Diacrylate composition, preparation method therefor, and curable composition comprising diacrylate composition

Abstract

The present invention relates to a diacrylate composition, a preparation method therefor, and a curable composition comprising the diacrylate composition and, more specifically, to a diacrylate composition, a preparation method therefor, and a curable composition comprising the diacrylate composition, the diacrylate composition comprising dianhydrosugar alcohol-derived diacrylate materials having a specific structure in a specific content range, and being capable of providing a cured coating layer having significantly improved heat resistance and scratch resistance, compared to conventional curable coating compositions, when used as a reactive diluent in curable coating compositions.

Description

Diacrylate composition and method for producing the same, and curable composition comprising the diacrylate composition

[0001] The present invention relates to a diacrylate composition and a method for producing the same, and a curable composition comprising the diacrylate composition, and more particularly, to a diacrylate composition comprising diacrylate substances derived from dianhydride alcohols having a specific structure in a specific content range, which, when used as a reactive diluent of a curable coating composition, can provide a cured coating layer having significantly improved heat resistance and scratch resistance compared to existing curable coating compositions, a method for producing the same, and a curable composition comprising the diacrylate composition.

[0002] Curable materials are widely used as adhesives, sealants, coatings, and paints in various industrial fields such as construction, packaging, automobiles, electrical and electronic products, optical products, and textiles, and have recently been applied to concrete as well.

[0003] Most curable materials contain components that form polymers, and these components are usually manufactured from petroleum-based raw materials. However, due to various reasons such as accelerated depletion of petroleum resources, demand for greenhouse gas reduction due to climate change, rising raw material prices, and increasing need for renewable raw materials, there is a demand for ways to partially or completely replace the components manufactured from petroleum-based raw materials with environmentally friendly components.

[0004] Hydrogenated sugars (also called “sugar alcohols”) are compounds obtained by adding hydrogen to the reducing end groups of sugars, generally HOCH2(CHOH). nIt 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.

[0005] Anhydrosugar alcohol is a substance formed by removing one or more water molecules from the interior of hydrogenated sugar. When one water molecule is removed, it has the form of a tetraol with four hydroxyl groups in the molecule. When two water molecules are removed, it has the form of a diol with two hydroxyl groups in the molecule. It can be manufactured using hexitol derived from starch (e.g., Korean Patent Registration No. 10-1079518, Korean Patent Publication No. 10-2012-0066904). Anhydrosugar alcohol has been the subject of much interest for a long time and research on its manufacturing method has been conducted because it is an environmentally friendly substance derived from renewable natural resources. Among these anhydrosugar alcohols, isosorbide manufactured from sorbitol currently has the widest range of industrial applications.

[0006] Anhydrous sugar alcohols have a wide range of applications, including treating heart and vascular diseases, as adhesives for patches, as pharmaceuticals such as mouthwashes, as solvents in cosmetics, and as emulsifiers in the food industry. Furthermore, they can raise the glass transition temperature of polymers such as polyester, PET, polycarbonate, polyurethane, and epoxy resins, improving their strength. Furthermore, as an eco-friendly material derived from natural resources, they are also very useful in the plastics industry, including bioplastics. Furthermore, they are known to be useful as eco-friendly solvents for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers. Due to their diverse applications, anhydrous sugar alcohols are attracting significant attention, and their industrial use is gradually increasing.

[0007] For example, Korean Patent Publication No. 10-2019-0047223 discloses a photocurable isosorbide derivative compound that can be used as an eco-friendly material to replace bisphenol-based polymers. However, the isosorbide derivative compound disclosed in the document is intended for use as a dental filling material, and no other uses (e.g., coatings) are disclosed.

[0008] Furthermore, European Patent Publication No. EP 3019501 A1 discloses a curable composition comprising a reaction product of isosorbide and caprolactone and an oligomer prepared using isosorbide and lactide, and its use in coatings. However, the cured coating formed from the curable composition disclosed in the above document needs to have further improved heat resistance and mechanical properties (e.g., scratch resistance).

[0009] The purpose of the present invention is to provide a diacrylate composition which is excellent in environmental friendliness and includes materials derived from anhydrous sugar alcohol, and which, when used as a reactive diluent of a curable coating composition, can provide a cured coating layer having significantly improved heat resistance and scratch resistance compared to existing curable coating compositions, and a method for producing the same, and an article including a curable composition including the diacrylate composition and a coating layer including a cured product thereof.

[0010] The present invention provides a diacrylate composition, comprising, based on 100 parts by weight of the total composition, 43 to 94 parts by weight of a dianhydride alcohol-diacrylate represented by the following chemical formula 1; and 6 to 57 parts by weight of a dianhydride alcohol-diacrylate oligomer represented by the following chemical formula 2:

[0011] [Chemical Formula 1]

[0012]

[0013] In the above chemical formula 1, R is a divalent organic group derived from a dihydric alcohol;

[0014] [Chemical Formula 2]

[0015]

[0016] In the above chemical formula 2, R is a divalent organic group derived from a dihydric alcohol; m and n independently represent integers of 0 to 5, and m+n is an integer of 1 to 10.

[0017] According to another aspect of the present invention, a method for producing a diacrylate composition is provided, comprising a step of esterifying a dianhydrosugar alcohol and acrylic acid in the presence of an acid catalyst, wherein the produced diacrylate composition comprises, based on 100 parts by weight of the total composition, 43 to 94 parts by weight of a dianhydrosugar alcohol-diacrylate represented by the above chemical formula 1; and 6 to 57 parts by weight of a dianhydrosugar alcohol-diacrylate oligomer represented by the above chemical formula 2.

[0018] According to another aspect of the present invention, a reactive diluent comprising the diacrylate composition of the present invention is provided.

[0019] According to another aspect of the present invention, a curable composition is provided comprising: a polymerizable compound; an initiator; and a reactive diluent of the present invention.

[0020] According to another aspect of the present invention, a coated article is provided, comprising a coating layer comprising a cured product of the curable composition of the present invention.

[0021] The diacrylate composition according to the present invention is excellent in environmental friendliness because it utilizes anhydrous sugar alcohol derived from natural resources, and a cured coating layer formed from a curable coating composition containing the diacrylate composition as a reactive diluent exhibits significantly improved heat resistance (increased glass transition temperature) and scratch resistance (increased surface hardness) compared to a cured product of a conventional curable coating composition.

[0022] Hereinafter, the present invention will be described in more detail.

[0023] In the present invention, the dihydric alcohol is an anhydrous sugar alcohol formed by removing two water molecules from the interior of hydrogenated sugar, has a diol form with two hydroxyl groups in the molecule, and can be manufactured by utilizing hexitol derived from starch.

[0024] Hydrogenated sugars (also called “sugar alcohols”) are compounds obtained by adding hydrogen to the reducing end groups of sugars, generally 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.

[0025] Isosorbide alcohols, derived from renewable natural resources, have long attracted considerable interest and research into their production methods has been ongoing. Among these isosorbide alcohols, produced from sorbitol, currently has the widest range of industrial applications.

[0026] The dihydrosugar alcohol may preferably be a dihydrosugar hexitol, more specifically 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

[0027] The diacrylate composition of the present invention comprises, based on 100 parts by weight of the total composition, 43 to 94 parts by weight of a dihydric alcohol-diacrylate represented by the following chemical formula 1; and 6 to 57 parts by weight of a dihydric alcohol-diacrylate oligomer represented by the following chemical formula 2:

[0028] [Chemical Formula 1]

[0029]

[0030] In the above chemical formula 1, R is a divalent organic group derived from a dihydric alcohol;

[0031] [Chemical Formula 2]

[0032]

[0033] In the above chemical formula 2, R is a divalent organic group derived from a dihydric alcohol; m and n independently represent integers of 0 to 5, and m+n is an integer of 1 to 10.

[0034] More specifically, in the above chemical formulas 1 and 2, R may each independently be a divalent organic group derived from isosorbide, isomannide, or isoidide.

[0035] More specifically, in the above chemical formulas 1 and 2, R may be independently selected from the following chemical formulas:

[0036]

[0037] (In the above, * indicates an attachment point to an adjacent oxygen atom.)

[0038] More specifically, in the above chemical formula 2, m and n can independently be integers of 0 to 4, and m+n can be an integer of 1 to 8.

[0039] More specifically, in the above chemical formula 2, m and n can each independently be an integer from 0 to 3, and m+n can be an integer from 1 to 6.

[0040] In one specific example, the dimethyl ether alcohol-diacrylate may be selected from the group consisting of compounds represented by the following chemical formulae 1-1 to 1-3, and the dimethyl ether alcohol-diacrylate oligomer may be selected from the group consisting of compounds represented by the following chemical formulae 2-1 to 2-3:

[0041] [Chemical Formula 1-1]

[0042]

[0043] [Chemical Formula 1-2]

[0044]

[0045] [Chemical Formula 1-3]

[0046]

[0047] [Chemical Formula 2-1]

[0048]

[0049] [Chemical Formula 2-2]

[0050]

[0051] [Chemical Formula 2-3]

[0052]

[0053] In the above chemical formulas 2-1 to 2-3, m, n and m+n are as defined in chemical formula 2 above.

[0054] More specifically, the above-mentioned dicarboxylic acid alcohol-diacrylate may be represented by the above-mentioned chemical formula 1-1, and the above-mentioned dicarboxylic acid alcohol-diacrylate oligomer may be represented by the above-mentioned chemical formula 2-1.

[0055] According to one specific example of the present invention, examples of the dianhydrosugar alcohol-diacrylate oligomer represented by the above chemical formula 2 include, but are not limited to, the following (the following examples are examples of the dianhydrosugar alcohol-diacrylate oligomer of the above chemical formula 2-1, and in the case of the above chemical formulas 2-2 and 2-3, the dianhydrosugar alcohol central portion having the stereochemistry shown in each of the chemical formulas 2-2 and 2-3 can be exemplified in the same manner):

[0056]

[0057] [Chemical Formula 2-1a-1] (in Chemical Formula 2-1, when m=0 and n=1; or m=1 and n=0;)

[0058]

[0059] [Chemical Formula 2-1a-2] (in Chemical Formula 2-1, when m=0 and n=2; or m=2 and n=0)

[0060]

[0061] [Chemical Formula 2-1a-3] (in Chemical Formula 2-1, when m=0 and n=3; or m=3 and n=0;)

[0062]

[0063] [Chemical Formula 2-1a-4] (in Chemical Formula 2-1, when m=0 and n=4; or m=4 and n=0;)

[0064]

[0065] [Chemical Formula 2-1a-5] (in Chemical Formula 2-1, when m=0 and n=5; or m=5 and n=0;)

[0066]

[0067] [Chemical Formula 2-1b-1] (Applies to the case where m=1 and n=1 in Chemical Formula 2-1)

[0068]

[0069] [Chemical Formula 2-1b-2] (in Chemical Formula 2-1, when m=1 and n=2; or m=2 and n=1;)

[0070]

[0071] [Chemical Formula 2-1b-3] (in Chemical Formula 2-1, when m=1 and n=3; or m=3 and n=1;)

[0072]

[0073] [Chemical Formula 2-1b-4] (in Chemical Formula 2-1, when m=1 and n=4; or m=4 and n=1;)

[0074]

[0075] [Chemical Formula 2-1b-5] (in Chemical Formula 2-1, when m=1 and n=5; or m=5 and n=1;)

[0076]

[0077] [Chemical Formula 2-1c-1] (Applies to the case where m=2 and n=2 in Chemical Formula 2-1)

[0078]

[0079] [Chemical Formula 2-1c-2] (in Chemical Formula 2-1, when m=2 and n=3; or m=3 and n=2;)

[0080]

[0081] [Chemical Formula 2-1c-3] (in Chemical Formula 2-1, when m=2 and n=4; or m=4 and n=2;)

[0082]

[0083] [Chemical Formula 2-1c-4] (in Chemical Formula 2-1, when m=2 and n=5; or m=5 and n=2;)

[0084]

[0085] [Chemical Formula 2-1d-1] (Applies to the case where m=3 and n=3 in Chemical Formula 2-1)

[0086]

[0087] [Chemical Formula 2-1d-2] (in Chemical Formula 2-1, when m=3 and n=4; or m=4 and n=3;)

[0088]

[0089] [Chemical Formula 2-1d-3] (in Chemical Formula 2-1, when m=3 and n=5; or m=5 and n=3)

[0090]

[0091] [Chemical Formula 2-1e-1] (Applies to the case where m=4 and n=4 in Chemical Formula 2-1)

[0092]

[0093] [Chemical Formula 2-1e-2] (in Chemical Formula 2-1, when m=4 and n=5; or m=5 and n=4)

[0094]

[0095] [Chemical Formula 2-1f] (Applies to the case where m=5 and n=5 in Chemical Formula 2-1)

[0096]

[0097]

[0098] The diacrylate composition of the present invention contains the dianhydrosugar alcohol-diacrylate represented by the above chemical formula 1 in an amount of 43 parts by weight to 94 parts by weight, based on 100 parts by weight of the total composition. If the content of the dianhydrosugar alcohol-diacrylate in 100 parts by weight of the diacrylate composition is less than 43 parts by weight, the scratch resistance and heat resistance of a cured product formed from a curable composition including such a diacrylate composition may be reduced. Conversely, if the content of the dianhydrosugar alcohol-diacrylate in 100 parts by weight of the diacrylate composition exceeds 94 parts by weight, the usability of a cured product formed from a curable composition including such a diacrylate composition may be limited due to crystallization, and the surface brittleness of the cured product may be increased, making it easily damaged.

[0099] More specifically, the content of the diacrylate alcohol-diacrylate in 100 parts by weight of the diacrylate composition of the present invention may be, for example, 43 parts by weight or more, 44 parts by weight or more, 45 parts by weight or more, 46 parts by weight or more, 47 parts by weight or more, 48 parts by weight or more, 49 parts by weight or more, 50 parts by weight or more, or 50.1 parts by weight or more, and may also be 94 parts by weight or less, 93.5 parts by weight or less, 93 parts by weight or less, 92.5 parts by weight or less, 92 parts by weight or less, 91.5 parts by weight or less, 91 parts by weight or less, or 90.8 parts by weight or less, but is not limited thereto.

[0100] The diacrylate composition of the present invention contains the dianhydrosugar alcohol-diacrylate oligomer represented by the above chemical formula 2 in an amount of 6 to 57 parts by weight, based on 100 parts by weight of the total composition. If the content of the dianhydrosugar alcohol-diacrylate oligomer in 100 parts by weight of the diacrylate composition is less than 6 parts by weight, the usability may be limited due to crystallization, and the surface of a cured product formed from a curable composition including such a diacrylate composition may become more brittle and easily be damaged. Conversely, if the content of the dianhydrosugar alcohol-diacrylate oligomer in 100 parts by weight of the diacrylate composition exceeds 57 parts by weight, the scratch resistance and heat resistance of a cured product formed from a curable composition including such a diacrylate composition may be reduced.

[0101] More specifically, the content of the diacrylate alcohol-diacrylate oligomer in 100 parts by weight of the diacrylate composition of the present invention may be, for example, 6 parts by weight or more, 6.5 parts by weight or more, 7 parts by weight or more, 7.5 parts by weight or more, 8 parts by weight or more, 8.5 parts by weight or more, 9 parts by weight or more, or 9.2 parts by weight or more, and may also be, but is not limited to, 57 parts by weight or less, 56 parts by weight or less, 55 parts by weight or less, 54 parts by weight or less, 53 parts by weight or less, 52 parts by weight or less, 51 parts by weight or less, 50 parts by weight or less, or 49.9 parts by weight or less.

[0102] There is no particular limitation on the viscosity of the diacrylate composition of the present invention, and it may have an appropriate viscosity according to its specific use (e.g., a reactive diluent of a curable composition), and, if necessary, may further include additional components (solvents, etc.) for viscosity control. In one specific example, the viscosity (measured at 25°C) of the diacrylate composition of the present invention may be less than 1,325 cps, 1,320 cps or less, 1,310 cps or less, 1,300 cps or less, 1,290 cps or less, 1,280 cps or less, 1,275 cps or less, or 1,274 cps or less, and preferably may be 400 cps to 1,000 cps, but is not particularly limited thereto.

[0103] According to another aspect of the present invention, a method for producing a diacrylate composition is provided, comprising a step of esterifying a dianhydrosugar alcohol and acrylic acid in the presence of an acid catalyst, wherein the produced diacrylate composition comprises, based on 100 parts by weight of the total composition, 43 to 94 parts by weight of a dianhydrosugar alcohol-diacrylate represented by the above chemical formula 1; and 6 to 57 parts by weight of a dianhydrosugar alcohol-diacrylate oligomer represented by the above chemical formula 2.

[0104] In one specific example, the dianhydrosugar alcohol may be a dianhydrosugar hexitol, more specifically 1,4:3,6-dianhydrohexitol, and even more specifically isosorbide, isomannide, isoidide or a mixture of two or more thereof, preferably isosorbide.

[0105] There is no special limitation on the above acid catalyst, and a catalyst commonly used in the esterification reaction of alcohol and carboxylic acid can be used.

[0106] In one specific example, the acid catalyst may be at least one selected from the group consisting of phosphoric acid, hypophosphoric acid, sulfuric acid, acetic acid, formic acid, heteropoly acid, paratoluenesulfonic acid, methanesulfonic acid, hydrochloric acid, acidic ion exchange resin, or a mixture thereof, but is not particularly limited thereto.

[0107] In one specific example, the type of acidic ion exchange resin is not particularly limited, but is preferably H + H-type acidic ion exchange resin, more preferably comprising sulfonic acid as an exchanger + It may be a type acidic ion exchange resin.

[0108] In one specific embodiment, the esterification reaction may be carried out in the presence of an additional additive other than an acid catalyst, specifically one or more additives selected from the group consisting of a polymerization inhibitor, an antioxidant, or a combination thereof.

[0109] In one specific example, the polymerization inhibitor may be at least one selected from the group consisting of, but not limited to, hydroquinones such as hydroquinone methyl ether, p-benzoquinone, hydroquinone, 2,5-diphenylparabenzoquinone; N-oxyradicals such as tetramethylpiperidinyl-N-oxyradical (TEMPO); substituted catechols such as t-butylcatechol; amines such as phenothiazine, diphenylamine, phenyl-β-naphthylamine; cuperone, nitrosobenzene, pickling acid, molecular oxygen, sulfur, copper(II) chloride, or a combination thereof.

[0110] In one specific example, as the antioxidant, one or more selected from the group consisting of sodium phosphite, sodium hypophosphite, potassium phosphite, magnesium phosphite, calcium phosphite, or a combination thereof may be used, but is not limited thereto.

[0111] According to one specific example, in the esterification reaction, 2.0 to 3.5 moles of acrylic acid per mole of dianhydride alcohol may be used, but is not limited thereto.

[0112] According to one specific example, the esterification reaction may be performed in a solvent (e.g., toluene) at a temperature of 60°C to 140°C (more specifically, 80°C to 120°C) for 5 to 30 hours (more specifically, 15 to 24 hours), but is not limited thereto.

[0113] For example, the reaction formulas in which isosorbide and acrylic acid as dianhydride alcohols undergo an esterification reaction to produce dianhydride alcohol-diacrylate of the above chemical formula 1 and dianhydride alcohol-diacrylate oligomer represented by the above chemical formula 2 are as follows:

[0114]

[0115] In one specific embodiment, the method for producing a diacrylate composition of the present invention may further include, after the esterification reaction step, one or more steps selected from a step of removing unreacted dianhydride alcohol and acrylic acid, if necessary; and a solvent removal step.

