified epoxy resin derived from phenol novolac, a (meth)acryl-modified epoxy resin derived from o-cresol novolac, a (meth)acryl-modified epoxy resin derived from naphthol, or a combination thereof.

[0172] In one specific example, the (meth)acryl-modified silicone compound may be a silicone compound having one or more (preferably 1 to 4) (meth)acryl groups in the molecule.

[0173] In one specific example, the (meth)acryl-modified silicone compound may include at least one selected from the group consisting of monomethacryloxypropyl terminated polydimethylsiloxane, dimethacryloxypropyl terminated polydimethylsiloxane, polydimethylsiloxane-co-polymethyl(meth)acrylate copolymer, or a combination thereof.

[0174] The two-component curable composition of the present invention may further comprise one or more components that can be conventionally included in an adhesive composition in addition to the components described above, within the scope that can achieve the purpose of the present invention. Such additional components may include, but are not limited to, one or more selected from an oxidizing agent other than the manganese compound described above, an initiator other than the phosphorus compound and dicarbonyl compound described above, a curing accelerator, a polymerization inhibitor, a filler, an antifoaming agent, a flame retardant, a reinforcing agent, or a combination thereof. However, preferably, the two-component curable composition of the present invention does not contain a peroxide.

[0175] According to another aspect of the present invention, an adhesive composition is provided obtained by mixing agent A and agent B included in the two-component curable composition of the present invention.

[0176] According to another aspect of the present invention, a method for producing an adhesive composition is provided, comprising a step of mixing agent A and agent B, wherein agent A includes a polymerizable compound and an oxidizing agent, agent B includes a polymerizable compound and a radical initiator, the oxidizing agent includes a manganese compound, and the radical initiator includes a phosphorus compound and a dicarbonyl compound.

[0177] In the method for producing the adhesive composition of the present invention, the descriptions regarding agent A, agent B, polymerizable compound, oxidizing agent, radical initiator, manganese compound, phosphorus compound, dicarbonyl compound, content of manganese compound, content of phosphorus compound, and content of dicarbonyl compound are as described above.

[0178] In one specific example, the mixing of Agent A and Agent B may be performed in an environment managed at room temperature (e.g., 30°C or lower, more specifically 20°C to 30°C).

[0179] In one specific example, the mixing weight ratio of Agent A and Agent B is not particularly limited, but for example, 50 to 200 parts by weight of Agent B may be mixed based on 100 parts by weight of Agent A.

[0180] According to another aspect of the present invention, an article to which the adhesive composition of the present invention is applied is provided.

[0181] In one specific example, the article may include a plurality of metal materials, and the adhesive composition may be applied between them.

[0182] In another specific example, the article may include a metal material and a non-metal material, and the adhesive composition may be applied therebetween.

[0183] Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the scope of the present invention is not limited to these examples.

[0184] [Example]

[0185] <Preparation of anhydrous alcohol-alkylene oxide adducts>

[0186] Manufacturing Example 1: Manufacturing of 5 mol isosorbide-ethylene oxide adduct

[0187] Into a pressurizable reactor, 146 g of isosorbide was placed, and 0.15 g of phosphoric acid (85%) was added as an acid component. The inside of the reactor was purged with nitrogen, heated to 100°C, and moisture inside the reactor was removed through vacuum depressurization. Next, 88 g of ethylene oxide was slowly added to the reactor for the first time, and the reaction was carried out at a temperature of 100°C to 140°C for 2 to 3 hours. The reaction temperature was controlled so as not to exceed 140°C. Afterwards, the internal temperature of the reactor was cooled to 50°C, 0.3 g of potassium hydroxide was added to the reactor, the inside of the reactor was purged with nitrogen, heated to 100°C, and moisture inside the reactor was removed through vacuum depressurization. Next, 132 g of ethylene oxide was slowly added for the second time, and the reaction was carried out at 100°C to 140°C for 2 to 3 hours. When the reaction was completed, the internal temperature of the reactor was cooled to 50°C, 4.0 g of Ambosol MP20 was added as an adsorbent, and the mixture was heated again and stirred at a temperature of 100°C to 120°C for 1 to 5 hours to remove metal ions. At this time, the interior of the reactor was purged with nitrogen and / or vacuum pressure was applied. When no more metal ions were detected, the internal temperature of the reactor was cooled to 60°C to 90°C, and the residual byproducts were removed, thereby obtaining 362 g of a transparent liquid isosorbide-ethylene oxide 5-mole adduct.

