Composition and coating agent

Abstract

The present invention provides a composition that, when cured, exhibits a well-balanced combination of self-healing properties against scratches, blockage resistance, flexibility, and excellent transparency. [Solution] A composition comprising a urethane (meth)acrylate compound (A) and a polysiloxane structure-containing compound (B), wherein the urethane (meth)acrylate compound (A) is a reaction product of a hydroxyl group-containing (meth)acrylate compound (x) containing a structural moiety derived from ε-caprolactone, a polyvalent isocyanate compound (y), and a polyol (z), and the polyvalent isocyanate compound (y) is at least one selected from the group consisting of biuret-type polymers, nurate-type polymers, and allophanate-type polymers of hexamethylene diisocyanate.

Description

[Technical Field]

[0001] The present invention relates to compositions and coating agents, and more particularly to compositions for forming a cured coating film with excellent self-healing properties against scratches, transparency, blocking resistance, and flexibility, and to coating agents using the same. [Background technology]

[0002] Active energy ray curable resin compositions are widely used as coating agents, adhesives, or anchor coating agents for various substrates because curing is completed by irradiation with active energy rays such as radiation for a very short time.

[0003] When the aforementioned active energy ray-curable resin composition is used as a coating agent, it is desirable that it be able to form a cured coating film with excellent self-healing properties against scratches, blocking resistance, transparency, and other properties. As an example of such an active energy ray-curable resin composition, Patent Document 1 discloses an active energy ray-curable resin composition containing a urethane (meth)acrylate compound obtained by reacting a hydroxyl group (meth)acrylate compound containing a structural moiety derived from ε-caprolactone with a polyvalent isocyanate compound, and a polysiloxane structure-containing compound. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-125058 [Overview of the project] [Problems that the invention aims to solve]

[0005] The active energy ray curable resin composition described in Patent Document 1 has sufficient resilience for practical use and excellent blocking resistance and transparency, but its flexibility after curing is insufficient, and further improvements are needed.

[0006] Therefore, against this background, the present invention aims to provide a composition that, when cured, exhibits a good balance of self-healing properties against scratches, blocking resistance, and flexibility, as well as excellent transparency. [Means for solving the problem]

[0007] However, in view of these circumstances, the inventors diligently conducted research and found that the above problems can be solved by using in combination a urethane (meth)acrylate compound obtained by reacting a hydroxyl group-containing (meth)acrylate compound containing a structural site derived from ε-caprolactone, a polyvalent isocyanate compound, and a polyol with a polysiloxane structure-containing compound, and thus completed the present invention.

[0008] In other words, the present invention has the following aspects. [1] A composition containing a urethane (meth)acrylate compound (A) and a polysiloxane structure-containing compound (B), A resin composition in which the urethane (meth)acrylate compound (A) is a reaction product of a hydroxyl group-containing (meth)acrylate compound (x) containing a structural moiety derived from ε-caprolactone, a polyvalent isocyanate compound (y), and a polyol (z). [2] The composition according to [1], wherein the hydroxyl group-containing (meth)acrylate compound (x) is a hydroxyl group-containing (meth)acrylate compound containing one ethylenically unsaturated group. [3] The composition according to [1] or [2], wherein the polyvalent isocyanate compound (y) is at least one selected from the group consisting of biuret-type polymers, nurate-type polymers, and allophanate-type polymers of hexamethylene diisocyanate. [4] The composition according to any one of [1] to [3], wherein the number average molecular weight of the polyvalent isocyanate compound (y) is 500 to 5,000. [5] The composition according to any one of [1] to [4], wherein the weight average molecular weight of the urethane (meth)acrylate compound (A) is 1,000 to 70,000. [6] The composition according to any one of [1] to [5], wherein the dispersity of the urethane (meth)acrylate compound (A) is 6 or less. [7] The composition according to any one of [1] to [6], wherein the polysiloxane structure-containing compound (B) contains one or more ethylenically unsaturated groups. [8] The composition according to any one of [1] to [7], wherein the polysiloxane structure-containing compound (B) is a polysiloxane structure-containing urethane (meth)acrylate compound (B1). [9] The composition according to any one of [1] to [8], wherein the silicon atom content of the polysiloxane structure-containing compound (B) is 0.1 to 80% by mass.

[10] The composition according to any one of [1] to [9], wherein the content of the polysiloxane structure-containing compound (B) is 0.01 to 100 parts by mass relative to 100 parts by mass of the urethane (meth)acrylate compound (A).

[11] A coating agent comprising the composition according to any one of [1] to

[10] .

[12] The coating agent according to

[11] , which is used as an outermost surface coating agent. Effects of the Invention

[0009] When formed into a cured coating film, the composition of the present invention is excellent in a well-balanced combination of self-healing property against scratches, blocking resistance and flexibility, and is also excellent in transparency. Therefore, the composition of the present invention is suitable as a coating agent. Mode for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described based on examples of modes for carrying out the present invention. However, the present invention is not limited to the embodiments described below.

[0011] As used herein, the expression "x and / or y (where x and y are any constituent elements)" means at least one of x and y, and encompasses the three cases of only x, only y, and both x and y. When the expression "X to Y" (where X and Y are any numerical values) is used herein, unless otherwise specified, it means "not less than X and not more than Y", and also includes the meaning of "preferably more than X" or "preferably less than Y". As used herein, when the expression "not less than X" (where X is any numerical value) or "not more than Y" (where Y is any numerical value) is used, it also includes the meaning of "preferably more than X" or "preferably less than Y". For stepwise described numerical ranges herein, the upper or lower limit of a numerical range at one stage may be arbitrarily combined with the upper or lower limit of a numerical range at another stage. Further, in the numerical ranges described herein, the upper or lower limit of the numerical range may be replaced with the values shown in the examples.

[0012] As used herein, "(meth)acryl" means acryl and / or methacryl, "(meth)acryloyl" means acryloyl and / or methacryloyl, and "(meth)acrylate" means acrylate and / or methacrylate, respectively.

[0013] A composition according to an embodiment of the present invention (hereinafter referred to as "the present composition") contains a urethane (meth)acrylate compound (A) and a polysiloxane structure-containing compound (B). Further, the present composition has active energy ray curability that enables it to be cured by irradiation with active energy rays. That is, the present composition can be suitably used as an active energy ray-curable resin composition. Each component will be described below.

[0014] <Urethane (meth)acrylate-based compound (A)> The urethane (meth)acrylate compound (A) is obtained by reacting a hydroxyl group-containing (meth)acrylate compound (x) containing a structural moiety derived from ε-caprolactone (hereinafter referred to as "hydroxyl group-containing (meth)acrylate compound (x)"), a polyvalent isocyanate compound (y), and a polyol (z). It is preferable that the urethane (meth)acrylate compound (A) does not contain a polysiloxane structure.

[0015] [Hydroxyl group-containing (meth)acrylate compound (x)] The hydroxyl group-containing (meth)acrylate compound (x) is preferably a compound obtained by ring-opening polymerization of ε-caprolactone to a hydroxyl group-containing (meth)acrylate compound.

[0016] The number of ethylenically unsaturated groups contained in the hydroxyl group-containing (meth)acrylate compound (x) is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1. When the number of ethylenically unsaturated groups is within the above range, the compound tends to exhibit excellent resilience.

[0017] The weight-average molecular weight of the hydroxyl group-containing (meth)acrylate compound (x) is typically 100 to 2,500, preferably 200 to 1,000, and more preferably 300 to 500. When the weight-average molecular weight is within this range, it tends to exhibit excellent blocking resistance and resilience.

[0018] A suitable specific example of the hydroxyl group-containing (meth)acrylate compound is the compound shown in the following general formula (1).

[0019] [ka]

[0020] In the general formula (1) above, m is usually an integer between 1 and 6, preferably between 1 and 4, more preferably between 2 and 3, and particularly preferably 2. When the value of m falls within the aforementioned range, it tends to exhibit superior blocking resistance.

[0021] In the general formula (1) above, n is usually an integer between 1 and 25, preferably between 1 and 15, more preferably between 1 and 10, and even more preferably between 2 and 5. When the value of n falls within the aforementioned range, the system tends to exhibit superior blocking resistance.

[0022] Examples of compounds represented by the general formula (1) include caprolactone adducts of 2-hydroxyethyl (meth)acrylate. Among these, the 1-mol adduct of 2-hydroxyethyl acrylate to caprolactone, the 2-mol adduct of 2-hydroxyethyl acrylate to caprolactone, and the 5-mol adduct of 2-hydroxyethyl acrylate to caprolactone are preferred, and the 2-mol adduct of 2-hydroxyethyl acrylate to caprolactone is more preferred, due to its excellent balance of resilience and anti-blocking properties.

[0023] The hydroxyl group-containing (meth)acrylate compound (x) may be a commercially available product. Examples of commercially available hydroxyl group-containing (meth)acrylate compounds (x) include Daicel's "Praxel FA1", "Praxel FA1DDM", "Praxel FA2D", "Praxel FA5", "Praxel FA10L", "Praxel FM1", "Praxel FM1D", "Praxel FM2D", "Praxel FM3", "Praxel FM4", and "Praxel FM5".

[0024] [Polyvalent isocyanate compounds (y)] The polyvalent isocyanate compound (y) is preferably at least one selected from the group consisting of biuret-type polymers, nurate-type polymers, and allophanate-type polymers of hexamethylene diisocyanate, in terms of excellent resilience.

[0025] The number-average molecular weight (Mn) of the polyvalent isocyanate compound (y) is typically 500 to 5,000, preferably 600 to 2,000, and more preferably 700 to 1,000. When the number-average molecular weight is within this range, it tends to exhibit excellent resilience.

[0026] The number-average molecular weight (Mn) of the aforementioned polyvalent isocyanate compound (y) is the number-average molecular weight calculated on a standard polystyrene molecular weight scale. The chromatograph used was a high-performance liquid chromatograph (Waters 2695 (main unit) and Waters 2414 (detector)) manufactured by Waters Japan, with a column (Shodex GPC KF-806L, exclusion limit molecular weight: 2 × 10⁻¹⁶). 7 Separation range: 100~2×10 7 This value is measured by using three tubes in series (theoretical plate count: 10,000 stages / tube, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm).

[0027] The average number of isocyanate groups in the polyvalent isocyanate compound (y) is usually 3.2 or more, preferably 3.5 or more, more preferably 3.8 or more, and even more preferably 4 or more. The upper limit of the average number of isocyanate groups is usually 10 or less, preferably 6 or less. When the average number of isocyanate groups in the polyvalent isocyanate compound (y) is within the above range, it tends to exhibit excellent resilience.

[0028] The average number of isocyanate groups is determined from the number-average molecular weight (Mn) and isocyanate group concentration (%) of the polyvalent isocyanate compound (y) using the following formula (1). TIFF2026142447000002.tif11170

[0029] The isocyanate group concentration (%) is a value measured by the method described in JIS K1603-1:2007.

[0030] The polyvalent isocyanate compound (y) is preferably a biuret-type polymer of hexamethylene diisocyanate, a nurate-type polymer of hexamethylene diisocyanate, or an allophanate-type polymer of hexamethylene diisocyanate, and more preferably a biuret-type polymer of hexamethylene diisocyanate.

[0031] [Polyol (z)] The polyol (z) is not particularly limited as long as it is a compound containing two or more hydroxyl groups.

[0032] The hydroxyl value of the polyol(z) is typically 10 to 500 mg KOH / g, preferably 20 to 300 mg KOH / g, and more preferably 40 to 200 mg KOH / g. When the hydroxyl value of the polyol(z) is within this range, it tends to exhibit excellent flexibility.

[0033] The number-average molecular weight of the polyol(z) is typically 60 to 10,000, preferably 100 to 5,000, more preferably 200 to 4,000, and particularly preferably 500 to 2,000. When the number-average molecular weight of the polyol(z) is within this range, it tends to exhibit excellent flexibility. The number-average molecular weight of the polyol(z) can be calculated from the hydroxyl value.

[0034] Examples of the polyol(z) include aliphatic polyols, alicyclic polyols, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, polyisoprene polyols, (meth)acrylic polyols, and polysiloxane polyols. These can be used individually or in combination of two or more.

[0035] Examples of the aliphatic polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, 1 Examples include aliphatic alcohols containing two hydroxyl groups, such as 6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, pentaerythritol diacrylate, 1,9-nonanediol, and 2-methyl-1,8-octanediol; sugar alcohols such as xylitol and sorbitol; and aliphatic alcohols containing three or more hydroxyl groups, such as glycerin, trimethylolpropane, and trimethylolethane.

[0036] Examples of the alicyclic polyols include cyclohexanediols such as 1,4-cyclohexanediol and cyclohexyldimethanol, hydrogenated bisphenols such as hydrogenated bisphenol A, and tricyclodecanedimethanol.

[0037] Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polypentamethylene glycol, and polyhexamethylene glycol, as well as random or block copolymers of these polyalkylene glycols.

[0038] Examples of the aforementioned polyester polyols include condensation polymers of polyhydric alcohols and polyhydric carboxylic acids; ring-opening polymers of cyclic esters (lactones); and reaction products of three components: polyhydric alcohols, polyhydric carboxylic acids, and cyclic esters.

[0039] Examples of the aforementioned polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol), and the like. Examples of the polycarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedionic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, and trimellitic acid. Examples of the cyclic esters mentioned above include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

[0040] Examples of the polycarbonate polyol include reaction products of polyhydric alcohols and phosgene; and ring-opening polymers of cyclic carbonate esters (such as alkylene carbonates). Examples of the polyhydric alcohol include the polyhydric alcohols exemplified in the description of the polyester polyol. Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. The polycarbonate polyol can be any compound having a carbonate bond within its molecule and a hydroxyl group at its terminus, and may also have ester bonds in addition to the carbonate bond.

[0041] Examples of the aforementioned polyolefin polyols include those having a homopolymer or copolymer of ethylene, propylene, butene, etc. as a saturated hydrocarbon backbone, and having hydroxyl groups at the molecular ends.

[0042] Examples of the polybutadiene polyols include those having a butadiene copolymer as the hydrocarbon backbone and having hydroxyl groups at the molecular ends. The polybutadiene-based polyol may also be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in its structure are hydrogenated.

[0043] Examples of the (meth)acrylic polyol include polymers or copolymers of (meth)acrylic acid esters that have at least two hydroxyl groups in the molecule. Examples of such (meth)acrylic acid esters include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and octadecyl (meth)acrylate.

[0044] Examples of the polysiloxane polyols include dimethylpolysiloxane polyol and methylphenylpolysiloxane polyol.

[0045] Among these, polyester polyols, polyether polyols, and polycarbonate polyols are preferred due to their excellent flexibility, and polyester polyols and polyether polyols are more preferred.

[0046] The urethane (meth)acrylate compound (A) is obtained by reacting the hydroxyl group-containing (meth)acrylate compound (x), the polyvalent isocyanate compound (y), and the polyol (z). The manufacturing method can be carried out according to known methods.

[0047] A specific method for producing the urethane (meth)acrylate compound (A) is, for example, (i) A method of reacting a hydroxyl group-containing (meth)acrylate compound (x), a polyvalent isocyanate compound (y), and a polyol (z) by charging them together or separately into a reactor. (ii) A method of reacting a hydroxyl group-containing (meth)acrylate compound (x) with a reaction product obtained by pre-reacting a polyvalent isocyanate compound (y) with a polyol (z), (iii) A method of reacting a polyol (z) with a reaction product obtained by pre-reacting a hydroxyl group-containing (meth)acrylate compound (x) with a polyvalent isocyanate compound (y), These are some examples. Among these, method (iii) is preferred because it can suppress the gelation of the urethane (meth)acrylate compound (A).

[0048] In the method described in (iii) above, the reaction between the hydroxyl group-containing (meth)acrylate compound (x) and the polyvalent isocyanate compound (y) can be carried out using known reaction methods. In this case, for example, by setting the molar ratio [hydroxyl group:isocyanate group] of the hydroxyl group in the hydroxyl group-containing (meth)acrylate compound (x) to the isocyanate group in the polyvalent isocyanate compound (y) to approximately (2n-2):2n [where n is an integer of 1 or more], an isocyanate group remains at the end of the reaction product, enabling an addition reaction with the polyol (z).

[0049] The molar ratio is such that n is 2 or more, preferably 3 or more, and the upper limit is usually 10 or less, preferably 9 or less, more preferably 8 or less, and even more preferably 7 or less. When the molar ratio is within the above range, there is a tendency to suppress the gelation of the urethane (meth)acrylate compound (A).

