KR20200140295A - Curable resin composition - Google Patents

Abstract

The resulting cured product not only has good abrasion resistance and scratch resistance, and high surface hardness, but also provides a curable resin composition having low tackiness after drying of the coating film (excellent in tack-free property). Further, a cured product having good abrasion resistance and scratch resistance, and high surface hardness obtained from the curable resin composition is provided. The curable resin composition of the present invention is a curable resin composition comprising a thermoplastic resin (A) and a resin (B) having 5 or more (meth)acryloyl groups, and the content of the thermoplastic resin (A) is the number of the curable resin composition. It is characterized in that it is 42% by weight or more with respect to the total amount of the stake.

Description

Curable resin composition

The present invention relates to a curable resin composition and a cured product thereof. This application claims the priority of Japanese Patent Application No. 2018-066687 for which it applied to Japan on March 30, 2018, and uses the content here.

Thermoplastic resins, such as acrylic resins, polycarbonate resins, ABS resins, urethane resins, and polyethylene, are widely used as coating agents from the viewpoint of easy molding due to their light weight and excellent impact resistance and transparency. However, the molded articles of these thermoplastic resins have problems such as easily scratching due to friction or the like, their transparency is lowered, or their appearance is damaged. Therefore, attempts have been made to apply a surface coating to the molded article to improve abrasion resistance, scratch resistance, and surface hardness. For example, Patent Document 1 describes a technique for imparting abrasion resistance and scratch resistance to a cured product thereof by blending a thermoplastic resin with a compound having a specific (meth)acryloyl group.

Japanese Patent Application Publication No. 2010-43150

However, a coating film (uncured product) obtained by applying and drying the composition described in Patent Literature 1 to a substrate has a problem that the surface thereof is sticky, that is, adhesiveness occurs.

Compositions with low adhesiveness are, for example, that the coating film is difficult to be destroyed even when hands or objects come into contact with the coating film after drying, even when the coating films are overlapped, they are not adhered, and cured after a certain period of time. There is an advantage in that no dust adheres to the surface, such as unnecessary lamination, and an advantage of excellent workability. Further, for example, even when the composition is used as a printing layer, there is an advantage in that it is possible to form a coating film overlaid, and finally, it is possible to collectively cure by irradiation or heating of an active energy ray. For this reason, it can be said that it is an important characteristic that the adhesiveness after drying of a coating film is low (excellent adhesiveness-free property).

Accordingly, an object of the present invention is to provide a curable resin composition in which the obtained cured product not only has good abrasion resistance and scratch resistance, and high surface hardness, but also has low tackiness after drying of the coating film (excellent in tack-free property). Further, it is to provide a cured product having good abrasion resistance and abrasion resistance, and high surface hardness obtained from the curable resin composition.

The inventors of the present invention, as a result of careful examination in order to achieve the above object, showed that a curable resin composition containing at least a specific amount of a thermoplastic resin and a resin having 5 or more (meth)acryloyl groups has low adhesiveness after drying of the coating film, and curing The present invention was completed by finding out that it gives a useful cured product.

That is, the present invention is a curable resin composition comprising a thermoplastic resin (A) and a resin (B) having 5 or more (meth)acryloyl groups,

There is provided a curable resin composition wherein the content of the thermoplastic resin (A) is 42% by weight or more with respect to the total amount of the resin content of the curable resin composition.

Further, it is preferable that the glass transition temperature of the thermoplastic resin (A) is 60 to 140°C.

Further, it is preferable that the thermoplastic resin (A) is an acrylic resin and/or a polyester resin.

Further, the acrylic resin preferably contains at least an alkyl (meth)acrylate as a monomer unit.

Moreover, it is preferable that the said alkyl (meth)acrylate is methyl (meth)acrylate.

Moreover, it is preferable that the said resin (B) which has 5 or more (meth)acryloyl groups contains dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

Moreover, it is preferable that the curable resin composition of this invention is used as a coating agent.

In addition, in the present invention, a cured product of the curable resin composition is also provided.

Further, in the present invention, a coating layer which is the cured product is also provided.

In the curable resin composition of the present invention, the obtained cured product not only has good abrasion resistance and scratch resistance, and high surface hardness, but also has low adhesiveness after drying the coating film. Further, the cured product of the curable resin composition has good wear resistance and scratch resistance, and high surface hardness.

The curable resin composition of the present invention contains a thermoplastic resin (A) and a resin (B) having 5 or more (meth)acryloyl groups, and the content of the thermoplastic resin (A) is based on the total amount of the resin content of the curable resin composition. , It is characterized in that 42% by weight or more. Moreover, the curable resin composition of this invention may contain a photoinitiator (C) and a volatile solvent (D) other than the said resin. In addition, examples of the resin powder include thermoplastic resin (A), resin (B) having 5 or more (meth)acryloyl groups, and other resins described later, but are not limited thereto.