[0188] Manufacturing Example 2: Manufacturing of 10 mol isosorbide-ethylene oxide adduct

[0189] Except that the secondary input of ethylene oxide was changed from 132 g to 352 g, the same method as in Manufacturing Example 1 was performed to obtain 551 g of a 10-mol isosorbide-ethylene oxide adduct in a transparent liquid state.

[0190] Manufacturing Example 3: Manufacturing of 5 mol isosorbide-propylene oxide adduct

[0191] Instead of using ethylene oxide as an additional reaction raw material, propylene oxide was used, and specifically, instead of first adding 88 g of ethylene oxide, 116 g of propylene oxide was first added, and instead of second adding 132 g of ethylene oxide, 174 g of propylene oxide was second added, the same method as in Manufacturing Example 1 was performed, thereby obtaining 423 g of a transparent liquid isosorbide-propylene oxide 5 mol adduct.

[0192] Manufacturing Example 4: Manufacturing of 10 mol isosorbide-propylene oxide adduct

[0193] Instead of using ethylene oxide as an additional reaction raw material, propylene oxide was used, and specifically, instead of first adding 88 g of ethylene oxide, 116 g of propylene oxide was first added, and instead of second adding 132 g of ethylene oxide, 465 g of propylene oxide was second added, the same method as in Manufacturing Example 1 was performed, thereby obtaining 698 g of a 10-mol isosorbide-propylene oxide adduct in a transparent liquid state.

[0194] <Preparation of (meth)acrylic-modified oligomers>

[0195] Manufacturing Example A1: Manufacturing of (meth)acrylic-modified polyurethane using 5 mol isosorbide-ethylene oxide adduct as polyol, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate.

[0196] In a three-necked glass reactor equipped with a stirrer, 222 g of isophorone diisocyanate (IPDI) and 0.1 g of dibutyltin dilaurate (DBTDL) as a reaction catalyst were added and mixed at room temperature. 183 g of the 5-mol isosorbide-ethylene oxide adduct obtained in Preparation Example 1 as a polyol was slowly added to carry out a crosslinking reaction. After the addition of the 5-mol isosorbide-ethylene oxide adduct was completed, the mixture was aged and stirred at 50°C for 1 hour, and then 65 g of 2-hydroxyethyl methacrylate was slowly added to carry out an acrylic modification reaction. After the addition of 2-hydroxyethyl methacrylate, the mixture was aged and stirred at 50°C for 1 hour, and the reaction product was cooled to room temperature, thereby obtaining 467 g of a (meth)acryl-modified polyurethane of the following chemical formula A.

[0197] [Chemical Formula A]

[0198]

[0199] Manufacturing Example A2: Manufacturing of (meth)acrylic-modified polyurethane using 10 mol isosorbide-ethylene oxide adduct as polyol, hexamethylene diisocyanate (HDI) as polyisocyanate, and 2-hydroxyethyl acrylate as hydroxyalkyl (meth)acrylate.

[0200] The same method as in Preparation Example A1 was performed except that 168 g of hexamethylene diisocyanate (HDI) was used instead of isophorone diisocyanate (IPDI) as the polyisocyanate, 293 g of the 10 mol isosorbide-ethylene oxide adduct obtained in Preparation Example 2 was used instead of the 5 mol isosorbide-ethylene oxide adduct obtained in Preparation Example 1 as the polyol, and 58 g of 2-hydroxyethyl acrylate was used instead of 2-hydroxyethyl methacrylate as the hydroxyalkyl (meth)acrylate, thereby obtaining 515 g of a (meth)acryl-modified polyurethane of the following chemical formula B.

[0201] [Chemical Formula B]

[0202]

[0203] Manufacturing Example A3: Manufacturing of (meth)acrylic-modified polyurethane using 5 mol isosorbide-propylene oxide adduct as polyol, methylenediphenyl diisocyanate (MDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate.

[0204] By performing the same method as in Preparation Example A1, except that 250 g of methylenediphenyl diisocyanate (MDI) was used instead of isophorone diisocyanate (IPDI) as the polyisocyanate, and 218 g of the 5 mol isosorbide-propylene oxide adduct obtained in Preparation Example 3 was used instead of the 5 mol isosorbide-ethylene oxide adduct obtained in Preparation Example 1 as the polyol, 529 g of a (meth)acryl-modified polyurethane of the following chemical formula C was obtained.

[0205] [Chemical Formula C]

[0206]

[0207] Manufacturing Example A4: Manufacturing of (meth)acryl-modified polyurethane using 10 mol isosorbide-propylene oxide adduct as polyol, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate.

[0208] By performing the same method as Manufacturing Example A1, except that 363 g of the 10 mol isosorbide-propylene oxide adduct obtained in Manufacturing Example 4 was used instead of the 5 mol isosorbide-ethylene oxide adduct obtained in Manufacturing Example 1 as the polyol, 643 g of a (meth)acryl-modified polyurethane of the following chemical formula D was obtained.

[0209] [Chemical Formula D]

[0210]

[0211] Manufacturing Example A5: Manufacturing of a (meth)acrylic-modified polyurethane component using polypropylene glycol (80 parts by weight based on 100 parts by weight of the total polyol) as a polyol and 5 molar isosorbide-ethylene oxide adduct (20 parts by weight based on 100 parts by weight of the total polyol), isophorone diisocyanate (IPDI) as a polyisocyanate, and 2-hydroxyethyl methacrylate as a hydroxyalkyl (meth)acrylate.

[0212] In a three-necked glass reactor equipped with a stirrer, 600 g of isophorone diisocyanate (IPDI) and 0.6 g of dibutyltin dilaurate (DBTDL) as a reaction catalyst were added and mixed at room temperature. Then, 800 g of polypropylene glycol (number average molecular weight: 1,000 g / mol, Kumho Petrochemical Co., Ltd.) as a polyol and 200 g of the 5 mol isosorbide-ethylene oxide adduct obtained in Manufacturing Example 1 were slowly added to carry out a crosslinking reaction. After the addition of the polyol component was completed, the mixture was aged and stirred at 50°C for 1 hour, and then 350 g of 2-hydroxyethyl methacrylate was slowly added to carry out an acrylic modification reaction. After the addition of 2-hydroxyethyl methacrylate, the reaction product was aged and stirred at 50°C for 1 hour and then cooled to room temperature, thereby obtaining 1,950 g of a (meth)acryl-modified polyurethane component including 390 g of a (meth)acryl-modified polyurethane of the following chemical formula A and 1,560 g of a (meth)acryl-modified polyurethane of the following chemical formula E.

[0213] [Chemical Formula A]

[0214]

[0215] [Chemical Formula E]

[0216]

[0217] Manufacturing Example A6: Manufacturing of a (meth)acrylic-modified polyurethane component using polytetrahydrofuran (50 parts by weight based on 100 parts by weight of the total polyol) as a polyol and 10 molar adduct of isosorbide-ethylene oxide (50 parts by weight based on 100 parts by weight of the total polyol), hexamethylene diisocyanate (HDI) as a polyisocyanate, and 2-hydroxyethyl acrylate as a hydroxyalkyl (meth)acrylate.

[0218] By performing the same method as Manufacturing Example A5 except that 270 g of hexamethylene diisocyanate (HDI) was used instead of isophorone diisocyanate (IPDI) as the polyisocyanate, 365 g of polytetrahydrofuran (number average molecular weight: 2,000 g / mol, manufactured by Kumho Petrochemical Co., Ltd.) was used instead of polypropylene glycol (number average molecular weight: 1,000 g / mol, manufactured by Kumho Petrochemical Co., Ltd.) as the polyol and 365 g of the 5 mol isosorbide-ethylene oxide adduct obtained in Manufacturing Example 1 and 365 g of the 10 mol isosorbide-ethylene oxide adduct obtained in Manufacturing Example 2 were used instead of the 2-hydroxyethyl methacrylate as the hydroxyalkyl (meth)acrylate, 186 g of 2-hydroxyethyl acrylate was used instead of 2-hydroxyethyl methacrylate, (meth)acryl-modified polymer having the following chemical formula B was prepared. 1,185 g of a (meth)acryl-modified polyurethane component comprising 593 g of polyurethane and 592 g of a (meth)acryl-modified polyurethane of the following chemical formula F was obtained.

[0219] [Chemical Formula B]

[0220]

[0221] [Chemical formula F]

[0222]

[0223] Manufacturing Example A7: Manufacturing of a (meth)acrylic-modified polyurethane component using polytetrahydrofuran (30 parts by weight based on 100 parts by weight of the total polyol) as a polyol and 10 molar adduct of isosorbide-propylene oxide (70 parts by weight based on 100 parts by weight of the total polyol), isophorone diisocyanate (IPDI) as a polyisocyanate, and 2-hydroxyethyl methacrylate as a hydroxyalkyl (meth)acrylate.

[0224] Except that 324 g of polytetrahydrofuran (number average molecular weight: 1,000 g / mol, manufactured by Aldrich Co., Ltd.) and 746 g of 10 mol isosorbide-propylene oxide adduct obtained in Manufacturing Example 4 were used instead of polypropylene glycol (number average molecular weight: 1,000 g / mol, manufactured by Kumho Petrochemical Co., Ltd.) as the polyol and the 5 mol isosorbide-ethylene oxide adduct obtained in Manufacturing Example 1, the same method as Manufacturing Example A5 was performed to obtain 2,020 g of a (meth)acryl-modified polyurethane component including 1,414 g of a (meth)acryl-modified polyurethane of the following chemical formula D and 606 g of a (meth)acryl-modified polyurethane of the following chemical formula G.

[0225] [Chemical Formula D]

[0226]

[0227] [Chemical formula G]

[0228]

[0229] Manufacturing Example A8: Manufacturing of (meth)acrylic modified polyurethane using polyethylene glycol as polyol, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate.

[0230] By performing the same method as Manufacturing Example A1, except that 500 g of polyethylene glycol (number average molecular weight: 500 g / mol) was used instead of the 5 mol isosorbide-ethylene oxide adduct obtained in Manufacturing Example 1 as a polyol, 782 g of (meth)acryl-modified polyurethane of the following chemical formula H was obtained.

[0231] [Chemical formula H]

[0232]

[0233] Manufacturing Example A9: Manufacturing of (meth)acrylic-modified epoxy compound derived from anhydrous sugar alcohol

[0234] In a three-necked glass reactor equipped with a stirrer, 100 g of isosorbide diglycidyl ether (Cheil Chemical Co., Ltd.) of the following chemical formula I as a reaction raw material, 500 g of methacrylic acid, 2 mL of triethylamine as a catalyst, and 0.5 g of mequinol (Aldrich Co., Ltd.) as a polymerization inhibitor were charged, and then the mixture was stirred at 100°C for 5 hours under a nitrogen atmosphere to carry out an acrylic modification reaction. After completion of the reaction, the reaction mixture was distilled under reduced pressure to remove unreacted methacrylic acid. The residue was diluted with 1.0 L of ethyl acetate, washed sequentially with 1 L of a 20% aqueous sodium bicarbonate solution and 1 L of distilled water, and distilled under reduced pressure to obtain 125 g of an isosorbide-derived (meth)acryl-modified epoxy compound (DGEI-AA) of the following chemical formula J.