[0050] The reaction molar ratio between the reaction product and polyol(z) can be, for example, such that there is 1 mole of hydroxyl groups of polyol(z) for every 1 mole of isocyanate groups of the reaction product.

[0051] In the addition reaction between this reaction product and polyol (z), the urethane (meth)acrylate compound (A) can be obtained by terminating the reaction when the residual isocyanate groups in the reaction system are typically 0.3% by mass or less.

[0052] In the reaction between the hydroxyl group-containing (meth)acrylate compound (x) and the polyvalent isocyanate compound (y), and in the reaction between the reaction product and the polyol (z), it is also preferable to use a catalyst to accelerate the reaction.

[0053] Examples of the catalysts include organometallic compounds such as dibutyltin dilaurate, trimethyltin hydroxide, and tetra-n-butyltin; metal salts such as zinc octate, tin octate, cobalt naphthenate, stannous chloride, and stannous chloride; amine catalysts such as triethylamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene, N,N,N',N'-tetramethyl-1,3-butanediamine, and N-ethylmorpholine; bismuth nitrate; and bismuth bromide. Examples of bismuth catalysts include organic bismuth compounds such as dibutylbismuth dilaurate and dioctylbismuth dilaurate, as well as organic acid bismuth salts such as bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth lybisneodecanoate, and bismuth disalicylate. These may be used individually or in combination of two or more. Among these, dibutylsin dilaurate is preferred.

[0054] Furthermore, in the production of urethane (meth)acrylate compound (A), organic solvents that do not have functional groups that react with isocyanate groups can be used, such as esters like ethyl acetate and butyl acetate, ketones like methyl ethyl ketone and methyl isobutyl ketone, and aromatics like toluene and xylene.

[0055] The reaction temperature in the production of the urethane (meth)acrylate compound (A) is usually 30 to 90°C, preferably 40 to 80°C, and the reaction time is usually 2 to 12 hours, preferably 3 to 10 hours.

[0056] The weight-average molecular weight (Mw) of the urethane (meth)acrylate compound (A) is preferably 1,000 to 70,000, more preferably 5,000 to 50,000, even more preferably 10,000 to 40,000, particularly preferably 15,000 to 35,000, and especially preferably 20,000 to 30,000. When the weight-average molecular weight is within the above range, gelation tends to be suppressed and the compound tends to have excellent flexibility.

[0057] The number-average molecular weight (Mn) of the urethane (meth)acrylate compound (A) is typically 500 to 50,000, preferably 1,000 to 30,000, more preferably 2,000 to 20,000, even more preferably 3,500 to 15,000, and particularly preferably 4,000 to 10,000. When the number-average molecular weight is within the above range, gelation tends to be suppressed, and the compound also tends to have excellent flexibility.

[0058] The degree of dispersion (weight-average molecular weight / number-average molecular weight) of the urethane (meth)acrylate compound (A) is preferably 6 or less, more preferably 5 or less, and even more preferably 4.5 or less. When the degree of dispersion is within this range, gelation tends to be suppressed and flexibility tends to be excellent. The lower limit of the degree of dispersion is usually 1.1, due to manufacturing limitations.

[0059] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the aforementioned urethane (meth)acrylate compound (A) are number-average molecular weights calculated on a standard polystyrene molecular weight scale. The measurements were performed using a high-performance liquid chromatograph (Waters Japan Co., Ltd., "Waters 2695 (main unit)" and "Waters 2414 (detector)") with a column (Shodex GPC KF-806L, exclusion limit molecular weight: 2 × 10⁻¹⁶). 7 Separation range: 100~2×10 7 This value is measured by using three tubes in series (theoretical plate count: 10,000 stages / tube, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm).

[0060] The number of ethylenically unsaturated groups contained in the urethane (meth)acrylate compound (A) is usually 1 to 10, preferably 3 to 8, and more preferably 4 to 6. When the number of ethylenically unsaturated groups is within this range, the compound tends to exhibit excellent self-restoring properties and flexibility.

[0061] The ethylenically unsaturated group content (mmol / g) of the urethane (meth)acrylate compound (A) is typically 0.1 to 10 mmol / g, preferably 1 to 5 mmol / g, and more preferably 1 to 3 mmol / g. When the ethylenically unsaturated group content (mmol / g) is within this range, the compound tends to exhibit excellent self-restoration properties.

[0062] The ethylenically unsaturated group content of the urethane (meth)acrylate compound (A) can be calculated, for example, using the following formula (2). The ethylenically unsaturated group content (mmol / g) of urethane (meth)acrylate compound (A) = the ethylenically unsaturated group content (mmol / g) of hydroxyl group-containing (meth)acrylate compound (x) × (mass of hydroxyl group-containing (meth)acrylate compound (x) in urethane (meth)acrylate compound (A) / mass of urethane (meth)acrylate compound (A)) ... (2)

[0063] The viscosity of the urethane (meth)acrylate compound (A) at 60°C is typically 100 to 10,000 mPa·s, preferably 300 to 8,000 mPa·s, and more preferably 500 to 5,000 mPa·s. When the viscosity is within this range, it tends to have excellent coating properties. The viscosity can be measured using an E-type viscometer.

[0064] The content of the urethane (meth)acrylate compound (A) in this composition is usually 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more. The upper limit is usually 99% by mass or less.

[0065] <Polysiloxane structure-containing compound (B)> The polysiloxane structure-containing compound (B) is included to improve blocking resistance, and any known polysiloxane structure-containing compound may be used.

[0066] The silicon atom content in the polysiloxane structure-containing compound (B) is preferably 0.1 to 80% by mass, more preferably 0.3 to 60% by mass, and even more preferably 0.5 to 30% by mass. When the silicon atom content is within the above range, it tends to have excellent compatibility with the urethane (meth)acrylate compound (A).

[0067] Examples of the polysiloxane structure-containing compound (B) include polysiloxane structure-containing poly(meth)acrylate compounds such as polysiloxane structure-containing (meth)acrylate monomers, polysiloxane structure-containing urethane (meth)acrylate compounds (B1), polysiloxane structure-containing polyether (meth)acrylate compounds, polysiloxane structure-containing polyester (meth)acrylate compounds, and polysiloxane structure-containing polycarbonate (meth)acrylate compounds; polysiloxane structure-containing polyester compounds; polysiloxane structure-containing polycarbonate compounds; polysiloxane structure-containing (meth)acrylic polymers; polysiloxane structure-containing (meth)acrylates containing unsaturated groups; and compounds into which a fluorine atom has been introduced.

[0068] Among these, polysiloxane structure-containing (meth)acrylate compounds are preferred because they form a crosslinked structure and exhibit excellent durability when cured by irradiation with active energy rays, and polysiloxane structure-containing urethane (meth)acrylate compound (B1) is preferred because it has excellent compatibility with urethane (meth)acrylate compound (A). The following describes a preferred polysiloxane structure-containing compound (B), which is a polysiloxane structure-containing urethane (meth)acrylate compound (B1) (hereinafter referred to as "urethane (meth)acrylate compound (B1)").

[0069] [Urethane (meth)acrylate compound (B1)] The urethane (meth)acrylate compound (B1) may contain a polysiloxane structure in its structure, but is preferably a urethane (meth)acrylate compound (B1-1) containing a structural moiety derived from a polysiloxane compound having a hydroxyl group at one end as shown in the following general formula (2) [hereinafter referred to as "urethane (meth)acrylate compound (B1-1)"], or a urethane (meth)acrylate compound (B1-2) containing a structural moiety derived from a polysiloxane compound having hydroxyl groups at both ends as shown in the following general formula (3) [hereinafter referred to as "urethane (meth)acrylate compound (B1-2)"]. Furthermore, the above-mentioned urethane (meth)acrylate compound (B1) may contain structural parts derived from both general formulas (2) and (3).

[0070] [ka]

[0071] [ka]

[0072] [Urethane (meth)acrylate compound (B1-1)] The urethane (meth)acrylate compound (B1-1) is obtained by reacting a polysiloxane compound (p1) having a hydroxyl group at one end represented by general formula (2) [hereinafter referred to as "polysiloxane compound (p1)"], a polyvalent isocyanate compound (p2), and a hydroxyl group-containing (meth)acrylate compound (p3), and optionally a polyol (p4).

[0073] (Polysiloxane compound (p1)) The aforementioned polysiloxane compound (p1) is a polysiloxane compound having a hydroxyl group at one end, as shown in the following general formula (2).