[0116] In one specific example, the step of removing the unreacted dimethyl ether and acrylic acid may be performed through a neutralization and washing process of the reaction product, but is not limited thereto.

[0117] In one specific example, neutralization and washing of the reaction product may be performed using a basic solution and water. Specifically, the basic solution may be an aqueous solution of a basic substance selected from the group consisting of an alkali metal hydroxide, an alkali metal bicarbonate compound, or a combination thereof, but is not limited thereto.

[0118] In one specific example, the solvent removal step may be performed through reduced pressure concentration at a temperature of 60°C to 90°C, specifically 70°C to 80°C, but is not limited thereto.

[0119] According to another aspect of the present invention, a reactive diluent comprising the diacrylate composition of the present invention is provided.

[0120] In one specific embodiment, the reactive diluent may consist solely of the diacrylate composition of the present invention, or may additionally include a conventional reactive diluent component other than the diacrylate composition of the present invention.

[0121] According to another aspect of the present invention, a curable composition is provided comprising a polymerizable compound; an initiator; and a reactive diluent of the present invention.

[0122] As the polymerizable compound included in the curable composition of the present invention, a compound having at least one polymerizable group can be used without any particular limitation.

[0123] In one specific embodiment, the polymerizable compound may be at least one selected from the group consisting of a polymerizable monomer, a polymerizable oligomer, a polymerizable polymer, or a combination thereof having at least one polymerizable group.

[0124] In one specific example, the polymerizable group may be, but is not limited to, an unsaturated group, a (meth)acrylic group, or a combination thereof. The unsaturated group refers to a functional group having a carbon double bond or a carbon triple bond.

[0125] In one specific example, the polymerizable monomer may include a (meth)acrylic monomer having at least one (meth)acrylic group in the molecule, the polymerizable oligomer may include a (meth)acrylic oligomer having at least one (meth)acrylic group in the molecule, and the polymerizable polymer may include a (meth)acrylic polymer having at least one (meth)acrylic group in the molecule.

[0126] According to one specific example, the (meth)acrylic monomer may be, but is not limited to, one or a mixture of two or more compounds having one or more (specifically, 1 to 6, more specifically, 1 to 4) (meth)acrylic groups in the molecule.

[0127] In one specific example, the monomer having one (meth)acrylic group as the (meth)acrylic monomer is, 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 It may be, but is 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, or mixtures thereof.

[0128] In another specific example, the monomer having two or more (meth)acryl groups as the (meth)acrylic monomer is, for example, 1,6-hexanediol diacrylate (HDDA), 1,4-butanediol diacrylate (BDDA), tripropylene glycol diacrylate (TPGDA), bisphenol A [EO]4~30 diacrylate (BPA[EO]4~30DA, EO is an ethylene oxide unit), trimethylolpropane triacrylate (TMPTA), trimethylolpropane [EO]3~15 triacrylate (TMP[EO]3~15TA, EO may be, but is not limited to, ethylene oxide units), pentaerythritol triacrylate (PETA), ), pentaerythritol tetraacrylate (PETTA), ditrimethylolpropane tetraacrylate (DTMPTTA), dipentaerythritol pentaacrylate (DPPA), dipentaerythritol hexaacrylate (DPHA), or mixtures thereof.

[0129] In one specific example, the (meth)acrylic oligomer may be 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, but is not limited thereto.

[0130] In one specific example, the content of the polymerizable compound in the curable composition of the present invention may be 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, or 40 parts by weight or more, based on 100 parts by weight of the total composition, and may also be 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, 75 parts by weight or less, 70 parts by weight or less, 65 parts by weight or less, 60 parts by weight or less, 55 parts by weight or less, or 50 parts by weight or less, for example, 10 to 90 parts by weight, 20 to 80 parts by weight, or 25 to 60 parts by weight, but is not particularly limited thereto. If the content of the polymerizable compound in the curable composition is too low compared to the above level, the mechanical properties of the cured product formed from the composition may not be sufficient, and conversely, if the content is too high compared to the above level, the coating properties of the composition may deteriorate and the appearance of the cured product may be poor.

[0131] The initiator included in the curable composition of the present invention may include at least one selected from the group consisting of photoinitiators, thermal initiators, and combinations thereof. The photoinitiators and thermal initiators may be any of those commonly used in this field without limitation.

[0132] In one specific example, the photoinitiator may be an acetophenone such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 4-t-butyltrichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzyl dimethyl ketal, acylphosphine oxides, titanocene compounds, benzophenone, Benzophenones such as benzoylbenzoic acid, benzoylbenzoic acid methyl ether, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzol-4'-methyldiphenyl sulfide, 3,3'-methyl-4-methoxybenzophenone, and thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, and isopropylthioxanthone can be used alone or in combination of two or more, but are not limited thereto.

[0133] Also, for example, photoinitiators include Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Benzionalkylether, Benzophenone, Benzyl dimethyl katal, Hydroxycyclohexyl phenylacetone, Chloroacetophenone, 1,1-Dichloro acetophenone, Diethoxy acetophenone, Hydroxy Acetophenone, 2-Chloro thioxanthone, 2-ETAQ (2-EthylAnthraquinone), 1-Hydroxy-cyclohexyl-phenyl-ketone, 2-Hydroxy-2-methyl-1-phenyl-1-propanone, 2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, methylbenzoylformate, etc. can be used alone or in combination of two or more, but are not limited thereto.

[0134] In one specific example, the thermal initiator may be selected from the group consisting of a compound represented by the following chemical formula 3, a compound represented by the following chemical formula 4, or a mixture thereof.

[0135] [Chemical Formula 3]

[0136]

[0137] In the above chemical formula 3,

[0138] R and R' are each independently a C2-C8 linear or C3-C8 branched alkyl group; a C3-C20 cycloalkyl group; a C6-C20 aryl group; or a C2-C8 linear or C3-C8 branched methoxy-alkyl group,

[0139] X is -CN or -CO2R", where R" is a C2-C8 linear or C3-C8 branched alkyl group; a C3-C20 cycloalkyl group; or a C6-C20 aryl group,

[0140] [Chemical Formula 4]

[0141]

[0142] In the above chemical formula 4,

[0143] R is each independently a C2-C8 linear or C3-C8 branched alkyl group; a C3-C20 cycloalkyl group; or a C6-C20 aryl group.

[0144] In one specific embodiment, the content of the initiator in the curable composition of the present invention may be 0.1 part by weight or more, 0.2 part by weight or more, 0.5 part by weight or more, 0.7 part by weight or more, or 1 part by weight or more, based on 100 parts by weight of the total composition, and may also be 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less, or 4 parts by weight or less, for example, 0.1 to 10 parts by weight, 0.2 to 5 parts by weight, or 0.5 to 4 parts by weight, but is not particularly limited thereto. If the content of the initiator in the curable composition is excessively less than the above level, the curing speed of the composition may be slowed down, and conversely, if it is excessively more than the above level, cracks may occur in the cured product due to excessive curing.

[0145] In one specific example, the content of the reactive diluent of the present invention included in the curable composition of the present invention may be 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, based on 100 parts by weight of the total composition, and may also be 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, 75 parts by weight or less, or 70 parts by weight or less, for example, 5 to 90 parts by weight, 10 to 80 parts by weight, or 20 to 70 parts by weight, but is not particularly limited thereto. If the content of the reactive diluent in the curable composition is excessively less than the above level, the appearance characteristics of a cured product formed from such composition may deteriorate, or the adhesion to other substrates may deteriorate, and conversely, if it is excessively more than the above level, the strength and heat resistance of the cured product may deteriorate.

[0146] In addition to the components described above, the curable composition of the present invention may additionally include one or more additives commonly used in curable compositions (e.g., coating compositions) as needed.

[0147] In one embodiment, the curable composition of the present invention may further comprise one or more additives selected from the group consisting of ultraviolet absorbers, stabilizers (light stabilizers and / or heat stabilizers), leveling agents, inorganic nanoparticles, antioxidants, wetting agents, thickeners, lubricants, softeners, surface conditioners, surfactants, defoamers, slip agents, stain inhibitors, or combinations thereof.

[0148] In one specific example, the ultraviolet absorbent may be, but is not limited to, a triazine-based ultraviolet absorbent, a phenyl salicylate-based ultraviolet absorbent, a benzophenone-based ultraviolet absorbent, a benzotriazole-based ultraviolet absorbent, a nickel derivative, a radical scavenger, or a combination thereof.

[0149] In one specific example, the stabilizer may be, but is not limited to, a hindered amine stabilizer, a phenyl salicylate stabilizer, a benzophenone stabilizer, a benzotriazole stabilizer, a polyphenol stabilizer, a phosphite stabilizer, a lactone stabilizer, or a combination thereof.

[0150] In one specific example, the leveling agent may be, but is not limited to, a silicone diacrylate-based compound, a silicone polyacrylate-based compound, or a combination thereof.

[0151] In one specific example, the inorganic nanoparticle may be, but is not limited to, one or more types of inorganic nanoparticles (e.g., Al2O3, SiO2, ZnO, ZrO2, BaTiO3, TiO2, Ta2O5, Ti3O5, ITO, IZO, ATO, ZnO-Al, Nb2O3, SnO, MgO, etc. having an average particle diameter of 1 to 100 nm) having a reactive functional group (e.g., an acryloyl group, a methacryloyl group, a vinyl group such as vinyl ether, or a hydroxyl group, etc.).

[0152] Additionally, in one specific example, the antioxidant may be, for example, a phenolic antioxidant; the humectant may be, for example, a polyether-modified polydimethylsiloxane; and the antifoaming agent may be, for example, dimethylpolysiloxane, but is not limited thereto.

[0153] When one or more of the above-described additive components are additionally included in the curable composition of the present invention, the content of each additive may be 0.1 parts by weight or more, 0.2 parts by weight or more, 0.5 parts by weight or more, 0.7 parts by weight or more, or 1 part by weight or more, based on 100 parts by weight of the total composition, and may also be 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, or 3 parts by weight or less, and for example, may be 0.1 to 10 parts by weight, 0.2 to 5 parts by weight, or 0.5 to 3 parts by weight, but is not particularly limited thereto. When the content of such additives is out of the above-described range, the improvement of the desired physical properties (e.g., workability, smoothness of the coating layer, etc.) may not be sufficient.

[0154] In one specific example, when a UV absorber is included in the curable composition of the present invention, the content thereof may be, for example, 0.1 to 10 parts by weight, 1 to 5 parts by weight, or 1 to 3 parts by weight, but is not particularly limited thereto. If the content of the UV absorber is outside the above-mentioned range, curing may be hindered during curing, and it may be difficult to expect weather resistance of the coating layer.

[0155] According to another aspect of the present invention, the present invention provides a novel compound, a dimethyl ether alcohol-diacrylate oligomer of the following chemical formula 2':

[0156] [Chemical Formula 2']

[0157]

[0158] In the above chemical formula 2', R is a divalent organic group derived from a dihydric alcohol; m and n independently represent integers of 0 to 5, and m+n is an integer of 2 to 10.

[0159] In the above chemical formula 2', R is the same as R defined in the chemical formula 2 above.

[0160] In one specific example, the dimethyl ether alcohol-diacrylate oligomer of the above chemical formula 2' may be selected from the group consisting of compounds represented by the following chemical formulas 2'-1 to 2'-3:

[0161] [Chemical Formula 2'-1]

[0162]

[0163] [Chemical Formula 2'-2]

[0164]

[0165] [Chemical Formula 2'-3]

[0166]

[0167] In the above chemical formulas 2'-1 to 2'-3, m and n are independently integers of 0 to 5, and m+n is an integer of 2 to 10. More specifically, m and n are independently integers of 1 to 5, and m+n may be an integer of 2 to 10, and even more specifically, m and n are independently integers of 1 to 3, and m+n may be an integer of 2 to 6, or 2 to 5.

[0168] Examples of the compounds of the above chemical formulas 2'-1 to 2'-3 may be the above chemical formulas 2-1a-2 to 2-1a-5, 2-1b-1 to 2-1b-5, 2-1c-1 to 2-1c-4, 2-1d-1 to 2-1d-3, 2-1e-1 to 2-1e-2, or 2-1f.

[0169] The dianhydrosugar alcohol-diacrylate oligomer of the above chemical formula 2' of the present invention can be used as a reactive diluent in a curable composition. When the dianhydrosugar alcohol-diacrylate oligomer of the above chemical formula 2' of the present invention is included as a reactive diluent in a curable composition, a cured coating layer having significantly improved heat resistance and scratch resistance compared to existing curable compositions can be provided.

[0170] In this respect, the present invention provides a reactive diluent or a composition for a reactive diluent comprising the dihydric alcohol-diacrylate oligomer of the above chemical formula 2'. The reactive diluent may be for use in a curable composition.

[0171] The dihydric alcohol-diacrylate oligomer of the above chemical formula 2' included in the reactive diluent or the composition for the reactive diluent of the present invention may be at least one of the compounds of the above chemical formulas 2-1a-2 to 2-1a-5, 2-1b-1 to 2-1b-5, 2-1c-1 to 2-1c-4, 2-1d-1 to 2-1d-3, 2-1e-1 to 2-1e-2, or 2-1f.

[0172] Specific details of the reactive diluent or composition for the reactive diluent are as described above.

[0173] In another aspect, the present invention provides a curable composition comprising an alcohol-diacrylate oligomer of the above chemical formula 2'.

[0174] The dihydric alcohol-diacrylate oligomer of the above-described chemical formula 2' included in the curable composition of the present invention may be at least one of the compounds of the above-described chemical formulas 2-1a-2 to 2-1a-5, 2-1b-1 to 2-1b-5, 2-1c-1 to 2-1c-4, 2-1d-1 to 2-1d-3, 2-1e-1 to 2-1e-2, or 2-1f.

[0175] The above curable composition may further include a polymerizable compound and an initiator in addition to the dimethyl ether alcohol-diacrylate oligomer of the above chemical formula 2' of the present invention.

[0176] Specific details of the above curable composition are as described above.

[0177] According to another aspect of the present invention, a coated article is provided, comprising a coating layer comprising a cured product of the curable composition of the present invention.

[0178] There are no particular limitations on the shape and use of the coated article of the present invention, and in one specific example, the coated article of the present invention may be a film, a sheet, a molded article, a machine part, an electrical part, or an electronic part, but is not limited thereto.

[0179] There are no particular limitations on the method for forming a coating layer of the curable composition of the present invention on the above-mentioned article, and it can be performed using conventional coating methods and equipment. 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 thereto.

[0180] [Example]

[0181] <Preparation of diacrylate composition>

[0182] Example A1: Preparation of diacrylate composition

[0183] In a 3,000 ml 5-neck reactor equipped with a nitrogen pipe, a trap for removing by-products, a stirrer, a thermometer, and a heater, 625.0 g of isosorbide, 616.4 g of acrylic acid, 744.8 g of toluene as a solvent, 3.4 g of hydroquinone methyl ether as a polymerization inhibitor, and 1.7 g of hypophosphoric acid as an acid catalyst were placed, and the temperature was raised to 80°C under a nitrogen atmosphere, and the reaction raw materials were dissolved while stirring as necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 120°C, and the esterification reaction was performed for 15 to 24 hours until the theoretical amount of water was removed, and then cooled.

[0184] After cooling to room temperature, neutralization washing and water washing were performed using a 0.1 M caustic soda aqueous solution and water to neutralize the reactants, thereby removing unreacted alcohol and acrylic acid. After neutralization and washing were completed, a desolvation process was performed for 3 hours under reduced pressure at 70°C to remove the solvent toluene, and after desolvation, the mixture was cooled to room temperature to obtain 990.7 g of a diacrylate composition including isosorbide diacrylate of the following chemical formula 1-1 and isosorbide diacrylate oligomer of the following chemical formula 2-1 (wherein, m+n=1 to 3). The contents of the isosorbide diacrylate and the isosorbide diacrylate oligomer in the diacrylate composition manufactured at this time were 90.8 wt% and 9.2 wt%, respectively, and the viscosity of the diacrylate composition was 1,274 cps (measurement temperature: 25°C), and the results are shown in Table 1 below.

[0185] [Chemical Formula 1-1]

[0186]

[0187] [Chemical Formula 2-1]

[0188]

[0189] Example A2: Preparation of diacrylate composition

[0190] Except that the amount of isosorbide used was changed from 625.0 g to 569.0 g and the amount of acrylic acid was changed from 616.4 g to 673.4 g, the same method as in Example A1 was performed to obtain 894.3 g of a diacrylate composition including the isosorbide diacrylate of the above chemical formula 1-1 and the isosorbide diacrylate oligomer of the above chemical formula 2-1 (wherein m+n=1 to 5). At this time, the contents of the isosorbide diacrylate and the isosorbide diacrylate oligomer in the prepared diacrylate composition were 78.5 wt% and 21.5 wt%, respectively, and the viscosity of the diacrylate composition was 418 cps (measurement temperature: 25°C), and the results are shown in Table 1 below.

[0191] Example A3: Preparation of diacrylate composition

[0192] Except that the amount of isosorbide used was changed from 625.0 g to 533.0 g and the amount of acrylic acid was changed from 616.4 g to 709.6 g, the same method as in Example A1 was performed to obtain 920.7 g of a diacrylate composition including the isosorbide diacrylate of the above chemical formula 1-1 and the isosorbide diacrylate oligomer of the above chemical formula 2-1 (wherein m+n=1 to 6). At this time, the contents of the isosorbide diacrylate and the isosorbide diacrylate oligomer in the prepared diacrylate composition were 69.4 wt% and 31.6 wt%, respectively, and the viscosity of the diacrylate composition was 676 cps (measurement temperature: 25°C), and the results are shown in Table 1 below.

[0193] Example A4: Preparation of diacrylate composition

[0194] Except for changing the amount of isosorbide used from 625.0 g to 501.0 g and changing the amount of acrylic acid used from 616.4 g to 741.1 g, the same method as Example A1 was performed to obtain 885.5 g of a diacrylate composition including the isosorbide diacrylate of the above chemical formula 1-1 and the isosorbide diacrylate oligomer of the above chemical formula 2-1 (wherein m+n=1 to 8). At this time, the contents of the isosorbide diacrylate and the isosorbide diacrylate oligomer in the prepared diacrylate composition were 58.8 wt% and 41.2 wt%, respectively, and the viscosity of the diacrylate composition was 863 cps (measurement temperature: 25°C), and the results are shown in Table 1 below.

[0195] Example A5: Preparation of diacrylate composition

[0196] Except for changing the amount of isosorbide used from 625.0 g to 456.0 g and changing the amount of acrylic acid used from 616.4 g to 787.0 g, the same method as Example A1 was performed to obtain 967.1 g of a diacrylate composition including the isosorbide diacrylate of the above chemical formula 1-1 and the isosorbide diacrylate oligomer of the above chemical formula 2-1 (wherein m+n=1 to 9). At this time, the contents of the isosorbide diacrylate and the isosorbide diacrylate oligomer in the prepared diacrylate composition were 50.1 wt% and 49.9 wt%, respectively, and the viscosity of the diacrylate composition was 1,090 cps (measurement temperature: 25°C), and the results are shown in Table 1 below.

[0197] Comparative Example A1: Preparation of isosorbide diacrylate

[0198] In a 3,000 ml jacketed five-neck reactor equipped with a nitrogen tube, a stirrer, a thermometer, and a hot and cold circulating water bath, 198.0 g of isosorbide and 750 mL of dichloromethane as a solvent were placed, and stirring was performed under a nitrogen atmosphere while maintaining the internal temperature of the reactor at 0°C using a coolant from the hot and cold circulating water bath. 329.0 g of triethylamine was added to the reactor maintained at 0°C, and 367.9 g of acryloyl chloride diluted in 500 ml of dichloromethane was slowly added dropwise over 2 hours. After adding the acryloyl chloride dropwise, the reaction was carried out with stirring for 24 to 28 hours while maintaining the temperature of the reaction mass at 20 to 25°C.

[0199] After the reaction was completed, the reaction product was neutralized with a saturated solution of sodium bicarbonate, washed three times with a saturated aqueous sodium chloride solution, and then washed three times with distilled water to remove impurities. The organic phase was then dried over anhydrous magnesium sulfate, and the solvent, dichloromethane, was removed under vacuum at 40°C.

[0200] The mixture obtained through the above process was subjected to a recrystallization process using petroleum ether to obtain 252.1 g of isosorbide diacrylate of the above chemical formula 1-1 in a solid state.

[0201] The purity of the solid-state isosorbide diacrylate obtained above was 99% or higher, and the results are shown in Table 1 below.

[0202] Comparative Example A2: Preparation of diacrylate composition

[0203] Except for changing the amount of isosorbide used from 625.0 g to 658.0 g and changing the amount of acrylic acid used from 616.4 g to 584.0 g, the same method as Example A1 was performed to obtain 745.2 g of a diacrylate composition including the isosorbide diacrylate of the above chemical formula 1-1 and the isosorbide diacrylate oligomer of the above chemical formula 2-1 (wherein m+n=1 to 2). At this time, the contents of the isosorbide diacrylate and the isosorbide diacrylate oligomer in the prepared diacrylate composition were 94.6 wt% and 5.4 wt%, respectively, and the viscosity of the diacrylate composition was 1,642 cps (measurement temperature: 25°C), and the results are shown in Table 1 below.

[0204] Comparative Example A3: Preparation of diacrylate composition

[0205] Except for changing the amount of isosorbide used from 625.0 g to 418.0 g and changing the amount of acrylic acid used from 616.4 g to 824.4 g, the same method as Example A1 was performed to obtain 736.9 g of a diacrylate composition including the isosorbide diacrylate of the above chemical formula 1-1 and the isosorbide diacrylate oligomer of the above chemical formula 2-1 (wherein m+n=1 to 11). At this time, the contents of the isosorbide diacrylate and the isosorbide diacrylate oligomer in the prepared diacrylate composition were 42.1 wt% and 57.9 wt%, respectively, and the viscosity of the diacrylate composition was 1,325 cps (measurement temperature: 25°C), and the results are shown in Table 1 below.

[0206] The components and contents of the reaction raw materials used in Examples A1 to A5 and Comparative Examples A1 to A3 are listed in Table 1 below.

[0207] <Analysis of diacrylate compositions>

[0208] 1. Composition analysis

[0209] Each of the diacrylate compositions prepared in Examples A1 to A5 and Comparative Examples A2 to A3 was dissolved in acetonitrile at 0.5 to 1 wt%, and then the content of isosorbide diacrylate of Chemical Formula 1-1 and isosorbide diacrylate oligomer of Chemical Formula 2-1 was measured using a high performance liquid chromatography (HPLC) device (Agilent).

[0210] More specifically, the column used for content measurement was ZORBAX Eclipse Plus C18 (4.6 x 250 mm, 5 μm, Agilent), and a flow rate of 1 mL / min was utilized in a column chamber set to 40°C. The developing solvent used for the analysis was water and acetonitrile, and the developing solvent composition was set to change from the volume ratio of water:acetonitrile = 80:20 (v / v%) to water:acetonitrile = 40:60 (v / v%) for approximately 40 min, a UV detector was used, and the injection amount of the analysis sample was set to 10 μL.

[0211] The content of isosorbide diacrylate in the result obtained in Comparative Example A1 was also measured using HPLC in the same manner.

[0212] 2. Viscosity measurement

[0213] Each of the diacrylate compositions prepared in Examples A1 to A5 and Comparative Examples A2 to A3 was stored in an oven maintained at 25°C for 30 minutes, then aliquoted into a viscosity-measuring container maintained at 25°C, and the viscosity of the diacrylate composition was measured using a viscometer (Brookfield, DV2T LV) at 30 rpm using a #LV-2(62) spindle.

[0214]

[0215]

[0216] <Manufacture of coating composition>

[0217] Examples B1 to B5 and Comparative Examples B1 to B7

[0218] A photocurable coating composition was prepared by placing a reactive diluent, an acrylic modified polyurethane resin (CN981, Sartomer Co., Ltd.) as a polymerizable compound, a photoinitiator, an ultraviolet absorber, and a light stabilizer in the types and contents listed in Table 2 below into a polyethylene container of a 200 ml paste mixer with separated upper and lower halves, mixing for 10 minutes using a paste mixer (manufactured by THINKY Co., Ltd.), and then performing defoaming mixing for 1 minute. At this time, the total content of the reactive diluent, the polymerizable compound, the photoinitiator, the ultraviolet absorber, and the light stabilizer was 100 parts by weight.

[0219] [Description of ingredients used]

[0220] - Example A1: Diacrylate composition prepared in Example A1

[0221] - Example A2: Diacrylate composition prepared in Example A2

[0222] - Example A3: Diacrylate composition prepared in Example A3

[0223] - Example A4: Diacrylate composition prepared in Example A4

[0224] - Example A5: Diacrylate composition prepared in Example A5

[0225] - Comparative Example A1: Isosorbide diacrylate (solid with a purity of 99% or more) manufactured in Comparative Example A1

[0226] - Comparative Example A2: Diacrylate composition manufactured in Comparative Example A2

[0227] - Comparative Example A3: Diacrylate composition manufactured in Comparative Example A3

[0228] - CN981: Acrylic-modified polyurethane resin (Sartomer)

[0229] - HDDA: 1,6-hexanediol diacrylate (TCI)

[0230] - DPGDA: Dipropylene glycol diacrylate (TCI)

[0231] - AA: Acrylic acid (TCI)

[0232] - Darocur 1173: Photoinitiator (2-hydroxy-2-methylpropiophenone, Sigma-Aldrich)

[0233] - TINUVIN 1577: UV absorber (BASF)

[0234] - TINUVIN 123: Light stabilizer (BASF)

[0235]

[0236]

[0237]

[0238] <Manufacturing of cured specimens and measurement of physical properties>

[0239] Examples C1 to C5 and Comparative Examples C1 to C7

[0240] The coating compositions prepared in Examples B1 to B5 and Comparative Examples B1 to B7 were coated on a PET film (SKC-V7000) coated with a urethane primer using a bar coater so that the wet film thickness was 90 μm. At this time, an appropriate bar coater was selected depending on the viscosity of each coating composition.

[0241] A cured specimen was prepared by passing a PET film coated with the above coating composition through a conveyor-type UV curing machine (UMC-HM4.8K-CVK2, UMV Korea) three times while irradiating it with ultraviolet rays from a mercury lamp (120 W). At this time, the belt speed of the UV curing machine was set to 5 m / min.

[0242] For each of the above-manufactured cured specimens, the physical properties were evaluated according to the following method, and the results are shown in Table 3 below.

[0243] 1. Glass transition temperature (Tg, unit: ℃)

[0244] The glass transition temperature of the cured specimen was measured using a differential scanning calorimeter (DSC Q100, manufactured by TA Instrument). Specifically, the temperature was increased from 20°C to 200°C at a heating rate of 10°C / min, then rapidly cooled to -70°C, and then increased again to 300°C to measure the glass transition temperature.

[0245] 2. Pencil hardness

[0246] The pencil hardness was measured using a Motorized Pencil Hardness Tester 191 (Ocean Science) according to ASTM D3363. Specifically, the pencil lead specified in KS G2603 (pencil) was placed on the hardened specimen at an angle of approximately 45° and moved 30 mm at a speed of 30 mm / min while pressing the surface with a load of approximately 1 kgf (9.8 N), and the hardness was indicated according to the degree of scratching of the surface of the hardened specimen. The hardness values ​​were indicated as 9H to 1H, F, HB, and 1B to 6B depending on the hardness and concentration of the pencil black lead, with 9H having the highest hardness, 6B having the lowest hardness, and the hardness decreasing sequentially.

[0247] 3. Modulus (unit: MPa)

[0248] The modulus of the cured specimens was measured at a speed of 5 mm / min using a UTM (Instron 5967, manufactured by Instron). Specifically, each cured specimen was cut into a size of 4 cm × 0.5 cm × 90 μm (width × length × thickness), and then a total of 5 measurements were taken for each cured specimen using a UTM (Instron 5967, manufactured by Instron) at a speed of 5 mm / min, and the average value of the measurements was calculated.

[0249]

[0250]

[0251] As described in Table 3 above, Examples C1 to C5 according to the present invention exhibited excellent heat resistance with a glass transition temperature of 48°C or higher, excellent scratch resistance with a pencil hardness of 2H or higher, and excellent rigidity with an average modulus of 1,200 MPa or higher. That is, it was confirmed that the cured coating formed from the curable composition using the diacrylate composition of the present invention as a reactive diluent had excellent heat resistance, scratch resistance, and rigidity.

[0252] On the other hand, in the case of Comparative Examples C1 to C3, the glass transition temperature was 46°C or lower, the pencil hardness was 1H or lower, and the average modulus was 1,144 MPa or lower, which were all measured properties inferior to those of Examples C1 to C5. In the case of Comparative Examples C4 to C6, the glass transition temperature was 36°C or lower, the pencil hardness was HB or lower, and the average modulus was 919 MPa or lower, which were inferior to those of Examples C1 to C5. In Comparative Example C7, the glass transition temperature was 34°C, the pencil hardness was HB, and the average modulus was 391 MPa, which were very inferior to those of Examples C1 to C5.

Claims

1. As a diacrylate composition, Based on 100 parts by weight of the total composition, 43 to 94 parts by weight of an alcohol-diacrylate represented by the following chemical formula 1; and Containing 6 to 57 parts by weight of an alcohol-diacrylate oligomer represented by the following chemical formula 2; Diacrylate composition: [Chemical Formula 1] In the above chemical formula 1, R is a divalent organic group derived from a dihydric alcohol; [Chemical Formula 2] In the above chemical formula 2, R is a divalent organic group derived from a dihydric alcohol; m and n independently represent integers of 0 to 5, and m+n is an integer of 1 to 10.

2. A diacrylate composition in paragraph 1, wherein in chemical formulas 1 and 2, R is each independently a divalent organic group derived from isosorbide, isomannide, or isoidide.

3. In the first paragraph, a diacrylate composition wherein in chemical formulae 1 and 2, R is each independently selected from the following chemical formulae: (In the above, * indicates an attachment point to an adjacent oxygen atom.) 4. In paragraph 1, The diacrylate alcohol is selected from the group consisting of compounds represented by the following chemical formulae 1-1 to 1-3, The dimethyl ether alcohol-diacrylate oligomer is selected from the group consisting of compounds represented by the following chemical formulas 2-1 to 2-3. Diacrylate composition: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] In the above chemical formulas 2-1 to 2-3, m, n and m+n are as defined in the first clause.

5. A method for producing a diacrylate composition, It includes a step of esterifying an alcohol and acrylic acid under an acid catalyst, The manufactured diacrylate composition comprises, based on 100 parts by weight of the total composition, 43 to 94 parts by weight of a dihydric alcohol-diacrylate represented by the following chemical formula 1; and 6 to 57 parts by weight of a dihydric alcohol-diacrylate oligomer represented by the following chemical formula 2. Method for preparing diacrylate composition: [Chemical Formula 1] In the above chemical formula 1, R is a divalent organic group derived from a dihydric alcohol; [Chemical Formula 2] In the above chemical formula 2, R is a divalent organic group derived from a dihydric alcohol; m and n independently represent integers of 0 to 5, and m+n is an integer of 1 to 10.

6. A reactive diluent comprising a diacrylate composition according to any one of claims 1 to 4.

7. Polymerizable compounds; Initiator; and Reactive diluent of Article 6; including; Curable composition.

8. A curable composition in the 7th paragraph, wherein the polymerizable compound is at least one selected from the group consisting of a polymerizable monomer, a polymerizable oligomer, a polymerizable polymer, or a combination thereof having at least one polymerizable group.

9. A curable composition according to claim 8, wherein the polymerizable monomer comprises a (meth)acrylic monomer having at least one (meth)acrylic group in the molecule, the polymerizable oligomer comprises a (meth)acrylic oligomer having at least one (meth)acrylic group in the molecule, and the polymerizable polymer comprises a (meth)acrylic polymer having at least one (meth)acrylic group in the molecule.

10. In the 9th paragraph, 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, a curable composition.

11. A curable composition according to claim 7, further comprising at least one additive selected from the group consisting of ultraviolet absorbers, stabilizers, leveling agents, inorganic nanoparticles, antioxidants, wetting agents, thickeners, lubricants, softeners, surface conditioners, surfactants, anti-foaming agents, slip agents, stain inhibitors, or combinations thereof.

12. A coated article comprising a coating layer comprising a cured product of the curable composition of paragraph 7.

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