[0235] [Chemical Formula I]

[0236]

[0237] [Chemical formula J]

[0238]

[0239] Manufacturing Example A10: Preparation of (meth)acrylic-modified epoxy compound derived from anhydrous sugar alcohol-alkylene oxide adduct

[0240] A three-necked glass reactor equipped with a stirrer was charged with 900 mL of chloroform, and then 183 g of the 5 mol isosorbide-ethylene oxide adduct obtained in Preparation Example 1 as a reaction raw material, 142 g of glycidyl methacrylate, and 3 mL of triethylamine as a catalyst were added, and the reaction mixture was stirred and heated at 70°C under a nitrogen atmosphere for 48 hours to proceed with the reaction. After completion of the reaction, the reaction mixture was sequentially washed with 500 mL of a 1 N HCl aqueous solution and distilled water, and distilled under reduced pressure to obtain 210 g of a (meth)acryl-modified epoxy compound (DGEI-E5-AA) derived from the 5 mol isosorbide-ethylene oxide adduct of the following chemical formula K.

[0241] [Chemical formula K]

[0242]

[0243] <Manufacture of Coated Steel Plate Adhesive Composition>

[0244] Examples A1 to A24 and Comparative Examples A1 to A31: Standard Manufacturing Method

[0245] A two-component curing composition comprising Agent A and Agent B, each having the types and contents described in Table 1 below, was prepared. Subsequently, Agents A and B were introduced into a mixing reactor maintained at 30°C or lower, and stirred and mixed at a temperature of 30°C or lower to prepare a liquid adhesive composition. At this time, the mixing weight ratio of Agent A and Agent B was 100:100.

[0246] <Ingredient Description>

[0247] - Manufacturing Examples A1 to A10: (Meth)acryl-modified oligomers obtained in Manufacturing Examples A1 to A10, respectively

[0248] - HDDA: Hexanediol dimethacrylate (Aldrich)

[0249] - DEGDMA: Diethylene glycol dimethacrylate (Aldrich)

[0250] - 2-HEMA: 2-Hydroxyethyl metharylate (Samjeon Sunyak)

[0251] - PETTA: Pentaerythritol Tetraacrylate (Miwon Corporation)

[0252] - BA: Butyl acrylate (Samjeon Pure Chemical Industries)

[0253] - TEGDMA: Triethylene glycol dimethacrylate (Aldrich)

[0254] - TMPTA: Trimethylolpropane triacrylate (Aldrich)

[0255] - MPTMS: 3-Methacryloxypropyl trimethoxysilane (Aldrich)

[0256] - DPDSM: Dimethacryloxypropyl terminated polydimethylsiloxane (Aldrich)

[0257] - Mn(OAc)3: Manganese(III) acetate (Aldrich)

[0258] - Mn(OAc)2: Manganese(II) acetate (Aldrich)

[0259] - Mn(acac)3: Manganese(III) acetylacetonate (Aldrich)

[0260] - Mn(acac)2: Manganese(II) acetylacetonate (Aldrich)

[0261] - MnO2: Manganese dioxide (Aldrich)

[0262] - MnCl2: Manganese dichloride (TCI)

[0263] - Mn2O3: Manganese(III) oxide (TCI)

[0264] - Cu(acac)2: Copper(II) acetylacetonate (TCI)

[0265] - DBP: Dibutyl phosphate (Aldrich)

[0266] - DPP: Diphenyl phosphate (Aldrich)

[0267] - PP: Phenyl phosphate (Aldrich)

[0268] - MAEP: Mono(2-methacryloyoxyethyl) phosphate (Kyoeisha)

[0269] - DAEP: Di(2-methacryloyoxyethyl) phosphate (Kyoeisha)

[0270] - PA: Phosphoric acid (Aldrich)

[0271] - IPP: Isopropyl phenyl phosphate (Aldrich)

[0272] - ABL: a-acetylbutyrolactone (Aldrich)

[0273] - AA: Acetyl acetone (Aldrich)

[0274] - MAA: Methyl acetoacetate (TCI)

[0275] - EMAA: Ethyl-2-methyl acetoacetate (Aldrich)

[0276] - ACP: 2-Acetylcyclopentanone (Aldrich)

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283] <Evaluation of physical properties of adhesive composition>

[0284] (1) Room temperature curing speed

[0285] The adhesive compositions prepared in Examples A1 to A24 and Comparative Examples A1 to A31 were each placed in 10 ml of a 20 ml glass vial and left to stand at room temperature (25±5°C) for 3 minutes. Thereafter, the adhesive compositions were visually observed to evaluate whether a cured product was formed within 3 minutes, and the results are shown in Table 2 below.

[0286] O: Cured product was formed within 3 minutes after leaving at room temperature.

[0287] X: No curing product was produced within 3 minutes after leaving at room temperature.

[0288] (2) Metal adhesion

[0289] The adhesive compositions manufactured in Examples A1 to A24 and Comparative Examples A1 to A31 were applied to the surfaces of two rolled steel plates (POSCO) cut to a size of 2.5 cm wide x 12 cm long in an area of ​​2.5 cm wide x 1.25 cm long, and then the applied areas were overlapped and clamped to manufacture an assembly. Thereafter, the assembly was cured at room temperature (25±5°C) for 3 minutes to manufacture a metal adhesive specimen. The metal adhesiveness of each specimen was evaluated by the following method, and the results are shown in Table 2 below.

[0290] [Method for evaluating metal adhesion]

[0291] To evaluate the metal adhesion of the adhesive composition to the rolled steel plate, the shear strength (Lap shear strength) (unit: MPa) of each metal bonded specimen manufactured above was measured using a UTM (Instron 5967 product, Instron). Specifically, the shear strength was measured a total of five times for each metal bonded specimen, and the average value was calculated.

[0292] A higher shear strength indicates better metal adhesion.

[0293] “Unmeasurable” means that when measuring the shear strength of a metal bonded specimen using UTM, the interface separation between the adherend (rolled steel plate) and the adhesive occurs, and the UTM cannot recognize the shear strength.

[0294]

[0295]

[0296] As shown in Table 2 above, the adhesive compositions of Examples A1 to A27 according to the present invention were cured within 3 minutes at room temperature, demonstrating excellent room temperature rapid curing properties. In addition, when Agent A and Agent B were left at room temperature, they remained liquid for 30 days without curing, demonstrating excellent room temperature storage stability. In addition, the adhesive compositions of Examples A1 to A24 also exhibited excellent metal adhesion properties, with the shear strength of the rapid adhesive specimens being 6 MPa or higher.

[0297] On the other hand, in Comparative Examples A1 to A4, A8, and A10, no curing reaction occurred due to the absence of an oxidation-reduction reaction. In addition, in Comparative Examples A5 and A6, which did not contain a phosphorus compound, the room temperature curing speed was slow, making it impossible to measure the shear strength, and in Comparative Example A7, which did not contain a dicarbonyl compound, the room temperature curing speed was slow, making it impossible to measure the shear strength. In addition, in Comparative Example A9, no curing reaction occurred due to the absence of an oxidation-reduction reaction.

Claims

1. (i) Agent A comprising a polymerizable compound and an oxidizing agent; and (ii) B agent comprising a polymerizable compound and a radical initiator; The above oxidizing agent comprises a manganese compound, The above radical initiator comprises a phosphorus compound and a dicarbonyl compound. Two-component curable composition.

2. In the first paragraph, the manganese compound is manganese(III) acetate (Mn(OAc)3), manganese(II) acetate (Mn(OAc)2), manganese(III) acetylacetonate (Mn(acac)3), manganese(II) acetylacetonate (Mn(acac)2), manganese dioxide (MnO2), manganese trioxide (Mn2O3), manganese chloride (MnCl2), manganese carbonate (MnCO3), manganese(II) sulfate (MnSO4), manganese 2-ethylhexanoate, potassium manganese salt (KMnO₄), manganese calcium oxide (CaMnO₃), sodium manganese salt (NaMnO₄), ammonium manganese salt ((NH₄)MnO₄), manganese acid, manganese ferrocyanate, manganese(II) phthalocyanine or a combination thereof. A two-component curable composition comprising at least one selected from the group consisting of:

3. A two-component curable composition according to claim 1, wherein the phosphorus compound comprises at least one selected from the group consisting of dibutyl phosphate, diphenyl phosphate, phenyl phosphate, mono(meth)acryloyloxyethyl phosphate, di(meth)acryloyloxyethyl phosphate, ethylene diphosphate, aminotrimethylene phosphate, phenylphosphonic dichloride, isopropyl acid phosphate, diisopropyl acid phosphate, isopropylphenyl phosphate, ortho phosphoric acid, polyphosphoric acid, butyl pyrophosphate, pyrophosphoric acid, or a combination thereof.

4. A two-component curable composition according to claim 1, wherein the dicarbonyl compound comprises at least one selected from the group consisting of a 1,2-dicarbonyl compound, a 1,3-dicarbonyl compound, a 1,4-dicarbonyl compound, or a combination thereof.

5. A two-component curable composition in the first paragraph, wherein the polymerizable compound is at least one selected from the group consisting of a polymerizable monomer, a polymerizable oligomer, or a combination thereof.

6. A two-component curable composition according to claim 5, wherein the polymerizable monomer or polymerizable oligomer contains at least one (meth)acrylic group in the molecule.

7. In the 6th paragraph, the polymerizable oligomer comprises a (meth)acrylic oligomer, A two-component curable composition, wherein the (meth)acrylic oligomer is at least one selected from the group consisting of (meth)acrylic-modified polyurethane, (meth)acrylic-modified epoxy, (meth)acrylic-modified silicone-based compound, or a combination thereof.

8. In the 7th paragraph, the (meth)acrylic-modified polyurethane is a two-component curable composition comprising at least one selected from the group consisting of hydrophilic (meth)acrylic-modified polyurethane, lipophilic (meth)acrylic-modified polyurethane, or a combination thereof.

9. In the 7th paragraph, the (meth)acryl-modified epoxy is a two-component curable composition comprising at least one selected from the group consisting of a petroleum-based (meth)acryl-modified epoxy resin, a (meth)acryl-modified epoxy compound derived from anhydrous sugar alcohol, a (meth)acryl-modified epoxy compound derived from anhydrous sugar alcohol-alkylene oxide adduct, or a combination thereof.

10. A two-component curable composition in claim 7, wherein the (meth)acryl-modified silicone compound comprises at least one selected from the group consisting of monomethacryloxypropyl-terminated polydimethylsiloxane, dimethacryloxypropyl-terminated polydimethylsiloxane, polydimethylsiloxane-co-polymethyl(meth)acrylate copolymer, or a combination thereof.

11. A two-component curable composition according to claim 1, wherein the manganese compound content in the agent A is more than 0.009 parts by weight and less than 5.5 parts by weight based on 100 parts by weight of the total agent A.

12. A two-component curable composition according to claim 1, wherein the content of the phosphorus compound in the B agent is more than 0.04 parts by weight and less than 20.5 parts by weight based on 100 parts by weight of the total of the B agent.

13. A two-component curable composition according to claim 1, wherein the content of the dicarbonyl compound in the B agent is more than 0.005 parts by weight and less than 11 parts by weight based on 100 parts by weight of the total of B agent.

14. An adhesive composition obtained by mixing agent A and agent B included in the two-component curable composition of any one of claims 1 to 13.

15. A method for manufacturing an adhesive composition, It includes a step of mixing agent A and agent B, The above agent A comprises a polymerizable compound and an oxidizing agent, The above B agent comprises a polymerizable compound and a radical initiator, The above oxidizing agent comprises a manganese compound, The above radical initiator includes a phosphorus compound and a dicarbonyl compound, Method for preparing an adhesive composition.

16. Articles to which the adhesive composition of Article 14 is applied.

17. An article comprising a plurality of metal materials in accordance with paragraph 16, and wherein the adhesive composition is applied between them.

18. An article comprising a metal material and a material other than a metal, and wherein the adhesive composition is applied between them in the 16th paragraph.

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