[0074] [ka]

[0075] In the above general formula (2), R 1 The alkyl group is an alkyl group, and it is preferable that the alkyl group has a relatively short number of carbon atoms. Specifically, the alkyl group usually has 1 to 15 carbon atoms, preferably 1 to 10, and particularly preferably 1 to 5 carbon atoms. Examples include methyl, ethyl, propyl, and butyl groups.

[0076] In the above general formula (2), R 2 Each of these is independently an alkyl group, a cycloalkyl group, or a phenyl group. The alkyl group preferably has a relatively short number of carbon atoms. Specifically, the alkyl group usually has 1 to 15 carbon atoms, preferably 1 to 10, and particularly preferably 1 to 5 carbon atoms. Examples include methyl, ethyl, propyl, and butyl groups. The number of carbon atoms in the cycloalkyl group is usually 3 to 10, preferably 5 to 8, and examples include cyclopentyl group, cyclohexyl group, and norbonyl group. Furthermore, the alkyl group, cycloalkyl group, and phenyl group may have substituents. Typical substituents include halogen atoms, hydroxyl groups, alkoxy groups, amino groups, mercapto groups, sulfanyl groups, vinyl groups, acryloxy groups, methacryloxy groups, aryl groups, heteroaryl groups, etc. If the substituent has a carbon atom, the carbon atom of the substituent is R 2 It shall not be included in the carbon count.

[0077] In the above general formula (2), R 3 This refers to an organic group containing a hydrocarbon group or a heteroatom. Examples of the hydrocarbon group include divalent or trivalent hydrocarbon groups, typically having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Examples of the divalent hydrocarbon group include alkylene groups. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and examples include ethylene groups, propylene groups, tetramethylene groups, and the like. Examples of organic groups containing the heteroatom include oxyalkylene groups, polyoxyalkylene groups, polycaprolactone groups, and amino groups.

[0078] In the general formula (2) above, a is an integer of 1 or more, preferably between 5 and 200, and particularly preferably between 5 and 120. b is an integer between 1 and 3, preferably between 1 and 2.

[0079] The weight-average molecular weight of the polysiloxane compound (p1) is preferably 100 to 50,000, more preferably 500 to 10,000, and even more preferably 1,000 to 10,000. When the weight-average molecular weight is within the above range, it tends to exhibit excellent blocking resistance and transparency.

[0080] Specific examples of the polysiloxane compound (p1) include, for example, Shin-Etsu Chemical Co., Ltd.'s "X-22-170BX", "X-22-170DX", "X-22-176DX", and "X-22-176F", and Chisso Corporation's "Siraplane FM-0411", "Siraplane FM-0421", "Siraplane FM-0425", "Siraplane FM-DA11", "Siraplane FM-DA21", and "Siraplane FM-DA26".

[0081] (Polyvalent isocyanate compounds (p2)) Examples of the polyvalent isocyanate compounds (p2) include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; and hydrogenated diphth Examples include alicyclic polyisocyanates such as phenylmethane diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and 1,4-bis(isocyanatomethyl)cyclohexane, or trimer compounds or polymer compounds of these polyisocyanates, allophanate-type polyisocyanates, burette-type polyisocyanates, and water-dispersible polyisocyanates (for example, "Aquanate 100," "Aquanate 105," "Aquanate 120," and "Aquanate 210" manufactured by Tosoh Corporation). These may be used individually or in combination of two or more. Among these, polyvalent isocyanate compounds having three or more isocyanate groups in one molecule are preferred, and more preferably are trimers or polymer compounds of polyvalent polyisocyanate compounds, as these reduce unreacted low molecular weight components that cause coating hardness and bleeding.

[0082] (Hydroxyl group-containing (meth)acrylate compound (p3)) Examples of the hydroxyl group-containing (meth)acrylate compound (p3) include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethyl acryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth)acrylate, fatty acid-modified glycidyl (meth)acrylate, and polyethylene glycol mono(meth)acrylate. Examples include acrylates, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, glycerin di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, and ethylene oxide-modified dipentaerythritol penta(meth)acrylate. These may be used individually or in combination of two or more. Among these, pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate are preferred because they provide a relatively high-hardness coating film.

[0083] The hydroxyl value of the hydroxyl group-containing (meth)acrylate compound (p3) is typically 10 to 500 mg KOH / g, preferably 20 to 300 mg KOH / g, and more preferably 40 to 200 mg KOH / g.

[0084] (Polyol (p4)) The urethane (meth)acrylate compound (B1-1) may have a structural moiety derived from the polyol (p4) to the extent that it does not impair the effects of the present invention. Examples of the polyol (p4) include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, and (meth)acrylic polyols.

[0085] Examples of the polyether polyols include alkylene structure-containing polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, as well as random or block copolymers of these polyalkylene glycols.

[0086] Examples of the polyester polyol include condensation polymers of polyhydric alcohols and polyhydric carboxylic acids, ring-opening polymers of cyclic esters (lactones), and reaction products of three components: polyhydric alcohols, polyhydric carboxylic acids, and cyclic esters. Examples of the aforementioned polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol). Examples of the polycarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedionic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, and trimellitic acid. Examples of the cyclic esters mentioned above include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

[0087] Examples of the polycarbonate polyol include reaction products of polyhydric alcohols and phosgene, and ring-opening polymers of cyclic carbonate esters (such as alkylene carbonates). Examples of the polyhydric alcohol include the polyhydric alcohols exemplified in the description of the polyester polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. Furthermore, polycarbonate-based polyols are any compounds that have a carbonate bond in their molecule and a hydroxyl group at one end, and may also have an ester bond in addition to the carbonate bond.

[0088] Examples of the aforementioned polyolefin polyols include those having a homopolymer or copolymer of ethylene, propylene, butene, etc. as a saturated hydrocarbon backbone, and having hydroxyl groups at the molecular ends.

[0089] Examples of the polybutadiene polyols include those having a butadiene copolymer as the hydrocarbon backbone and having hydroxyl groups at the molecular termini. The polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in its structure are hydrogenated.

[0090] Examples of the (meth)acrylic polyol include polymers or copolymers of (meth)acrylic acid esters that have at least two hydroxyl groups in the molecule. Examples of the (meth)acrylic acid esters include alkyl (meth)acrylate esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and octadecyl (meth)acrylate.

[0091] The weight-average molecular weight of the polyol (p4) is preferably 50 to 8,000, more preferably 100 to 5,000, and even more preferably 200 to 3,000. When the weight-average molecular weight is within this range, the coating exhibits excellent mechanical properties such as hardness during curing, and curing shrinkage tends to be suppressed.

[0092] The method for producing the urethane (meth)acrylate compound (B1-1) is not particularly limited, but for example, (1) A method of simultaneously charging and reacting a polysiloxane compound (p1), a polyvalent isocyanate compound (p2) [if necessary, a polyvalent isocyanate compound (p2) that has been previously reacted with a polyol (p4)], and a hydroxyl group-containing (meth)acrylate compound (p3), (2) A method in which a polysiloxane compound (p1) and a polyvalent isocyanate compound (p2) [if necessary, a polyvalent isocyanate compound (p2) that has been previously reacted with a polyol (p4)] are reacted, followed by a hydroxyl group-containing (meth)acrylate compound (p3). (3) A method in which a polyvalent isocyanate compound (p2) [if necessary, a polyvalent isocyanate compound (p2) that has been previously reacted with a polyol (p4)] is reacted with a hydroxyl group-containing (meth)acrylate compound (p3), and then a polysiloxane compound (p1) is reacted. (4) A method in which a polyvalent isocyanate compound (p2) [if necessary, a polyvalent isocyanate compound (p2) that has been previously reacted with a polyol (p4)] is reacted with a portion of a hydroxyl group-containing (meth)acrylate compound (p3), then a polysiloxane compound (p1) is reacted, and then the remaining hydroxyl group-containing (meth)acrylate compound (p3) is reacted. These are some examples, but among them, methods (2) and (4) are preferred, and method (2) is particularly preferred in terms of the stability of reaction control.

[0093] If the polyol (p4) and the polyvalent isocyanate compound (p2) are to be reacted beforehand, for example, the production methods for commonly known urethane polyols can be followed.

[0094] The preferred manufacturing method, method (2), will be described below. In method (2) above, the hydroxyl group of a polysiloxane compound (p1) and the isocyanate group of a polyvalent isocyanate compound (p2) are reacted under conditions that leave the isocyanate group intact. Then, the remaining isocyanate group in the resulting reaction product is reacted with the hydroxyl group of a hydroxyl-containing (meth)acrylate compound (p3).

[0095] The reaction molar ratio of the polysiloxane compound (p1) and the polyvalent isocyanate compound (p2) is, for example, when the polysiloxane compound (p1) has one hydroxyl group and the polyisocyanate compound (p2) has two isocyanate groups, the ratio of polysiloxane compound (p1) to polyvalent isocyanate compound (p2) is approximately 1:0.8 to 10, and when the polysiloxane compound (p1) has one hydroxyl group and the polyvalent isocyanate compound (p2) has three isocyanate groups, the ratio of polysiloxane compound (p1) to polyvalent isocyanate compound (p2) is approximately 1:0.2 to 5.

[0096] Subsequently, the reaction product is reacted with a hydroxyl group-containing (meth)acrylate compound (p3), and the reaction is terminated when the remaining isocyanate groups in the reaction system become 0.5% by mass or less, thereby obtaining a urethane (meth)acrylate compound (B1-1).

[0097] In the above reaction, it is also preferable to use a catalyst to promote the reaction, and examples of such catalysts are the same as those listed in the production of the urethane (meth)acrylate compound (A).

[0098] Furthermore, in the above reaction, organic solvents that do not have functional groups that react with isocyanate groups can be used, such as esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene.

[0099] The reaction temperature for the above reaction is usually 30 to 100°C, preferably 40 to 90°C, and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

[0100] The content of the structural portion derived from the polysiloxane compound (p1) in the urethane (meth)acrylate compound (B1-1) is preferably 0.1 to 80% by mass.

[0101] The number of ethylenically unsaturated groups in the urethane (meth)acrylate compound (B1-1) is preferably one or more, more preferably three or more, and even more preferably six or more, in terms of the hardness of the cured coating film. The upper limit of the number of ethylenically unsaturated groups is usually 30 or less, and preferably 25 or less.

[0102] The weight-average molecular weight of the urethane (meth)acrylate compound (B1-1) is preferably 500 to 50,000, and more preferably 500 to 30,000. When the weight-average molecular weight is within this range, it tends to exhibit excellent blocking resistance and transparency.

[0103] The viscosity of a 40% methyl isobutyl ketone solution of the urethane (meth)acrylate compound (B1-1) at 20°C is preferably 5 to 5,000 mPa·s, more preferably 5 to 2,500 mPa·s, and still more preferably 5 to 1,000 mPa·s. When the viscosity is within the above range, coating properties tend to be excellent. The viscosity is measured using a B-type viscometer.

[0104] The urethane (meth)acrylate compound (B1-1) may be used alone in one kind, or two or more kinds may be used in combination.

[0105] [Urethane (meth)acrylate Compound (B1-2)] The urethane (meth)acrylate compound (B1-2) is obtained by reacting a polysiloxane compound (q1) having hydroxyl groups at both ends represented by general formula (3) [hereinafter referred to as "polysiloxane compound (q1)"], a polyvalent isocyanate compound (q2), a hydroxyl group-containing (meth)acrylate compound (q3), and optionally a polyol (q4).

[0106] (Polysiloxane Compound (q1)) The polysiloxane compound (p1) is a polysiloxane compound having hydroxyl groups at both ends represented by the following general formula (3).

[0107] [Chemical Formula]

[0108] R in the general formula (3) 4 , R 6 is a hydrocarbon group or an organic group containing a hetero atom. The hydrocarbon group generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and includes divalent or trivalent hydrocarbon groups. Examples of the divalent hydrocarbon group include alkylene groups. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and examples include ethylene groups, propylene groups, tetramethylene groups, and the like. Examples of organic groups containing the heteroatom include oxyalkylene groups, polyoxyalkylene groups, polycaprolactone groups, and amino groups.

[0109] R in the general formula (3) 5 Each of these is independently an alkyl group, a cycloalkyl group, or a phenyl group. The alkyl group preferably has a relatively short number of carbon atoms. Specifically, the alkyl group usually has 1 to 15 carbon atoms, preferably 1 to 10, and particularly preferably 1 to 5 carbon atoms. Examples include methyl, ethyl, propyl, and butyl groups. The number of carbon atoms in the cycloalkyl group is usually 3 to 10, preferably 5 to 8, and examples include cyclopentyl group, cyclohexyl group, and norbonyl group. Furthermore, the alkyl group, cycloalkyl group, and phenyl group may have substituents. Examples of the substituents include halogen atoms, hydroxyl groups, alkoxy groups, amino groups, mercapto groups, sulfanyl groups, vinyl groups, acryloxy groups, methacryloxy groups, aryl groups, heteroaryl groups, etc. If the substituent has a carbon atom, the carbon atom of the substituent is R 5 This carbon number is not to be included in the calculation.

[0110] In the general formula (3) above, c is an integer of 1 or more, preferably between 5 and 200, and particularly preferably between 5 and 120. d and e are integers between 1 and 3, preferably between 1 and 2.

[0111] The weight-average molecular weight of the polysiloxane compound (q1) is preferably 100 to 50,000, more preferably 500 to 10,000, and even more preferably 1,000 to 10,000. When the weight-average molecular weight is within the above range, it tends to exhibit excellent blocking resistance and transparency.

[0112] Specific examples of the polysiloxane compound (q1) include "X-22-160AS", "KF-6001", "KF-6002", and "KF-6003" from Shin-Etsu Chemical Co., Ltd., "Sylaplane FM-4411", "Sylaplane FM-4421", and "Sylaplane FM-4425" from JNC Corporation, "XF42-B0970" from Momentive Performance Materials Japan, "BY 16-004" and "SF 8427" from Toray Dow Corning, Inc., "Macromonomer HK-20" from Toagosei Co., Ltd., and "DMS-C21", "DMS-C23", "DBL-C31", and "DMS-CA21" from GELEST Corporation.

[0113] (Polyvalent isocyanate compounds (q2)) Examples of polyvalent isocyanate compounds (q2) include those similar to those exemplified in the above-mentioned polyvalent isocyanate compound (p2).

[0114] (Hydroxyl group-containing (meth)acrylate compound (q3)) Examples of hydroxyl group-containing (meth)acrylate compounds (q3) include those similar to those exemplified in the hydroxyl group-containing (meth)acrylate compound (p3) above.

[0115] (Polyol (q4)) Examples of the polyol compound (q4) include those similar to those exemplified for polyol (p4).

[0116] The method for producing the urethane (meth)acrylate compound (B1-2) is not particularly limited, for example, (5) A method of reacting a polysiloxane compound (q1), a polyvalent isocyanate compound (q2) [if necessary, a polyvalent isocyanate compound (q2) that has been previously reacted with a polyol (q4)], and a hydroxyl group-containing (meth)acrylate compound (q3) all at once. (6) A method in which a polysiloxane compound (q1) and a polyisocyanate compound (q2) [if necessary, a polyvalent isocyanate compound (q2) that has been previously reacted with a polyol (q4)] are reacted, followed by a hydroxyl group-containing (meth)acrylate compound (q3). (7) A method in which a polyvalent isocyanate compound (q2) [if necessary, a polyvalent isocyanate compound (q2) that has been previously reacted with a polyol (q4)] is reacted with a hydroxyl group-containing (meth)acrylate compound (q3), and then a polysiloxane compound (q1) is reacted. (8) A method in which a polyvalent isocyanate compound (q2) [if necessary, a polyvalent isocyanate compound (q2) that has been previously reacted with a polyol (q4)] is reacted with a portion of a hydroxyl group-containing (meth)acrylate compound (q3), then a polysiloxane compound (q1) is reacted, and then the remaining hydroxyl group-containing (meth)acrylate compound (q3) is reacted. These are some examples, but among them, methods (6) and (8) are preferred, and method (6) is particularly preferred in terms of reaction control stability and compatibility.

[0117] If the polyol (q4) and the polyvalent isocyanate compound (q2) are to be reacted beforehand, the process can be carried out according to, for example, the general known methods for producing urethane-based polyols.

[0118] The preferred manufacturing method, method (6), will be described below. In the method described in (6) above, the hydroxyl group of the polysiloxane compound (q1) and the isocyanate group of the polyvalent isocyanate compound (q2) are reacted under conditions that leave the isocyanate group intact. Then, the remaining isocyanate group in the resulting reaction product is reacted with the hydroxyl group of the hydroxyl group-containing (meth)acrylate compound (q3).