[Thermoplastic resin (A)]

The thermoplastic resin (A) is not particularly limited as long as it is a resin polymer softened by heating. The glass transition temperature of the thermoplastic resin (A) is not particularly limited, but the lower limit thereof is preferably -120°C, more preferably 60°C, more preferably 100°C, and the upper limit is, for example It is preferably 200°C, more preferably 140°C, and still more preferably 110°C. When the lower limit is in the above range, there is a tendency for excellent adhesion-free properties after drying the coating film. Moreover, when the upper limit is in the above range, there is a tendency for excellent handling of the curable resin composition. In addition, the glass transition temperature was measured by a differential scanning calorimeter (DSC) method.

The weight average molecular weight of the thermoplastic resin (A) is not particularly limited, but the lower limit thereof is, for example, preferably 1000, more preferably 5000, still more preferably 10000. In addition, the upper limit is preferably 250000, more preferably 140000, and still more preferably 130000, for example. When the lower limit is in the above range, there is a tendency for excellent adhesion to the substrate. When the upper limit is in the above range, the surface hardness of the cured product tends to be excellent. In addition, the weight average molecular weight is a standard substance measured as polystyrene by a gel permeation chromatography (GPC) method.

Although it does not specifically limit as a thermoplastic resin (A), For example, polyethylene, polypropylene, polyvinyl chloride, polystyrene, AS resin, ABS resin, polyethylene terephthalate, acrylic resin, polyvinyl alcohol, polyvinylidene chloride, polycarbo Nate resin, urethane resin, and polyester resin are mentioned, Among them, acrylic resin and polyester resin are preferable from the viewpoint of non-adhesiveness. However, the thermoplastic resin (A) does not include those corresponding to the resin (B) having 5 or more (meth)acryloyl groups described later. Although the thermoplastic resin (A) may have a photo or thermosetting group (for example, a (meth)acryloyl group, a vinyl group, an epoxy group, a glycidyl group, or an oxetanyl group), it is preferable not to have it. When using the curable resin composition of the present invention as a coating agent, the thermoplastic resin (A) can be appropriately selected and used depending on the adhesion to the substrate. Moreover, these may be used individually by 1 type, and may be used in combination of 2 or more types.

The acrylic resin means a resin mainly containing a (meth)acrylic acid ester as a monomer unit. As an acrylic resin, for example, [1] a resin containing only one type of (meth)acrylic acid ester as a monomer unit (ie, a homopolymer of (meth)acrylic acid ester), and [2] two or more types of (meth) as monomer units A resin containing an acrylic acid ester (ie, a copolymer of two or more (meth)acrylic acid esters), [3] As a monomer unit, a resin containing a (meth)acrylic acid ester and a monomer other than (meth)acrylic acid ester (( Copolymers of monomers other than meth)acrylic acid ester and (meth)acrylic acid ester) are mentioned. In addition, (meth)acrylic acid ester means acrylic acid ester and/or methacrylic acid ester.

In the present invention, the thermoplastic resin (A) preferably contains an acrylic resin from the viewpoint of improving the adhesion to the substrate, and more preferably an acrylic resin containing an alkyl (meth)acrylate as a monomer unit. The ratio of the alkyl (meth)acrylate in the acrylic resin is preferably 30% by weight or more (for example, 30 to 99.9% by weight), more preferably 60% by weight or more with respect to the total amount of the monomer units of the acrylic resin. , More preferably 80% by weight or more, and most preferably 95% by weight or more.

Although it does not specifically limit as (meth)acrylate alkyl ester, For example, (meth)acrylate alkyl ester which has a C1-C20 linear or branched alkyl group is mentioned. As an alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, Isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth) ) Octyl acrylate, (meth) acrylate 2-ethylhexyl (2-ethylhexyl (meth) acrylate), (meth) acrylate isooctyl, (meth) acrylate, isononyl (meth) acrylate, (meth) acrylate , Isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, (Meth)acrylic acid C _1-20 alkyl esters such as heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate [preferably (meth)acrylic acid C _{1- 14} alkyl ester, more preferably (meth)acrylic acid C _1-10 alkyl ester] is mentioned. Among these, methyl (meth)acrylate is most preferred. These may be used alone or in combination of two or more.

Examples of (meth)acrylic acid esters other than the (meth)acrylate alkyl esters include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate having alicyclic hydrocarbon groups ( Meth)acrylic acid ester; (Meth)acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth)acrylate; The (meth)acrylic acid ester obtained from the terpene compound derivative alcohol is mentioned. These may be used singly or in combination of two or more.

As described above, the acrylic resin may contain a monomer other than the (meth)acrylic acid ester (hereinafter, simply referred to as “another monomer component”) as needed for the purpose of modification such as surface hardness.

