Photocurable composition, cured product, article and method for producing article

Abstract

To provide a photocurable composition containing biomass material and forming a cured film that is resistant to scratches.SOLUTION: A photocurable composition comprises epoxidized vegetable oil (meth)acrylate (A1), glycerol poly(meth)acrylate or a derivative thereof (A2), and a photopolymerization initiator (B).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photocurable composition, a cured product, an article, and a method for producing the article. More specifically, the present invention relates to a photocurable composition containing a specific component, a cured product thereof, an article including the cured product, and a method for producing the article. [Background technology]

[0002] Photocurable compositions have been developed in various ways due to their wide range of applications, such as coatings and inks.

[0003] Patent Document 1 describes a curable composition containing the following components (A) and (B): Component (A): A (meth)acrylate mixture containing glycerin tri(meth)acrylate as the main component, in which the amount of high molecular weight substances in the mixture is less than 30% as the area percentage of high molecular weight substances defined by a specific formula, as measured by gel permeation chromatography. Component (B): Oligomer having two or more (meth)acryloyl groups and / or a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate

[0004] Patent Document 2 describes an active energy ray-curable composition containing the following components (A), (B), and (C), in which the total of the components (A), (B), and (C) is 100% by weight, and the composition contains 40 to 95% by weight of the component (A), 5 to 60% by weight of the component (B), and 0 to 55% by weight of the component (C). Component (A): A (meth)acrylate mixture containing glycerin tri(meth)acrylate as a main component, in which the high molecular weight component in component (A) is less than 30% in terms of area % according to gel permeation chromatography based on formula (1) Area% of polymers = [(RIL) / R] × 100 (1) The symbols and terms in formula (1) have the following meanings: R: Total area of ​​detected peaks in component (A) I: Area of ​​the detected peak containing glycerin tri(meth)acrylate L: Total area of ​​detection peaks having a weight average molecular weight smaller than that of the detection peak containing glycerin tri(meth)acrylate (B) Component: Filler Component (C): a compound having an ethylenically unsaturated group other than component (A)

[0005] Patent Document 3 describes a curable composition containing the following component (A): Component (A): A mixture containing a compound having three or more (meth)acryloyl groups, alkylene oxide units, and a tertiary amino group, which is a Michael addition reaction product of the following mixture (a) and compound (b): Mixture (a): A (meth)acrylate mixture containing a compound (a1) having four or more (meth)acryloyl groups and an alkylene oxide unit. Compound (b): Secondary amine

[0006] Patent Document 4 describes an active energy ray-curable composition containing the following components (A), (B), and (C), in which the total of the components (A), (B), and (C) is 100% by weight, and the composition contains 50% by weight to 90% by weight of the component (A), 5% by weight to 35% by weight of the component (B), and 0% by weight to 45% by weight of the component (C). Component (A): An acrylate mixture containing glycerin triacrylate as a main component, in which the amount of high molecular weight components in the mixture is less than 30% as the area percentage of high molecular weight components defined by the following formula (1) as measured by gel permeation chromatography: Area% of polymers = [(RIL) / R] × 100 (1) The symbols and terms in formula (1) have the following meanings: R: Total area of ​​detected peaks in component (A) I: Area of ​​the detected peak containing glycerol triacrylate L: Total area of ​​detection peaks with a weight average molecular weight smaller than that of the detection peak containing glycerin triacrylate Component (B): A compound having a viscosity of less than 20 mPa·s, a homopolymer glass transition temperature of more than 50°C, and having one or two ethylenically unsaturated groups. Component (C): A compound other than component (A) that has three or more ethylenically unsaturated groups. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2017 / 033732 [Patent Document 2] International Publication No. 2018 / 092785 [Patent Document 3] JP 2018-165363 A [Patent Document 4] JP 2019-196461 A Summary of the Invention [Problem to be solved by the invention]

[0008] From the viewpoint of environmental protection, the need for products using biomass raw materials has been increasing in recent years. It is considered that the photocurable composition also uses biomass raw materials as a part of its raw materials. For example, it is considered that the biomass raw materials are used as polymerizable (meth)acrylate in the photocurable composition.

[0009] However, compared to the rich lineup of petroleum-derived raw materials, the lineup of biomass raw materials is limited. Biomass raw materials with the same chemical structure as petroleum-derived raw materials are not always available on the market. For this reason, it may be difficult to achieve the same level of performance using biomass raw materials as conventional photocurable compositions produced using only petroleum-derived raw materials. According to the inventors' preliminary investigation, a cured film formed from a photocurable composition using a biomass raw material has a tendency to be easily damaged by, for example, an external force.

[0010] The present invention has been made in view of the above circumstances. One of the objects of the present invention is to provide a photocurable composition that contains a biomass raw material and is resistant to scratches when formed into a cured film. [Means for solving the problem]

[0011] The present inventors have completed the invention provided below and have solved the above problems.

[0012] 1. an epoxidized vegetable oil (meth)acrylate (A1); Glycerin poly(meth)acrylate or a derivative thereof (A2), A photopolymerization initiator (B); 1. A photocurable composition comprising: 2. 1. The photocurable composition according to claim 1, The derivative is a photocurable composition comprising a poly(meth)acrylate formed by reaction of a hydroxy group in a glycerin poly(meth)acrylate with an isocyanate group in a polyisocyanate. 3. 1. The photocurable composition according to 1. or 2., The content of (A1) in the composition is a 1 The content of (A2) in the composition is a 2 , then a 2 / a 1 is a mass ratio of 0.3 to 3.0. 4. The photocurable composition according to any one of 1. to 3., The (A2) is a photocurable composition containing glycerin poly(meth)acrylate or a derivative thereof synthesized using biologically derived glycerin as a raw material. 5. The photocurable composition according to any one of 1. to 4., The (A2) is a photocurable composition containing at least one selected from the group consisting of glycerin di(meth)acrylate, glycerin tri(meth)acrylate, and a tetrafunctional glycerin poly(meth)acrylate obtained by reacting glycerin di(meth)acrylate with 1,5-pentamethylene diisocyanate in a molar ratio of 2:1. 6. The photocurable composition according to any one of 1. to 5., The (A1) is a photocurable composition containing epoxidized soybean oil (meth)acrylate. 7. The photocurable composition according to any one of 1. to 6., The (B) is a photocurable composition containing a photopolymerization initiator (B1) that satisfies the following [light absorption characteristics]. [Light absorption characteristics] A solution of 0.1% by mass of photopolymerization initiator (B1) dissolved in acetonitrile is placed in a cell with a light path length of 1 cm, and the absorbance (Abs) of light at a wavelength of 380 nm is measured. 380 is 0.3 or more. 8. The photocurable composition according to any one of 1. to 7., The (B) is a photocurable composition containing an acylphosphine compound. 9. The photocurable composition according to any one of 1. to 8., A photocurable composition comprising a polymerizable monomer (A3) which does not fall under either (A1) or (A2). 10. The photocurable composition according to any one of 1. to 9., A photocurable composition, in which the total ratio of (A1) and (A2) in all polymerizable components in the composition is 40 mass% or more. 11. The photocurable composition according to any one of 1. to 10., A photocurable composition having a biomass ratio of 10% or more. 12. The photocurable composition according to any one of 1. to 11., The photocurable composition further comprises a pigment. 13. A cured product of the photocurable composition according to any one of 1. to 12. 14. 13. An article comprising the cured product described above. 15. a film-forming step of forming a film on a substrate using the photocurable composition according to any one of 1. to 12.; a light irradiation step of irradiating the film with light; A method for manufacturing an article, comprising: 16. 15. A method for producing an article according to claim 1, comprising the steps of: The method for manufacturing an article, wherein the light is ultraviolet light. 17. A method for producing an article according to claim 15 or 16, comprising the steps of: In the light irradiation step, the film is irradiated with ultraviolet light emitted from an ultraviolet light emitting diode. Effect of the Invention

[0013] According to the present invention, there is provided a photocurable composition which contains a biomass raw material and which, when formed into a cured film, is resistant to scratches. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Hereinafter, an embodiment of the present invention will be described in detail.

[0015] In this specification, unless otherwise specified, the expression "X to Y" in the explanation of a numerical range means from X to Y. For example, "1 to 5% by mass" means "from 1% by mass to 5% by mass". In the description of groups (atomic groups) in this specification, when a description is made without specifying whether the group is substituted or unsubstituted, the description includes both groups having no substituents and groups having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituents (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, the term "(meth)acrylic" refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate."

[0016] <Photocurable composition> The photocurable composition of this embodiment is an epoxidized vegetable oil (meth)acrylate (A1); Glycerin poly(meth)acrylate or a derivative thereof (A2), A photopolymerization initiator (B); Includes.

[0017] Hereinafter, the epoxidized vegetable oil (meth)acrylate (A1) may be simply referred to as (A1). The glycerin poly(meth)acrylate or its derivative (A2) may be simply referred to as (A2). The photopolymerization initiator (B) may be simply referred to as (B).

[0018] (A1) is relatively easy to obtain and is easy to use as a biomass raw material. However, according to the preliminary study by the present inventors, the cured film formed using the photocurable composition containing (A1) was prone to being scratched by external forces. There are several possible reasons for this, but it is speculated that the vegetable oil, which is the raw material for (A1), is a mixture of various fatty acids, which leads to non-uniformity in the cured film, that the vegetable oil contains chemical structures that lead to performance deterioration, and that the amount of carbon-carbon double bonds per unit mass is small.

[0019] For this reason, in designing a photocurable composition, the present inventors have considered using (A1) in combination with other (meth)acrylates as a polymerizable (meth)acrylate, rather than using only (A1), in an attempt to make up for the lack of performance when only (A1) is used. As a result of trial and error, the present inventors have succeeded in compensating for the lack of performance when only (A1) is used by using (A2) in combination. Incidentally, known examples of (A2) include glycerin poly(meth)acrylate or its derivatives synthesized using plant-derived glycerin as a raw material. By using such (A2), the performance of the cured film can be improved without significantly decreasing the biomass content of the entire composition.

[0020] Incidentally, photocurable compositions containing both (A1) and (A2) are not easily scratched when formed into a cured film, but may also have other good properties. Examples of other properties include sensitivity, stain resistance, and discoloration resistance. It is presumed that these properties are also due to (A2) compensating for the shortcomings of (A1). The inventors have found that the viscosity of (A1) is relatively high. Therefore, photocurable compositions using only (A1) as a polymerizable component tend to have poor coating suitability. When the coating suitability is poor, various properties of the coating film formed also tend to deteriorate. On the other hand, the viscosity of (A2) is relatively low. Therefore, it is expected that the coating suitability can be improved by using (A1) and (A2) in combination, and thus various properties of the coating film formed can also be improved.

[0021] The curable composition of this embodiment will now be described.

[0022] (Epoxidized vegetable oil (meth)acrylate (A1)) (A1) is a compound usually produced by ring-opening addition polymerization of (meth)acrylic acid to the epoxy groups of epoxidized vegetable oil, which is obtained by epoxidizing the double bonds of unsaturated vegetable oil with peracetic acid, perbenzoic acid, or the like. Vegetable oils are usually triglycerides of glycerin and fatty acids, in which at least one fatty acid has at least one carbon-carbon unsaturated bond. Representative compounds of such vegetable oils include hemp seed oil, linseed oil, perilla oil, oiticica oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, apricot kernel oil, tung oil, kukui oil, walnut oil, poppy seed oil, sesame oil, safflower oil, radish seed oil, soybean oil, tung oil, camellia oil, corn oil, rapeseed oil, niger oil, rice bran oil, palm oil, castor oil, sunflower oil, grape seed oil, almond oil, pine seed oil, cottonseed oil, coconut oil, peanut oil, dehydrated castor oil, etc. Among these, soybean oil is preferred as vegetable oil from the viewpoint of availability and various performances. That is, (A1) preferably contains epoxidized soybean oil (meth)acrylate. As (A1), any known or commercially available compound can be used without any particular limitation. Compounds corresponding to (A1) can be purchased from, for example, Miwon Specialty Chemical Co., Ltd., Eternal Materials Co., Ltd., etc.

[0023] The photocurable composition of this embodiment may contain only one (A1), or may contain two or more (A1). The amount of (A1) in the total non-volatile components of the photocurable composition of this embodiment is preferably from 5 to 50 mass %, more preferably from 10 to 40 mass %, and even more preferably from 10 to 30 mass %.

[0024] (Glycerin poly(meth)acrylate or its derivative (A2)) Specific examples of the glycerin poly(meth)acrylate preferably include glycerin di(meth)acrylate and glycerin tri(meth)acrylate. For reference, the structural formulae of glycerin diacrylate and glycerin triacrylate are shown below.

[0025] [ka]

[0026] A preferred example of the derivative of glycerin poly(meth)acrylate is a poly(meth)acrylate formed by reacting a hydroxy group in glycerin poly(meth)acrylate with an isocyanate group in a polyisocyanate. More specifically, a tetrafunctional glycerin poly(meth)acrylate formed by reacting glycerin di(meth)acrylate with 1,5-pentamethylene diisocyanate in a molar ratio of 2:1 can be mentioned.

[0027] (A2) preferably contains glycerin poly(meth)acrylate or a derivative thereof synthesized using biologically derived glycerin as a raw material. Known biologically derived glycerin includes plant-derived glycerin and animal-derived glycerin such as tallow. For example, Aronix® M-920 and M-930 from Toagosei are glycerin poly(meth)acrylates made from plant-derived glycerin. M-920 is a mixture of glycerin di / triacrylate, and M-930 is glycerin triacrylate. As another example, a tetrafunctional glycerin polyacrylate obtained by reacting glycerin diacrylate, which is synthesized using plant-derived glycerin as a raw material, with 1,5-pentamethylene diisocyanate in a molar ratio of 2:1 can be used as (A2).

[0028] In terms of improving various performances, (A2) preferably contains a tri- or higher functional glycerin poly(meth)acrylate or a derivative thereof, and more preferably contains a tri- or tetrafunctional glycerin poly(meth)acrylate or a derivative thereof. The photocurable composition of this embodiment may contain only one (A2), or may contain two or more (A2). The amount of (A2) in the total non-volatile components of the photocurable composition of this embodiment is preferably from 10 to 80 mass %, more preferably from 15 to 70 mass %.

[0029] (Ratio of (A2) to (A1)) From the viewpoint of optimizing performance and adjusting the degree of biomass, it is preferable that the ratio of (A1) to (A2) is appropriately adjusted. The content of (A1) in the photocurable composition is a 1 The content of (A2) in the photocurable composition is a 2 , then a 2 / a 1 is a mass ratio, and is preferably 0.3 to 3.0, and more preferably 0.4 to 2.5.

[0030] (Polymerizable monomer (A3)) The photocurable composition of this embodiment may contain a polymerizable monomer (A3) that does not fall under either (A1) or (A2). By using an appropriate polymerizable monomer (A3), further improvement in performance can be expected. The polymerizable monomer (A3) may be derived from biomass or petroleum. All of the polymerizable monomers (A3) used in the examples described below are derived from petroleum.

[0031] The polymerizable monomer (A3) is preferably a polyfunctional (meth)acrylate having 3 or more functional groups, more preferably a polyfunctional (meth)acrylate having 3 to 6 functional groups, and even more preferably a polyfunctional (meth)acrylate having 4 to 6 functional groups. The use of a polyfunctional (meth)acrylate may improve the sensitivity, the hardness of the cured film, and various other performances. Specific examples of polyfunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin propoxy tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, and caprolactam-modified dipentaerythritol hexa(meth)acrylate. By using an EO (ethylene oxide)-modified or caprolactone-modified polymerizable monomer (A3), the final cured film may become appropriately flexible, and the properties of the cured film may be further improved.

[0032] As the polymerizable monomer (A3), a monofunctional (meth)acrylate may be used. By using a monofunctional (meth)acrylate, it may be possible to make the cured film moderately flexible and suppress cracking. Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acryloylmorpholine, tetrahydrofurfuryl (meth)acrylate, and ethoxy-diethylene glycol (meth)acrylate.

[0033] As the polymerizable monomer (A3), a (meth)acrylamide monomer can also be used. By using such a monomer, for example, it can be expected that the adhesion of the cured film to the substrate can be improved. Specific examples of the (meth)acrylamide monomer include (meth)acryloylmorpholine, dimethyl(meth)acrylamide, diethyl(meth)acrylamide, di-n-propyl(meth)acrylamide, dibutyl(meth)acrylamide, and diacetone(meth)acrylamide.

[0034] When the polymerizable monomer (A3) is used, only one polymerizable monomer (A3) may be used, or two or more polymerizable monomers (A3) may be used.

[0035] When the polymerizable monomer (A3) is used, its amount is not particularly limited, however, from the viewpoint of sufficiently increasing the biomass degree and further reducing the risk of scratches when formed into a cured film, it is preferable that the amounts of (A1) and (A2) are relatively large, and it is preferable that the amount of the polymerizable monomer (A3) is not too large. Specifically, the total ratio of (A1) and (A2) in all polymerizable components in the curable composition (usually the above (A1), (A2) and (A3)) is preferably 40 mass% or more, more preferably 40 to 100 mass%, and even more preferably 45 to 100 mass%. In other words, the amount of the polymerizable monomer (A3) in all polymerizable components in the curable composition is preferably 0 to 60 mass%, more preferably 0 to 55 mass%.

[0036] (Photopolymerization initiator (B)) The photopolymerization initiator (B) is not particularly limited so long as it is capable of generating an activated chemical species by light and initiating a polymerization reaction of the carbon-carbon double bond in the (meth)acrylate structure of (A1) or (A2), or, in some cases, the polymerizable monomer (A3).

[0037] The photopolymerization initiator (B) typically includes a photoradical polymerization initiator. Specific examples of the photoradical polymerization initiator include an α-hydroxyketone-based photopolymerization initiator, an α-aminoketone-based photopolymerization initiator, a bisacylphosphine-based photopolymerization initiator, a monoacylphosphine oxide-based photopolymerization initiator, a bisacylphosphine oxide-based photopolymerization initiator, a mono- and bis-acylphosphine-based photopolymerization initiator, a benzyl dimethyl ketal-based photopolymerization initiator, and the like.

[0038] The photopolymerization initiator (B) preferably contains a photopolymerization initiator (B1) that satisfies the following [light absorption characteristics]. [Light absorption characteristics] A solution of 0.1% by mass of photopolymerization initiator (B1) dissolved in acetonitrile is placed in a cell with a light path length of 1 cm, and the absorbance (Abs) of light at a wavelength of 380 nm is measured. 380 is 0.3 or more.

[0039] Abs 380 Although there is no particular upper limit for Abs, taking into consideration the types of photopolymerization initiators available, 380 The upper limit is, for example, 3.0 or less, preferably 2.5 or less.

[0040] By including the photopolymerization initiator (B1) in the photocurable composition, sufficient sensitivity is easily obtained even when an ultraviolet light emitting diode (UV-LED) is used as an exposure light source. UV-LEDs have a longer light source life and are more energy-efficient than conventional light sources. Therefore, in recent years, they have been increasingly used as light sources for ultraviolet light exposure. However, because the emission spectrum of UV-LEDs is sharp, the total amount of ultraviolet energy may be smaller than that of conventional light sources with broad emission spectra. It is believed that the photopolymerization initiator (B1) having the above-mentioned light absorption characteristics efficiently absorbs the light emitted from the UV-LED and efficiently produces active chemical species. Therefore, it is believed that sufficient sensitivity can be easily obtained even when a UV-LED is used as the exposure light source.

[0041] Just to be clear, as long as the photocurable composition of the present embodiment is cured by light irradiation, it does not contain a photopolymerization initiator (B) that corresponds to the photopolymerization initiator (B1), and may contain a photopolymerization initiator (B) that does not correspond to the photopolymerization initiator (B1). The photocurable composition of the present embodiment may be cured by exposure to a light source other than a UV-LED (such as a halogen lamp or a mercury lamp).

[0042] Examples of the photopolymerization initiator (B1) that satisfies the above [light absorption characteristics] include the following. Omnirad TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide, Abs 380 = 1.6), Omnirad TPO-L (Ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, Abs 380 =0.7), Omnirad 369 (2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, Abs 380 is greater than 2.0), Omnirad 819 (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, Abs 380 = 1.9), Omnirad EMK (4,4'-bis(diethylamino)benzophenone, Abs 380 =0.8), Omnirad 379 (2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, Abs 380 = 1.2), (All of the above are manufactured by IGM Resins.) Irgacure OXE01 (1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyloxime), Abs 380 is greater than 2.0), Irgacure OXE02 (Ethanone, 1-[8-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), Abs 380 =0.6), Irgacure 784 (di-H5-cyclopentadienylbis[2,6-difluoro-3-(pyrrol-1-yl)phenyltitanium(4)], Abs 380 =1.9) (All of the above are manufactured by BASF)

[0043] The photopolymerization initiator (B) preferably contains a compound having a benzoyl group. The hydrogen atom on the benzene ring of the benzoyl group may be substituted with any group. Examples of the photopolymerization initiator (B) containing a compound having a benzoyl group include the following agents. Omnirad TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide, Abs 380 = 1.6), Omnirad TPO-L (Ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, Abs 380 =0.7), Omnirad 369 (2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, Abs 380 is greater than 2.0), Omnirad 819 (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, Abs 380 = 1.9), Omnirad EMK (4,4'-bis(diethylamino)benzophenone, Abs 380 =0.8), Omnirad 379 (2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, Abs 380 = 1.2), (All of the above are manufactured by IGM Resins.) Irgacure OXE01 (1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyloxime), Abs 380 is greater than 2.0), Irgacure OXE02 (Ethanone, 1-[8-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), Abs 380 =0.6), (All of the above are manufactured by BASF)

[0044] The photopolymerization initiator (B) more preferably contains an acylphosphine compound or an α-alkylaminophenone compound, and further preferably contains an acylphosphine compound.

[0045] Examples of the photopolymerization initiator (B) containing an acylphosphine compound include the following agents. Omnirad TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide, Abs 380 = 1.6), Omnirad 819 (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, Abs 380 =1.9) Those containing acylphosphine oxide compounds such as Omnirad TPO-L (Ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, Abs 380 =0.7) Those containing acylphosphine ester compounds such as (All of the above are manufactured by IGM Resins.)

[0046] Examples of the photopolymerization initiator (B) containing an α-alkylaminophenone compound include the following agents. Omnirad 369 (2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, Abs 380 is greater than 2.0), Omnirad 379 (2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, Abs 380 = 1.2), (All of the above are manufactured by IGM Resins.)

[0047] Just to be clear, the photopolymerization initiator (B) is not limited to only the photopolymerization initiator (B1), so long as the photocurable composition is photosensitive and can solve the above-mentioned problems.

[0048] The photocurable composition of this embodiment may contain only one photopolymerization initiator (B), or may contain two or more photopolymerization initiators (B). The amount of the photopolymerization initiator (B) in the total non-volatile components of the photocurable composition of this embodiment is preferably from 1 to 20 mass %, more preferably from 5 to 15 mass %.

[0049] (Pigments) The photocurable composition of the present embodiment may contain a pigment. By containing a pigment in the photocurable composition, for example, the cured film can be given a desired color, thereby improving the design. In addition, depending on the type of pigment, some improvement in the properties of the cured film can be expected in addition to the design.

[0050] The pigment that can be used is not particularly limited, and for example, a color pigment such as a known inorganic pigment or organic pigment can be used. Specific examples of the pigments include white pigments such as titanium dioxide (titanium white), zinc oxide, white lead, basic lead sulfate, lead sulfate, lithopone, zinc sulfide, and antimony white; black pigments such as carbon black, acetylene black, lamp black, graphite, iron black (black iron oxide), and aniline black; yellow pigments such as naphthol yellow S, Hansa yellow, Pigment yellow L, benzidine yellow, permanent yellow, and yellow iron oxide; orange pigments such as chrome orange, chrome vermilion, and permanent orange; brown pigments such as iron oxide and amber; red pigments such as red iron oxide, red lead, permanent red, quinacridone red pigments, and diketopyrrolopyrrole red pigments; purple pigments such as cobalt purple, fast violet, and methyl violet lake; blue pigments such as ultramarine, Prussian blue, cobalt blue, phthalocyanine blue, and indigo; and green pigments such as chrome green, pigment green B, and phthalocyanine green.

[0051] As the pigment, a body pigment may be used. The usable body pigment is not particularly limited. For example, baryta powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, magnesium silicate hydrate, alumina white, gloss white, mica powder, etc. may be mentioned.

[0052] As the pigment, inorganic pigments and extender pigments are preferably used because they are less likely to fade, although organic pigments can also be used if fading is not an issue.

[0053] The pigment may include anti-rust pigments known in the field of powder coatings, such as zinc oxide, phosphite compounds, phosphate compounds, molybdate compounds, bismuth compounds, and metal ion-exchanged silica.

[0054] When a pigment is used, only one type may be used, or a plurality of types may be used in combination. When a pigment is used, its amount is not particularly limited. The amount used may be appropriately adjusted depending on the balance between the desired color tone and other properties. For example, the amount of the pigment is typically 1 to 150 parts by mass, preferably 2 to 100 parts by mass, when the non-volatile components other than the pigment in the composition are 100 parts by mass.

[0055] (Other added ingredients) The photocurable composition of this embodiment may contain any component other than those described above. Examples of optional components include colorants other than pigments (such as dyes), defoamers, leveling agents, surfactants, polymerization inhibitors, waxes, antioxidants, non-reactive polymers, fine inorganic fillers, silane coupling agents, light stabilizers, ultraviolet absorbers, antistatic agents, slip agents, and antibacterial agents.

[0056] (solvent) The photocurable composition of this embodiment may or may not contain a solvent. If some or all of the above (A1), (A2) and (A3) are liquid at room temperature, they can be applied to a substrate without using a solvent, so there are cases where a solvent is not required. However, even if some or all of the above (A1), (A2) and (A3) are liquid at room temperature, a solvent may be used to adjust the viscosity or applicability.

[0057] The solvent includes water or an organic solvent, and preferably includes an organic solvent. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol (2-methyl-2-propanol), tert-amyl alcohol, and diacetone alcohol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and isobutyl acetate.

[0058] When the film-forming resin composition of the present embodiment contains a solvent, it may contain only one type of solvent, or may contain two or more types of solvents. When the film-forming resin composition of the present embodiment contains a solvent, the amount of the solvent is not particularly limited. For example, the solvent is preferably used in an amount such that the solid content (non-volatile component) concentration of the composition is 5 to 99% by mass, preferably 10 to 70% by mass.

[0059] (Biomass ratio) As a result of using raw materials of biological origin, the biomass ratio of the photocurable composition of this embodiment is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. A high biomass ratio means that the product is environmentally friendly. In addition, if the biomass ratio is 10% or more, the product can use the biomass mark certified by the Japan Organics Resources Association (JORA), which will appeal to customers and users. The higher the biomass ratio, the more preferable it is in terms of appealing to the environmental performance, but in terms of the balance with other performance factors, the upper limit of the biomass ratio is, for example, 60%. In the Biomass Mark certification process at JORA, the biomass degree is calculated by measuring the amount of carbon-14 in the target product. This is because organic matter derived from living organisms contains carbon-14 at a concentration similar to that in the atmosphere, but organic matter derived from petroleum contains virtually no carbon-14. If the amount of carbon-14 in the target product cannot be measured, the biomass degree can be calculated from the biomass degree and usage ratio (dry weight ratio) of each raw material used. In the examples shown below, the biomass degree is calculated in the latter manner.

[0060] <Cured product, article, and method for producing article> By curing the above-mentioned photocurable composition, a cured product or an article including the cured product can be produced. The cured product is provided on the surface of various articles, for example, wooden articles such as flooring and furniture in homes, paper articles such as books, plastic articles such as exterior materials for home appliances and electronic devices, metal articles such as vehicle bodies, etc. The photocurable composition is applied to the surface of these articles to form an uncured film, which is then irradiated with light to cure, thereby providing a cured product on the surface of the article. On the surface of the article before providing a cured product of the above-mentioned photocurable composition, a layer other than the cured layer formed by curing the above-mentioned photocurable composition, such as an underlayer film, a primer layer, a colored layer, or the like, may or may not be provided.

[0061] Alternatively, a film or sheet-like cured product can be obtained by applying a photocurable composition to any surface to form an uncured film, irradiating the uncured film with light to cure it into a cured film, and then peeling off the cured film.

[0062] As already mentioned, the cured product (cured film) of the above-mentioned photocurable composition is not easily scratched. This means that an article having the cured product (cured film) of the above-mentioned photocurable composition on its surface is not easily scratched and is likely to maintain a beautiful appearance for a long period of time.

[0063] The article comprising the cured product is a film forming step of forming a film on a substrate using the photocurable composition; a light irradiation step of irradiating the formed film with light; The composition can be produced by a method comprising the steps of:

[0064] In the film-forming step, the coating amount of the photocurable composition is, for example, 2 to 220 g / m 2 , preferably 4 to 110 g / m 2 It is.

[0065] The photocurable composition can be applied by any method / apparatus. Preferably, the film-forming step is performed by roll coating, flow coating (also called curtain coating) or spraying. These methods are industrially easy to form a uniform film on a substrate. Therefore, they are preferably applied to the film-forming step. When the photocurable composition contains a solvent, it is preferable to volatilize the solvent by heating.

[0066] In the light irradiation process, the light irradiated onto the formed film is usually ultraviolet light. Examples of light sources that emit ultraviolet light include mercury lamps, xenon lamps, metal halide lamps, and ultraviolet light-emitting diodes (UV-LEDs). As mentioned in the explanation of the photopolymerization initiator (B), when the photocurable composition contains the photopolymerization initiator (B1), sufficient sensitivity is easily obtained even when a UV-LED is used as an exposure light source. In other words, in the light irradiation step, it is preferable to irradiate the film with ultraviolet light emitted from a UV-LED. The wavelength range of the ultraviolet light emitted from the UV-LED is, for example, 350 to 420 nm, and preferably 360 to 410 nm.

[0067] The amount of light irradiation in the light irradiation step is, for example, 50 to 800 mJ / cm 2 , preferably 100 to 600 mJ / cm 2 Of course, the amount of irradiation may be appropriately adjusted depending on the sensitivity of the photocurable composition, the film thickness, etc.

[0068] The light intensity in the light irradiation step is, for example, 10 to 5000 W / cm 2 , preferably 50 to 2000 W / cm 2 Of course, the intensity of the light may be appropriately adjusted depending on the sensitivity of the resin composition used, the film thickness, etc.

[0069] In the light irradiation step, one film may be irradiated with light multiple times. In this case, it is preferable that at least one of the multiple light irradiations is by a UV-LED.

[0070] The method for producing a cured product may further include a heating step of accelerating the curing reaction by heating, in addition to the film formation step and the light irradiation step.

[0071] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of the present invention are included in the present invention. EXAMPLES

[0072] The embodiments of the present invention will be described in detail based on Examples and Comparative Examples. It should be noted that the present invention is not limited to the Examples.

[0073] <Preparation of raw materials> The following raw materials were prepared:

[0074] (Epoxidized vegetable oil (meth)acrylate (A1)) Miramer PE310: Epoxidized soybean oil acrylate manufactured by Miwon Specialty Chemical Co., Ltd. Etercure 6261: Epoxidized soybean oil acrylate manufactured by Eternal Materials Co., Ltd.

[0075] (Glycerin poly(meth)acrylate or its derivative (A2)) Aronix M930: Glycerin triacrylate, manufactured by Toagosei Co., Ltd. Aronix M920: Glycerin di / triacrylate, manufactured by Toagosei Co., Ltd. (a2): A tetrafunctional glycerin polyacrylate synthesized as follows, in which glycerin diacrylate and 1,5-pentamethylene diisocyanate were reacted in a molar ratio of 2:1. [Synthesis of (a2)] A flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 77 parts by mass of ARONIX M920 and a catalyst. While stirring the components in the flask with a stirrer, 23 parts by mass of STABIO PDI (1,5-pentamethylene diisocyanate with a biomass content of 70%, manufactured by Mitsui Chemicals, Inc.) was added dropwise over one hour. The mixture was allowed to react at 70°C for six hours. After that, the reaction was terminated after it was confirmed by infrared absorption analysis that the peak of the remaining isocyanate group had disappeared. In this manner, (a2) was obtained.

[0076] Just to be clear, all three of the glycerin raw materials for (A2) mentioned above are derived from plants.

[0077] (Polymerizable monomer (A3)) PETIA: Pentaerythritol (tri / tetra)acrylate, manufactured by Daicel Allnex Corporation DPHA: Dipentaerythritol hexaacrylate, manufactured by Daicel Allnex TMPTA(EO)15: Ethylene oxide modified trimethylolpropane triacrylate, manufactured by MIWON ACMO: acryloylmorpholine, KJ Chemicals

[0078] (Photopolymerization initiator (B)) Omnirad TPO: Acylphosphine photoinitiator, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, IGM Resins, Abs 380 =1.6 Omnirad TPO-L: Acylphosphine photoinitiator, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, IGM Resins, Abs 380 =0.7 Omnirad 819: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, Abs 380 =1.9

[0079] (Pigments) Silica (registered trademark) 550: Silica particles manufactured by Fuji Silysia Chemical Ltd. Clay: Takehara Chemical Industry Co., Ltd. (These two pigments are used as extender pigments.)

[0080] (Dispersant) DISPERBYK-2008: BYK, solvent-free wetting and dispersing agent

[0081] <Preparation of Composition> The above components were uniformly mixed in the amounts shown in the table below to prepare photocurable compositions.

[0082] <Preparation and evaluation of test panels> First, a piece of plywood measuring 60 cm in length, 30 cm in width, and 1.2 cm in total thickness was prepared, with a 0.25 mm thick oak veneer attached to the surface. A colored paint (Flora No. 300, a urethane dispersion type colored paint manufactured by Natoco) was applied to the plywood at a rate of 33 g / m. 2 The board was then dried with hot air at 100°C for 60 seconds to obtain a colored plywood board.

[0083] The undercoat composition obtained by mixing the following components was applied to the colored plywood at a coating weight of 44 g / m2. 2 This was then coated with ultraviolet light (exposure dose 100mJ / cm 2 , maximum irradiation intensity 80mW / cm 2 ) to cure the applied undercoat composition and provide an undercoat layer. (Ingredients for Undercoat Composition) - 40 parts by weight of urethane acrylate (product name: EBECRYL210, manufactured by Daicel Allnex Co., Ltd.) 30 parts by weight of acryloylmorpholine (KJ Chemicals) Radical polymerization initiator (product name: OMNIRAD1173, manufactured by IGM Resins) 6 parts by weight Talc 24 parts by weight

[0084] Thereafter, the plywood provided with the undercoat layer was sanded with waterproof paper #320 to obtain a substrate (substrate to which the photocurable composition is to be applied).

[0085] The prepared photocurable composition was applied to the above substrate using a roll coater at a coating amount of 16 g / m 2 The coating was performed so that the film thickness was 15 μm. Next, the surface coated with the photocurable composition was passed through a UV-LED irradiation device (UELCLP385-20028T, 385 nm, irradiation port 40 cm, manufactured by iGraphics Co., Ltd.) so that the light emitted from the UV-LED was irradiated. The speed of passing was measured when the integrated light amount in the UV-V region (395 to 445 nm) measured with an ultraviolet light actinometer UV Power Puck (registered trademark) II (manufactured by EIT Co., Ltd.) was 200 mJ / cm. 2 , with an intensity of 2000mW / cm 2 Depending on the sensitivity of the composition, one or more passes were performed (see Sensitivity Evaluation below).

[0086] [Sensitivity evaluation] The above-mentioned UV-LED irradiation device was used to perform light irradiation once or multiple times. The number of passes was repeated until it was determined that the coating had cured according to the following criteria. A cured film was then obtained. To determine whether the coating has hardened, place steel wool #000 on the surface irradiated with UV-LED and measure at 1kg / cm 2 When no visible scratches were observed after 10 reciprocating strokes under a load of 100 mm, the specimen was judged to have hardened. 5: 1 pass 4: 2 passes 3: 3 passes 2: 4 passes 1: 5 or more passes

[0087] [Evaluation of scratch resistance of cured film (coin scratch resistance)] As described above, a 10 yen coin was placed at a 45° angle on the cured film that had been sufficiently cured by one or more light exposures, and scratched once with a load of 2 kg. The degree of scratching was then visually evaluated on a 5-point scale according to the following criteria. 5: No scratches were found. 4: Very slight scratches were observed, but no whitening was observed. 3: Slight scratches were observed, but almost no whitening was observed. 2: There were slight scratches and the surface was slightly whitened. 1: Scratches or whitening were significantly noticeable.

[0088] [Evaluation of stain resistance] The stain resistance of the above-mentioned coated board was evaluated according to the JAS plywood staining test A. Specifically, the following procedure was performed. (1) As described above, a 10 mm wide line was drawn with blue ink on the surface of the cured film that had been sufficiently cured by one or more light exposures, and the film was left for 4 hours. (2) Next, the area where the blue ink was drawn was wiped off with a cloth soaked in methanol. (3) After (2) was completed, the color difference (ΔE) between the part where the blue ink was wiped off and the untested part (the part where the blue ink was not drawn and the ink was not wiped off) was measured according to JIS Z 8781-4:2013. The results were then evaluated on a 5-point scale based on the following criteria. 5: ΔE is less than 0.5 4: ΔE is 0.5 or more and less than 1 3: ΔE is 1 or more and less than 1.5 2: ΔE is 1.5 or more and less than 2 1: ΔE is 2 or more

[0089] [Evaluation of discoloration resistance] As described above, the color difference (ΔE) between the surface of the cured film that was sufficiently cured by one or more light exposures and the surface of the plywood with the undercoat layer before the photocured film was applied was measured according to JIS Z 8781-4:2013, and the discoloration of the resin composition was evaluated on a 5-point scale based on the following criteria. The smaller the ΔE, the less discoloration caused by UV-LED exposure is suppressed (the better the discoloration resistance). 5: ΔE is less than 3 4: ΔE is 3 or more and less than 3.5 3: ΔE is 3.5 or more and less than 4 2: ΔE is 4 or more and less than 5 1: ΔE is 5 or more

[0090] [Biomass Degree Evaluation] The biomass degree was calculated based on the ratio of biological raw materials used in the table below and the biomass degree of the biological raw materials themselves (provided by the raw material manufacturer). It was then rated on the following five-point scale. Incidentally, as mentioned above, if the biomass degree is 10% or more, the biomass mark certified by the Japan Organics Recycling Association can be used, which will appeal to customers and users. 5: Biomass content 40% or more 4: Biomass content: 30% to less than 40% 3: Biomass content: 20% to 30% 2: Biomass content: 10% to less than 20% 1: Biomass content less than 10%

[0091] The composition and evaluation results are summarized in the table below.

[0092] [Table 1]

[0093] [Table 2]

[0094] As shown in Tables 1 and 2, the scratch resistance (coin scratch resistance) of the cured films formed using the compositions of the examples was rated at 2 or more, and the biomass degree of the compositions of the examples was rated at 2 or more (biomass degree of 10% or more). In other words, the compositions of the examples were photocurable compositions that contained a relatively large amount of biomass raw material to such an extent that a biomass mark could be used, and were resistant to scratches when formed into a cured film. Furthermore, the results of the sensitivity evaluation in the examples were good, which confirmed that the compositions of the examples had sufficient sensitivity when irradiated with UV-LED light. Furthermore, in the examples, the evaluations of sensitivity, stain resistance, and discoloration resistance were also good.

[0095] In comparison with the compositions of the Examples, the composition of Comparative Example 1 had a good resistance to scratches on the cured film (coin scratch resistance). However, since the composition of Comparative Example 1 did not contain (A1), the biomass degree was evaluated as 1, the lowest. Furthermore, the biomass degree of the compositions of Comparative Examples 2 and 3, which did not contain (A2), was at the same level as that of the Examples, but the evaluation results for scratch resistance (coin scratch resistance) of the cured films of these compositions were 1, the lowest.

[0096] As described above, by comparing the Examples and Comparative Examples, it can be seen that the combined use of (A1) and (A2) makes it easy to design the photocurable composition to have a high biomass degree, and also makes it possible to prepare a photocurable composition that is resistant to scratches when formed into a cured film.

Claims

1. epoxidized vegetable oil (meth)acrylate (A1); Glycerin poly(meth)acrylate or a derivative thereof (A2), A photopolymerization initiator (B); 1. A photocurable composition comprising:

2. The photocurable composition according to claim 1 , The photocurable composition, wherein the derivative contains a poly(meth)acrylate formed by reaction of a hydroxy group in a glycerin poly(meth)acrylate with an isocyanate group in a polyisocyanate.

3. The photocurable composition according to claim 1 or 2, The content of (A1) in the composition is a １ The content of (A2) in the composition is a ２ , then a ２ / a １ The photocurable composition according to claim 1, wherein the mass ratio of

4. The photocurable composition according to claim 1 or 2, The (A2) is a photocurable composition containing glycerin poly(meth)acrylate or a derivative thereof synthesized using biologically derived glycerin as a raw material.

5. The photocurable composition according to claim 1 or 2, The (A2) is a photocurable composition containing at least one selected from the group consisting of glycerin di(meth)acrylate, glycerin tri(meth)acrylate, and a tetrafunctional glycerin poly(meth)acrylate obtained by reacting glycerin di(meth)acrylate with 1,5-pentamethylene diisocyanate in a molar ratio of 2:

1.

6. The photocurable composition according to claim 1 or 2, The (A1) is a photocurable composition containing epoxidized soybean oil (meth)acrylate.

7. The photocurable composition according to claim 1 or 2, The (B) is a photocurable composition containing a photopolymerization initiator (B1) that satisfies the following [light absorption characteristics]. [Light absorption characteristics] A solution of the photopolymerization initiator (B1) dissolved in acetonitrile at a concentration of 0.1% by mass is placed in a cell having an optical path length of 1 cm, and the absorbance (Abs) of light at a wavelength of 380 nm is measured. ３８０ is 0.3 or more.

8. The photocurable composition according to claim 1 or 2, The (B) is a photocurable composition containing an acylphosphine compound.

9. The photocurable composition according to claim 1 or 2, A photocurable composition comprising a polymerizable monomer (A3) which does not fall under either (A1) or (A2).

10. The photocurable composition according to claim 1 or 2, A photocurable composition, wherein the total ratio of the (A1) and the (A2) in all polymerizable components in the composition is 40 mass% or more.

11. The photocurable composition according to claim 1 or 2, A photocurable composition having a biomass ratio of 10% or more.

12. The photocurable composition according to claim 1 or 2, The photocurable composition further comprises a pigment.

13. A cured product of the photocurable composition according to claim 1 or 2.

14. An article comprising the cured product of claim 13.

15. A film forming step of forming a film on a substrate using the photocurable composition according to claim 1 or 2; a light irradiation step of irradiating the film with light; A method for manufacturing an article, comprising:

16. A method for producing the article of claim 15, comprising the steps of: The method for manufacturing an article, wherein the light is ultraviolet light.

17. A method for producing the article of claim 15, comprising the steps of: In the light irradiation step, the film is irradiated with ultraviolet light emitted from an ultraviolet light emitting diode.

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