[0119] The reaction molar ratio of the polysiloxane compound (q1) to the polyvalent isocyanate compound (q2) is, for example, when the polysiloxane compound (q1) has two hydroxyl groups and the polyvalent isocyanate compound (q2) has two isocyanate groups, the ratio of polysiloxane compound (q1) to polyvalent isocyanate compound (q2) is approximately 1:1.1 to 2.2, and when the polysiloxane compound (q1) has two hydroxyl groups and the polyvalent isocyanate compound (q2) has three isocyanate groups, the ratio of polysiloxane compound (q1) to polyvalent isocyanate compound (q2) is approximately 1:0.5 to 2.2.

[0120] Subsequently, the reactive organism is reacted with a hydroxyl group-containing (meth)acrylate compound (q3), and the reaction is terminated when the remaining isocyanate groups in the reaction system become 0.5% by mass or less, thereby obtaining urethane (meth)acrylate compounds (B1-2).

[0121] In the above reaction, it is also preferable to use a catalyst to promote the reaction, and examples of such catalysts are the same as those listed in the production of the urethane (meth)acrylate compound (A).

[0122] Furthermore, in the above reaction, organic solvents that do not have functional groups that react with isocyanate groups can be used, such as esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene.

[0123] The reaction temperature for the above reaction is usually 30 to 100°C, preferably 40 to 90°C, and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

[0124] The content of the structural portion derived from the polysiloxane compound (q1) in the urethane (meth)acrylate compound (B1-2) is preferably 0.1 to 80% by mass.

[0125] The number of ethylenically unsaturated groups in the urethane (meth)acrylate compound (B1-2) is preferably two or more, more preferably four or more, and even more preferably six or more, in terms of the hardness of the cured coating film. The upper limit of the number of ethylenically unsaturated groups is usually 30 or less, and preferably 25 or less.

[0126] The weight-average molecular weight of the urethane (meth)acrylate compound (B1-2) is preferably 500 to 50,000, and more preferably 500 to 30,000. When the weight-average molecular weight is within this range, it tends to exhibit excellent blocking resistance and transparency.

[0127] The viscosity of a 40% methyl isobutyl ketone solution of the urethane (meth)acrylate compound (B1-2) at 20°C is preferably 5 to 5,000 mPa·s, more preferably 10 to 2,500 mPa·s, and even more preferably 15 to 1,000 mPa·s. When the viscosity is within this range, the coating properties tend to be excellent. The viscosity was measured using a Type B viscometer.

[0128] The aforementioned urethane (meth)acrylate compounds (B1-2) may be used individually or in combination of two or more.

[0129] As the urethane (meth)acrylate compound (B1), the urethane (meth)acrylate compound (B1-1) and / or urethane (meth)acrylate compound (B1-2) are preferred, but the urethane (meth)acrylate compound (B1-2) is particularly preferred because it is less likely to leave unreacted polysiloxane compounds.

[0130] The content of the polysiloxane structure-containing compound (B) is preferably 0.01 to 100 parts by mass, more preferably 0.5 to 25 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the urethane (meth)acrylate compound (A).

[0131] Furthermore, when using both urethane (meth)acrylate compound (B1-1) and urethane (meth)acrylate compound (B1-2), the blending ratio (mass ratio) of urethane (meth)acrylate compound (B1-1) and urethane (meth)acrylate compound (B1-2) is preferably (B1-1) / (B1-2)=5 / 95 to 95 / 5, and more preferably (B1-1) / (B1-2)=20 / 80 to 80 / 20.

[0132] This composition may optionally contain a photopolymerization initiator, ethylenically unsaturated monomers and oligomers other than (A) and (B) above, acrylic resin, surface modifier, leveling agent, polymerization inhibitor, oil, antioxidant, flame retardant, antistatic agent, filler, stabilizer, reinforcing agent, matting agent, abrasive, organic fine particles, inorganic particles, etc.

[0133] Examples of the photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, benzyldimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxyethyl Acetophenones such as lohexylphenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, and 4-phenyl Benzophenones such as benzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminonium bromide, (4-benzoylbenzyl)trimethylammonium chloride, etc.; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2 Examples include thioxanthones such as 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride; and acyl phosphonate oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. These may be used individually or in combination of two or more.

[0134] Among these, it is preferable to use benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin isopropyl ether, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

[0135] The content of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of urethane (meth)acrylate compound (A) [if the composition contains compounds having ethylenically unsaturated groups other than urethane (meth)acrylate compound (A), the total of all compounds having ethylenically unsaturated groups]. When the content of the photopolymerization initiator is within the above range, film formation is good and discoloration such as yellowing tends to be suppressed.

[0136] Furthermore, it is also possible to use, for example, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc., as auxiliary agents for photopolymerization.

[0137] Examples of the ethylenically unsaturated monomers and ethylenically unsaturated oligomers include monofunctional monomers, difunctional monomers, monomers with three or more functions, epoxy (meth)acrylate compounds, polyester (meth)acrylate compounds, and urethane (meth)acrylate compounds (excluding urethane (meth)acrylate compound (A) and urethane (meth)acrylate compound (B1)).

[0138] Examples of the monofunctional monomers include styrene-based monomers such as styrene, vinyltoluene, chlorostyrene, and α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, acrylonitrile, 2-methoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono (meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclo Lopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)-methyl (meth)acrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl)-methyl (meth)acrylate, cyclic trimethylolpropaneformal acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, γ-butyrolactone (meth)acrylate, n- Butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, n-stearyl (meth)acrylate, benzyl (meth)acrylate, phenol ethylene oxide modified (n=2) (meth)acrylate, nonylphenol propylene oxide modified (n=2).5) Examples include (meth)acrylate monomers such as (meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, half-(meth)acrylate, furfuryl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, carbitol(meth)acrylate, benzyl(meth)acrylate, butoxyethyl(meth)acrylate, allyl(meth)acrylate, (meth)acryloylmorpholine, polyoxyethylene secondary alkyl ether acrylate, 2-hydroxyethylacrylamide, N-methylol(meth)acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, and vinyl acetate.

[0139] Other examples of monofunctional monomers include Michael adducts of (meth)acrylic acid and 2-acryloyloxyethyl dicarboxylic acid monoesters. Examples of the Michael adducts of (meth)acrylic acid include (meth)acrylic acid dimers, (meth)acrylic acid trimers, and (meth)acrylic acid tetramers. The 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyloxyethyl succinate monoester, 2-methacryloyloxyethyl succinate monoester, 2-acryloyloxyethyl phthalate monoester, 2-methacryloyloxyethyl phthalate monoester, 2-acryloyloxyethyl hexahydrophthalate monoester, and 2-methacryloyloxyethyl hexahydrophthalate monoester. In addition, other oligoester acrylates can also be mentioned.

[0140] Examples of the aforementioned bifunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified bisphenol A type di(meth)acrylate, propylene oxide-modified bisphenol A type di(meth)acrylate, and cyclohexanedimethanol di(meth)acrylate. Examples include hydrate, ethoxylated cyclohexanedimethanol di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate, and isocyanurate-modified ethylene oxide diacrylate.

[0141] Examples of the above-mentioned monomers with three or more functionalities include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, isocyanurate ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, and Examples include prolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, and ethoxylated glycerin triacrylate.

[0142] Examples of the surface modifiers include cellulose resin and alkyd resin. Such cellulose resin has the effect of improving the surface smoothness of the coating film, and alkyd resin has the effect of providing film-forming properties during coating.

[0143] As the leveling agent, any known leveling agent can be used, as long as it has the effect of imparting wettability to the substrate of the coating liquid and reducing surface tension. For example, silicone-modified resins, fluorine-modified resins, alkyl-modified resins, etc., can be used.

[0144] Examples of polymerization inhibitors include p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, and pt-butylcatechol.

[0145] This composition can be obtained by mixing these components, but the method of mixing each of the components (A), (B), and other components is not particularly limited and can be done by various methods.

[0146] Furthermore, this composition may be diluted with an organic solvent as needed to achieve an appropriate viscosity during coating. Examples of the aforementioned organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol, and i-butanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; cellosolves such as ethyl cellosolve; aromatics such as toluene and xylene; glycol ethers such as propylene glycol monomethyl ether; acetic acid esters such as methyl acetate, ethyl acetate, and butyl acetate; and diacetone alcohol. These may be used individually or in combination of two or more. Furthermore, when using two or more types in combination, it is preferable to select and combine two or more from glycol ethers, ketones, and alcohols in terms of the appearance of the coating film.