Examples of the other monomer components include carboxyl group-containing monomers such as (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid; Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, (meth)acrylate ) Hydroxyl group-containing monomers such as hydroxyalkyl (meth)acrylates such as hydroxylauryl acrylate and (4-hydroxymethylcyclohexyl)methylmethacrylate; Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; Olefinic monomers such as ethylene, butadiene, isoprene, and isobutylene; Vinyl ether-based monomers such as methyl vinyl ether and ethyl vinyl ether; And aromatic vinyl monomers such as vinyl toluene and styrene. These may be used singly or in combination of two or more.

As the thermoplastic resin (A), a commercial item can be used, and for example, a product name "Paraloid A-21" (acrylic resin (a homopolymer of methyl methacrylate), manufactured by Dow Chemical) can be mentioned.

The content of the thermoplastic resin (A) relative to the total amount of the resin content of the curable resin composition is not particularly limited as long as it is 42% by weight or more, but is more preferably 44 to 95% by weight, particularly preferably 47 to 90% by weight, most preferably It is preferably 48 to 80% by weight. When the thermoplastic resin (A) is in the above range, the adhesion to the substrate is improved, and the adhesion after drying the coating film tends to be improved.

The content of the thermoplastic resin (A) relative to the total amount of the nonvolatile matter in the curable resin composition is not particularly limited, but, for example, 42% by weight or more is preferable, more preferably 44 to 95% by weight, particularly preferably 47 to 90 % By weight, most preferably 48 to 80% by weight. When the thermoplastic resin (A) is in the above range, the adhesion to the substrate is improved, and the adhesion after drying the coating film tends to be improved.

[Resin (B) having 5 or more (meth)acryloyl groups]

Although it does not specifically limit as resin (B) which has 5 or more (meth)acryloyl groups, For example, dipentaerythritol penta (meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol penta Having 5 or more (meth)acryloyl groups such as (meth)acrylate, tripentaerythritol hexa (meth)acrylate, tripentaerythritol hepta (meth)acrylate and tripentaerythritol octa (meth)acrylate Low molecular weight (e.g., 200 to 800 molecular weight) compounds, silicone (meth)acrylates having 5 or more (meth)acryloyl groups, and urethane (meth)acrylates having 5 or more (meth)acryloyl groups. have. These may be used singly or in combination of two or more.

As a silicone (meth)acrylate having 5 or more (meth)acryloyl groups, for example, 5 or more (meth)acryloyl groups and organosiloxane units [-Si(-R) ₂ -O-] (R is organic A group is shown.). The silicone (meth)acrylate may be a silicone (meth)acrylate having an average number of (meth)acryloyl groups of 5 or more. The above-described R is not particularly limited as long as it is an organic group, and examples thereof include a C _1-6 alkyl group and a C _1-6 alkoxy group. The Si atom (or organosiloxane unit) in one molecule of the silicon (meth)acrylate is, for example, 1 to 30, preferably 1 to 20, and more preferably 1 to 15. The number of (meth)acryloyl groups in the silicone (meth)acrylate (or the average number of (meth)acryloyl groups) is not particularly limited as long as it is 5 or more, but for example 5 to 20, preferably 5 to 15, more preferably 5 to 10.

Here, the "average number of (meth)acryloyl groups" can be defined as an average value of the number of (meth)acryloyl groups per molecule of silicone (meth)acrylate. For example, a mixture of a dialkyldialkoxysilane or a polymer thereof and an alkoxysilane having two (meth)acryloyl groups and an alkoxysilane having three (meth)acryloyl groups (molar ratio is 1:1) is reacted. The average number of (meth)acryloyl groups in the obtained silicone (meth)acrylate is 5.

Further, the silicone (meth)acrylate may be a mixture of two or more of the same or different average number of functional groups. The average number of functional groups in the mixture can also be determined by weighted average. For example, in the case of a mixture of 0.6 moles of silicone (meth)acrylate having an average number of functional groups of 4 and 0.4 moles of silicone (meth)acrylate having an average number of functional groups of 6, the average number of functional groups of the silicone (meth)acrylate is: It can be calculated according to the equation, and it becomes 4.8.

(4×0.6+6×0.4)/(0.6+0.4)=4.8

The urethane (meth)acrylate having 5 or more (meth)acryloyl groups specifically refers to a urethane (meth)acrylate having an average number of (meth)acryloyl groups 5 or more. The urethane (meth)acrylate may be, for example, one obtained by reacting a polyol (X), a polyisocyanate (Y), and a hydroxy group-containing (meth)acrylate (Z) (that is, a reactant thereof).

Here, the "average number of (meth)acryloyl groups" is an average value of the number of (meth)acryloyl groups per molecule of urethane (meth)acrylate. For example, 1 mole of diol (X1) as polyol (X), 2 moles of diisocyanate (Y1) as polyisocyanate (Y), and one hydroxyl group as a hydroxy group-containing (meth)acrylate (Z) and one ( