Photocurable resin composition

Abstract

To provide a photocurable resin composition which suppresses glossiness when coated onto a base material, is extremely reduced in damage when brought into contact with chemicals, and is excellent in bendability.SOLUTION: A photocurable resin composition contains polyfunctional (meth)acrylate (A), surface-treated talc particles (B), a leveling agent (C) and a photopolymerization initiator (D), and uses a polyfunctional (meth)acrylate monomer (a1) and / or a polyfunctional (meth)acrylate oligomer (a2) as the polyfunctional (meth)acrylate (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photocurable resin composition. [Background technology]

[0002] In general, photocurable resin compositions can be cured in a short time and are very easy to handle, so they are widely used in electronic and electrical parts, printing, painting, and other applications.

[0003] Previously, the applicant invented a photocurable resin composition that possesses hardness, extensibility, and solvent resistance. Specifically, the applicant obtained a photocurable resin composition characterized by containing a urethane acrylate with a polyester main chain and a monofunctional acrylate having an aromatic ring, and containing either a monofunctional acrylate or a monofunctional acrylamide having a bulky functional group (Patent Document 1). Because the composition possesses hardness and extensibility as well as excellent solvent resistance, it has properties that make it suitable for sealing, bonding, and filling mechanical parts that require deformation. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-077069 Summary of the Invention [Problem to be solved by the invention]

[0005] Conventionally, flooring materials have been generally provided in which a photocurable resin composition is applied to a substrate such as a vinyl chloride resin. In particular, photocurable resin compositions do not contain solvents and do not require a drying process, making it possible to mass-produce inexpensive flooring materials in a short period of time.

[0006] In recent years, to simplify the manufacturing and application processes, a method has been adopted in which a photocurable resin composition is applied to a substrate on-line using a die coater, immediately cured, wound up on a roll and stored, and then cut off the required amount when needed for application on site. However, the photocurable resin composition described in Patent Document 1 has relatively high hardness and strength, so there is a possibility that cracks or whitening may occur during winding.

[0007] In addition, since the photocurable resin composition constitutes the surface layer of the flooring material, it is necessary to suppress gloss due to reflection of sunlight, etc. Furthermore, there is a strong demand for improved durability against chemicals, etc., and there is room for improvement.

[0008] The problem to be solved by the present invention is to provide a photocurable resin composition which, when applied to a substrate, exhibits reduced gloss, is extremely resistant to damage when contacted with chemicals, and has excellent flexibility. [Means for solving the problem]

[0009] The present invention is a photocurable resin composition comprising a polyfunctional (meth)acrylate (A), surface-treated talc particles (B), a leveling agent (C), and a photopolymerization initiator (D). [Effects of the Invention]

[0010] The photocurable resin composition of the present invention has the advantages of suppressing gloss when applied to a substrate, being extremely resistant to damage when in contact with chemicals, and having excellent flexibility. DETAILED DESCRIPTION OF THE INVENTION

[0011] <Multifunctional (meth)acrylate> In the present invention, a polyfunctional (meth)acrylate (A) is used. Examples of the (A) component include a polyfunctional (meth)acrylate monomer (a1) and a polyfunctional (meth)acrylate oligomer (a2). Either the (a1) component or the (a2) component may be used alone, or they may be used in combination. The (A) component is the main component of the photocurable resin composition of the present invention, and it is necessary to use a bifunctional or higher functional component to increase reactivity.

[0012] Specific examples of the component (a1) include bifunctional acrylates such as (poly)ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 4,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5 pentanediol diacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dimethyloltricyclodecane diacrylate, and dicyclopentanyl diacrylate.

[0013] Furthermore, examples of trifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, tris(2-acryloxyethyl)isocyanurate, and ε-caprolactone-modified tris(2-acryloxyethyl)isocyanurate.

[0014] Furthermore, examples of tetrafunctional (meth)acrylates include trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and alkyl-modified dipentaerythritol tetra(meth)acrylate; examples of pentafunctional (meth)acrylates include dipentaerythritol penta(meth)acrylate and alkyl-modified dipentaerythritol penta(meth)acrylate; and examples of hexafunctional (meth)acrylates include dipentaerythritol hexa(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate.

[0015] Specific examples of the component (a2) include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, as well as (meth)acrylate oligomers having a polyether skeleton, (meth)acrylate oligomers having a polybutadiene skeleton, (meth)acrylate oligomers having a polyester skeleton, etc. Among these, it is preferable to use urethane (meth)acrylate oligomers.

[0016] The number average molecular weight of the component (a2) is preferably 1,000 to 30,000, more preferably 1,200 to 20,000, and particularly preferably 1,500 to 10,000.

[0017] Commercially available products of the component (a2) include SUA-008 (trade name, manufactured by Asia Industries Co., Ltd., polyether skeleton, bifunctional), SUA-023 (trade name, manufactured by Asia Industries Co., Ltd., polyether skeleton, bifunctional), and RUA-074 (trade name, manufactured by Asia Industries Co., Ltd., polyester skeleton, bifunctional).

[0018] In the present invention, surface-treated talc particles (B) are used. The component (B) can be obtained, for example, by surface-treating talc particles with an organic or inorganic substance. In particular, in the present invention, it is preferable to use talc particles treated with a silane coupling agent, which are talc particles surface-treated with a silane coupling agent.

[0019] Conventionally, calcium carbonate particles and the like have been used to improve durability against chemicals, etc., but in such cases, the intensity of gloss when sunlight, etc. is reflected has been an issue. Therefore, a method has been seen in which untreated silica particles or surface-treated silica particles are used to suppress gloss, but according to tests by the present inventors, these tend to lack durability against chemicals, etc., and damage caused by high-concentration alkaline aqueous solutions in particular has been observed, leaving room for improvement.

[0020] Therefore, the inventors of the present invention discovered that by using component (B), gloss is suppressed when applied to a substrate, damage when contacted with chemicals is extremely small, and flexibility is also excellent, leading to the completion of the present invention. Although the detailed reaction mechanism is unknown, it is believed that component (B) in the photocurable resin composition exerts a certain action and effect.

[0021] The average particle size of the component (B), as measured by a laser method, is preferably 0.1 to 100 μm, more preferably 0.3 to 50 μm, and particularly preferably 0.5 to 20 μm.

[0022] The blending ratio of the (B) component is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 80 parts by weight, and particularly preferably 1 to 50 parts by weight, per 100 parts by weight of the (A) component.

[0023] Commercially available products of the component (B) include Talc FH104S (trade name, manufactured by Fuji Talc Industries Co., Ltd., talc particles treated with an epoxy-based silane coupling agent, average particle size: 4 μm) and P-4 (trade name, manufactured by Nippon Talc Co., Ltd., talc particles treated with an epoxy-based silane coupling agent, average particle size: 5 μm).

[0024] <Leveling agent> In the present invention, a leveling agent (C) is used. Component (C) can improve the smoothness of the coating surface when applied to a substrate. Therefore, by using component (C), the occurrence of unevenness on the coating surface is suppressed, which has the effect of suppressing the adhesion of contaminants and making it easy to wipe off any contaminants that do occur.

[0025] Component (C) is preferably a silicone-based component to further improve smoothness. It also preferably contains a functional group with an unsaturated bond in its structure, such as an acrylic group or a vinyl group. Of these, an acrylic group is particularly preferred.

[0026] Furthermore, the component (C) is preferably polyether- or polyester-modified, and in particular, by incorporating such a modified material, the above-mentioned effects tend to be further improved.

[0027] The blending ratio of the (C) component is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight, and particularly preferably 0.1 to 10 parts by weight, per 100 parts by weight of the (A) component.

[0028] Commercially available products of the component (C) include BYK-UV3500 (trade name, manufactured by BYK-Chemie, polyether-modified polydimethylsiloxane having an acrylic group), BYK-UV3505 (trade name, manufactured by BYK-Chemie, modified polydimethylsiloxane having an acrylic group), and BYK-UV3570 (trade name, manufactured by BYK-Chemie, polyester-modified polydimethylsiloxane having an acrylic group).

[0029] <Photopolymerization initiator> In the present invention, a photopolymerization initiator (D) is used. Specific examples of the component (D) include, but are not limited to, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0030] The blending ratio of the component (D) is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight, per 100 parts by weight of the component (A). Blending within this range tends to enable efficient polymerization of the photocurable resin composition of the present invention.

[0031] Commercially available products containing component (D) include Omnirad 127, Omnirad 184, Omnirad 369, Omnirad 500, Omnirad 754, Omnirad 819, Omnirad 907, Omnirad 1173, Omnirad 2959, Omnirad TPO, Omnirad MBF (trade names, all of which are iGM). RESINS), Irgacure OXE01, Irgacure OXE02, Irgacure OXE04 (product names, all manufactured by BASF Japan), DAIDO UV-CURE PMB, DAIDO UV-CURE OMB, DAIDO UV-CURE BMS, DAIDO UV-CURE 171, DAIDO UV-CURE D-177F, DAIDO UV-CURE #174, PHOTOCURE 550 (trade name, all manufactured by Daido Chemical Industry Co., Ltd.).

[0032] <Other ingredients> In the present invention, in addition to the above components (A) to (D), other components can be blended within a range that does not impair the effects of the present invention.

[0033] In the present invention, for example, a monofunctional (meth)acrylate monomer having a caprolactone skeleton can be used. The use of this component tends to improve adhesion when applied to a substrate. The blending ratio of this component can be, for example, about 0.1 to 20 parts by weight per 100 parts by weight of the component (A). Commercially available products of this component include Aronix M-5300 (trade name, manufactured by Toagosei Co., Ltd., ω-carboxy-polycaprolactone monoacrylate) and Placcel FA1 (trade name, manufactured by Daicel Corporation, unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone).

[0034] In the present invention, for example, a monofunctional (meth)acrylate monomer having an alkyl group can be used. This component acts as a diluent, and therefore tends to improve workability during application. Specific examples of this component include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate. The blending ratio of this component can be, for example, about 1 to 1,000 parts by weight per 100 parts by weight of the above-mentioned component (A).

[0035] Furthermore, various additives can be added to the photocurable resin composition of the present invention within the range that does not impair the effects of the present invention.

[0036] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but these are given as specific examples and are not intended to limit the scope of the present invention. [Example]

[0037] Photocurable resin compositions of Examples and Comparative Examples were obtained by preparing mixtures according to the formulations shown in Table 1. The numerical values ​​in Table 1 represent parts by weight. The raw materials used are listed below. Miramer M340 (trade name, manufactured by MIWON, pentaerythritol triacrylate) SUA-023 (trade name, manufactured by Asia Kogyo Co., Ltd., polyether-based urethane acrylate, bifunctional, weight-average molecular weight: 2,700) Talc FH104S (product name, manufactured by Fuji Talc Industries Co., Ltd., talc particles treated with an epoxy-based silane coupling agent, average particle size: 4 μm) P-4 (trade name, manufactured by Nippon Talc Co., Ltd., talc particles treated with an epoxy-based silane coupling agent, average particle size: 5 μm) Talc FH104 (trade name, manufactured by Fuji Talc Industries Co., Ltd., untreated talc particles, average particle size: 4 μm) No. 30 (product name, manufactured by Mizusawa Industrial Chemicals, silica particles treated with a methacrylic silane coupling agent, average particle size: 4 μm) MIZUKASIL P-73 (product name, manufactured by Mizusawa Industrial Chemicals, untreated silica particles, average particle size: 4 μm) ACEMATT OK607 (trade name, manufactured by Evonik, polyethylene-treated silica particles, average particle size: 4 μm) ACEMATT 3600 (trade name, manufactured by Evonik, polyethylene-treated silica particles, average particle size: 5 μm) CERAFLOUR 970 (product name, BYK, polypropylene wax) Super SS (product name, manufactured by Maruo Calcium Co., Ltd., untreated calcium carbonate particles, average particle size: 4 μm) BYK-UV3570 (product name, manufactured by BYK Chemie, polyester-modified polydimethylsiloxane with acrylic groups) DAIDO UV-CURE #174 (Product name, manufactured by Daido Kasei Kogyo Co., Ltd.) Aronix M-5300 (trade name, manufactured by Toagosei Co., Ltd., ω-carboxy-polycaprolactone monoacrylate) 2-EHA (Mitsubishi Chemical Corporation, 2-ethylhexyl acrylate)

[0038] [Table 1]

[0039] Test specimens were prepared using the photocurable resin compositions obtained in the above examples and the like in the following manner, and the physical properties were evaluated. The results are shown in Table 2.

[0040] <Preparation of test specimen> A vinyl chloride resin sheet (product name: Style Floor Y110-S, manufactured by Fuso Gosei Co., Ltd., thickness: 1.8 mm) was used as a substrate, and the photocurable resin composition was applied to a film thickness of 15 μm. An electrode high-pressure mercury lamp (product name: iGrandage ECS4011GX / N, manufactured by iGraphics Co., Ltd.) was used to apply the composition to the film at an irradiation intensity of 100 mW / cm. 2 , cumulative light intensity 800mJ / cm 2 The composition was cured by irradiating it with ultraviolet light at 1000 kJ / cm 3 ... to prepare a test specimen.

[0041] <Glossiness> The 60° gloss of the test specimen was measured in accordance with JIS Z 8741 using a Micro Trigloss (manufactured by Byck-Gardner Co.).

[0042] <Flexibility> The test specimen was wrapped around a mandrel rod (6 mm diameter), pressed for 5 seconds, and then returned to its original position, and the coating film was visually inspected for cracks or whitening. ◯: No cracks or whitening were observed in the coating film. ×: Cracks or whitening were observed in the coating film.

[0043] <Chemical resistance> Eight drops of sodium hydroxide solution of various concentrations were soaked into a 1cm square piece of cloth, which was then placed on the test piece and left to stand at room temperature for 24 hours, after which any changes in the coating were observed. ○: Almost no damage is visible to the naked eye, and the surface appearance is not impaired. △: Damage was visually confirmed in some areas, and the appearance of the surface was partially impaired. ×: Damage was visually confirmed throughout the entire surface, and the appearance of the surface was significantly impaired.

[0044] [Table 2]

Claims

1. A photocurable resin composition comprising a polyfunctional (meth)acrylate (A), talc particles treated with an epoxy-based silane coupling agent (B), a leveling agent (C), and a photopolymerization initiator (D).

2. 2. The photocurable resin composition according to claim 1, wherein the leveling agent (C) is a silicone-based leveling agent.

3. 3. The photocurable resin composition according to claim 1, which is used as a flooring material.

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