[0147] When diluting this composition with an organic solvent, the solid content concentration should be reduced to approximately 3 to 90% by mass, preferably 5 to 60% by mass.

[0148] This composition is effectively used as a curable resin composition for forming coating films, such as a topcoat or anchor coat, on various substrates. After applying this composition to a substrate (or after drying if the composition is diluted with an organic solvent), it is cured by irradiation with active energy rays.

[0149] Examples of substrates to be coated with this composition include plastic substrates such as polyolefin resins, polyester resins, polycarbonate resins, acrylic resins, acrylonitrile butadiene styrene copolymers (ABS), polystyrene resins, etc., and molded products thereof (films, sheets, cups, etc.), composite substrates thereof, or composite substrates of the above materials mixed with glass fibers or inorganic materials, as well as substrates with a primer layer provided on a substrate such as metal (aluminum, copper, iron, SUS, zinc, magnesium, alloys thereof, metal vapor-deposited films, etc.) or glass.

[0150] Examples of coating methods for this composition include wet coating methods such as spraying, showering, dipping, dispensing, rolling, spinning, screen printing, and inkjet printing, and the coating should normally be applied to the substrate at room temperature (23°C).

[0151] Furthermore, when this composition is diluted with an organic solvent, the drying conditions are typically a temperature of 40 to 120°C, preferably 50 to 100°C, and a drying time of typically 1 to 20 minutes, preferably 2 to 10 minutes.

[0152] Examples of active energy rays used to cure this composition coated on a substrate include far-ultraviolet light, ultraviolet light, near-ultraviolet light, infrared light, electromagnetic waves such as X-rays and gamma rays, as well as electron beams, proton beams, and neutron beams. However, ultraviolet light is preferred due to its curing speed, availability of irradiation equipment, and cost. When curing is performed using electron beams, curing can be achieved without the use of a photopolymerization initiator.

[0153] When curing with ultraviolet light, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, LEDs, etc., emitting light in the 150-450 nm wavelength range are used, typically at a pressure of 30-3,000 mJ / cm². 2 (Preferably 100 to 1,500 mJ / cm²) 2 ) You just need to irradiate it with ultraviolet light. After UV irradiation, heating can be performed as needed to ensure complete curing.

[0154] The coating film thickness (film thickness after curing) is related to the depth of the scratch assumed for scratch recovery. Therefore, it can be set to any thickness such that the depth of the scratch does not exceed the film thickness of the coating. Considering light transmission so that the photopolymerization initiator reacts uniformly as an ultraviolet-curable coating, it is usually sufficient to have a thickness of 3 to 1000 μm, preferably 5 to 500 μm, and more preferably 10 to 200 μm.

[0155] The elongation of the cured coating obtained by curing this composition is usually 60% or more, preferably 70% or more, and more preferably 80% or more. The upper limit is usually 300% or less. The elongation can be measured according to the method described in the embodiment below.

[0156] Furthermore, the haze of the cured coating obtained by curing this composition is usually less than 3.0%, preferably less than 2.0%, and more preferably less than 1.0%. The haze can be measured according to the method described in the examples below. Note that the haze is the sum of the haze of the polyethylene terephthalate film and the cured coating.

[0157] By using this composition to form a cured coating film, it exhibits a well-balanced and excellent combination of self-healing properties against scratches, transparency, blocking resistance, and flexibility. Therefore, this composition is useful in paints, inks, and coatings, and is particularly useful as a top-surface coating agent and a coating agent for metal surfaces. [Examples]

[0158] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. In the examples, "parts" and "%" refer to mass.

[0159] First, various acrylic resins (A) were prepared as described below. The weight-average molecular weight, degree of dispersion, glass transition temperature, and viscosity of the acrylic resin (A) were measured according to the method described above.

[0160] The following urethane (meth)acrylate compound (A) was prepared.

[0161] [Urethane (meth)acrylate compound (A-1)] In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 239.2 g (0.45 mol) of biuret-type polymer (y1) of hexamethylene diisocyanate with an average number of isocyanate groups of 4.1, 308.1 g (0.90 mol) of 2-hydroxyethyl acrylate adduct to caprolactone (x1), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, and 0.02 g of dibutyltin dilaurate as a reaction catalyst were added. The mixture was prepared and reacted at 60°C for 4 hours. When the remaining amount of isocyanate groups was 0.3%, 452.7g (0.22 mol) of a bifunctional polyester polyol (z1) [hydroxyl value 56 mg KOH / g, number average molecular weight calculated from the hydroxyl value 2,000] was added and the reaction was continued. The reaction was terminated when the remaining isocyanate groups were 0.3%, yielding a urethane (meth)acrylate compound (A-1) [weight average molecular weight 28,000, dispersion degree 4.1].

[0162] [Urethane (meth)acrylate compound (A-2)] In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 307.4 g (0.58 mol) of biuret-type polymer (y1) of hexamethylene diisocyanate with an average number of isocyanate groups of 4.1, 395.9 g (1.15 mol) of 2-hydroxyethyl acrylate adduct to caprolactone (x1), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, and 0.02 g of dibutyltin dilaurate as a reaction catalyst were added. The mixture was then reacted at 60°C for 4 hours. When the remaining amount of isocyanate groups was 0.3%, 296.7 g (0.29 mol) of a bifunctional polyester polyol (z1) [hydroxyl value 110 mg KOH / g, number average molecular weight calculated from the hydroxyl value 1,000] was added, and the reaction was continued. The reaction was terminated when the remaining isocyanate groups were 0.3%, yielding a urethane (meth)acrylate compound (A-2) [weight average molecular weight 25,000, dispersion degree 4.3].

[0163] [Urethane (meth)acrylate compound (A-3)] In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 309.3 g (0.58 mol) of biuret-type polymer (y1) of hexamethylene diisocyanate with an average number of isocyanate groups of 4.1, 398.5 g (1.16 mol) of a 2-mol adduct of 2-hydroxyethyl acrylate to caprolactone (x1), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, and 0.02 g of dibutyltin dilaurate as a reaction catalyst were used. The mixture was then reacted at 60°C for 4 hours. When the remaining amount of isocyanate groups was 0.3%, 292.2 g (0.29 mol) of a bifunctional polyether polyol (z1) [hydroxyl value 110 mg KOH / g, number average molecular weight calculated from the hydroxyl value 1,000] was added, and the reaction was continued. The reaction was terminated when the remaining isocyanate groups were 0.3%, yielding a urethane (meth)acrylate compound (A-3) [weight average molecular weight 26,000, dispersion degree 4.0].

[0164] [Urethane (meth)acrylate compound (A'-1)] In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 341.1 g (0.64 mol) of a biuret-type polymer (y1) of hexamethylene diisocyanate with an average number of isocyanate groups of 4.1, 659.0 g (1.92 mol) of a 2-mol adduct of caprolactone to 2-hydroxyethyl acrylate (x1), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, and 0.02 g of dibutyltin dilaurate as a reaction catalyst were charged. The reaction was carried out at 60°C for 6 hours, and the reaction was terminated when the remaining isocyanate groups reached 0.3%, yielding a urethane (meth)acrylate compound (A'-1) [weight-average molecular weight 4,000, dispersion degree 1.5].

[0165] The following compound (B) containing a polysiloxane structure was prepared.

[0166] <Polysiloxane structure-containing compound (B-1)> A four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet contains 69.1 g of hexamethylene diisocyanate trimer (q2) [isocyanate group content 21.0%] and a polysiloxane compound represented by general formula (3) (q1) [R 4 =C2H4OC3H6, R 5 =methyl group, R 6 172.6g of [C3H6OC2H4, d=1, e=1, weight-average molecular weight 6,000], 500g of methyl isobutyl ketone, 1.0g of hydroquinone methyl ether as a polymerization inhibitor, and 0.1g of dibutyltin dilaurate as a reaction catalyst were charged and reacted at 60°C for 3 hours. When the residual isocyanate was reduced to 4.0%, 258.3g of dipentaerythritol pentaacrylate (q3) [a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 50mgKOH / g)] was charged and the reaction was continued until the isocyanate group disappeared, at which point the reaction was terminated to obtain a polysiloxane group-containing urethane (meth)arylate compound (B-1) solution (solid content concentration 50%).

[0167] <Polysiloxane structure-containing compound (B-2)> A four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet contains 115.7 g of isophorone diisocyanate trimer (q2) [isocyanate group content 17.2%] and a polysiloxane compound (q1) represented by general formula (3) [R 4 =C2H4OC3H6, R 5 =methyl group, R 6 236.7g of [=C3H6OC2H4, d=1, e=1, weight-average molecular weight 6,000], 500g of methyl isobutyl ketone, 0.5g of 2,6-di-tert-butyl cresol as a polymerization inhibitor, and 0.05g of dibutyltin dilaurate as a reaction catalyst were charged and reacted at 60°C for 3 hours. When the residual isocyanate was 3.8%, 147.6g of pentaerythritol triacrylate (q3) [a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (hydroxyl value 120mgKOH / g)] was charged and the reaction was continued until the isocyanate group disappeared, at which point the reaction was terminated to obtain a polysiloxane group-containing urethane (meth)acrylate compound (B-2) solution (solid content concentration 50%).

[0168] <Examples 1-7, Comparative Example 1> The urethane (meth)acrylate compound (A) and the polysiloxane structure-containing compound (B) described above were prepared to the compositions shown in Table 1 below, and four parts of a photopolymerization initiator ("Omnirad 184" manufactured by IGM Resins BV) were added to obtain the composition. Subsequently, this active energy ray-curable resin composition was diluted with methyl isobutyl ketone to a solid content concentration of 40% to obtain the composition solution. The obtained composition solutions were evaluated for self-restoration, elongation, blocking resistance, and transparency (haze). The evaluation results are shown in Table 1.

[0169] [Self-restoring properties] The composition solution was applied to a black polycarbonate substrate (manufactured by Nippon Test Panel Co., Ltd., 2 x 70 x 150 mm) using an applicator to create a cured film with a thickness of 40 μm. After drying at 90°C for 5 minutes, it was irradiated with ultraviolet light in two passes from a height of 18 cm at a conveyor speed of 3.4 m / min using one 80W high-pressure mercury lamp (cumulative irradiation dose of 800 mJ / cm²). 2 The procedure was performed to obtain a cured coating film. The resulting cured coating was subjected to five back-and-forth strokes using a brass double-digit brush under conditions of 23°C and 50% Rh to scratch the coating. The time it took for the scratches to disappear visually was measured, and the coating was evaluated according to the following evaluation criteria. [Evaluation Criteria] ◎: The wound disappeared within 1 minute. ○: The wound was no longer visible after more than 1 minute but within 5 minutes. △: The wound was no longer visible between 5 and 10 minutes. ×: The wound was still visible after more than 10 minutes.

[0170] [Elongation] The composition solution was applied to a black polycarbonate substrate (manufactured by Nippon Test Panel Co., Ltd., 2 x 70 x 150 mm) using an applicator to create a cured film with a thickness of 40 μm. After drying at 90°C for 5 minutes, it was irradiated with ultraviolet light in two passes from a height of 18 cm at a conveyor speed of 3.4 m / min using one 80W high-pressure mercury lamp (cumulative irradiation dose of 800 mJ / cm²). 2 The procedure was performed to obtain a cured coating film. The resulting cured coating film was cut out along with the substrate into samples measuring 10 mm in width and 60 mm in length. These samples were subjected to tensile testing using an electric measuring stand (IMADA Corporation, "MX2-500N-FA") with a chuck distance of 40 mm, a tensile speed of 50 mm / min, and an ambient temperature of 80°C. The yield point was defined as elongation (%).

[0171] [Blocking resistance] The composition solution was applied to a black polycarbonate substrate (manufactured by Nippon Test Panel Co., Ltd., 2 x 70 x 150 mm) using an applicator to create a cured film with a thickness of 40 μm. After drying at 90°C for 5 minutes, it was irradiated with ultraviolet light in two passes from a height of 18 cm at a conveyor speed of 3.4 m / min using one 80W high-pressure mercury lamp (cumulative irradiation dose of 800 mJ / cm²). 2 The procedure was performed to obtain a cured coating film. The obtained cured coating film was subjected to a procedure at 23°C and 50% Rh conditions. A PET film was placed on the surface of the cured coating film, and it was bonded by rolling it back and forth once with a 2kg load roller. After 5 minutes, the PET film was peeled off to observe the blocking properties of the cured coating film surface, and it was evaluated according to the following evaluation criteria. [Evaluation Criteria] ◎: PET film does not adhere at all ○: The PET film adheres slightly, but leaves no residue when removed. △: The PET film adheres well, but leaves no residue when removed. ×: The PET film adheres tightly, leaving a residue when removed.

[0172] [Transparency (Hayes)] The composition was applied to a 125 μm easy-adhesion PET film (Toyobo Co., Ltd., "A4300") using an applicator to achieve a cured coating thickness of 40 μm. After drying at 90°C for 5 minutes, it was irradiated with ultraviolet light in two passes from a height of 18 cm at a conveyor speed of 3.4 m / min using one 80W high-pressure mercury lamp (cumulative irradiation dose of 800 mJ / cm²). 2 The procedure was performed to obtain a cured coating film. The resulting cured coating film was subjected to a haze meter (NDH 2000, manufactured by Nippon Denshoku Industries Co., Ltd.) to measure the combined haze value of the PET film and the cured coating film, and was evaluated according to the following evaluation criteria. The haze value of the PET film itself was 0.52. [Evaluation Criteria] ○: Haze value less than 1.0 △: Haze value is 1.0 or higher, but less than 3.0. ×: Haze value is 3.0 or higher

[0173] [Table 1]

[0174] As shown in Table 1 above, the cured coatings obtained from the compositions of Examples 1 to 7, which use a urethane (meth)acrylate compound (A) and a polysiloxane structure-containing compound (B) in combination, exhibited excellent self-restoring properties, flexibility, blocking resistance, and transparency. On the other hand, the cured coating film obtained from the composition of Comparative Example 1, which used a urethane (meth)acrylate compound (A'-1) that did not contain a structural site derived from polyol (z), had low elongation and poor flexibility. [Industrial applicability]

[0175] This composition, when formed into a cured coating, exhibits a well-balanced and excellent combination of self-healing properties against scratches, blocking resistance, and elongation, as well as superior transparency, making it useful for paints, inks, coatings, and the like. In particular, it is useful as a top-surface coating, a coating for metal surfaces, and an inkjet ink.

Claims

1. A composition containing a urethane (meth)acrylate compound (A) and a polysiloxane structure-containing compound (B), A composition in which the urethane (meth)acrylate compound (A) is a reaction product of a hydroxyl group-containing (meth)acrylate compound (x) containing a structural moiety derived from ε-caprolactone, a polyvalent isocyanate compound (y), and a polyol (z).

2. The composition according to claim 1, wherein the hydroxyl group-containing (meth)acrylate compound (x) is a hydroxyl group-containing (meth)acrylate compound containing one ethylenically unsaturated group.

3. The composition according to claim 1, wherein the polyvalent isocyanate compound (y) is at least one selected from the group consisting of biuret-type polymers, nurate-type polymers, and allophanate-type polymers of hexamethylene diisocyanate.

4. The composition according to claim 1, wherein the number average molecular weight of the polyvalent isocyanate compound (y) is 500 to 5,000.

5. The composition according to claim 1, wherein the weight-average molecular weight of the urethane (meth)acrylate compound (A) is 1,000 to 70,000.

6. The composition according to claim 1, wherein the degree of dispersion of the urethane (meth)acrylate compound (A) is 6 or less.

7. The composition according to claim 1, wherein the polysiloxane structure-containing compound (B) contains one or more ethylenically unsaturated groups.

8. The composition according to claim 1, wherein the polysiloxane structure-containing compound (B) is a polysiloxane structure-containing urethane (meth)acrylate compound (B1).

9. The composition according to claim 1, wherein the silicon atom content of the polysiloxane structure-containing compound (B) is 0.1 to 80% by mass.

10. The composition according to claim 1, wherein the content of the polysiloxane structure-containing compound (B) is 0.01 to 100 parts by mass per 100 parts by mass of the urethane (meth)acrylate compound (A).

11. A coating agent comprising the composition described in any one of claims 1 to 10.

12. The coating agent according to claim 11, to be used as a coating agent for the outermost surface.

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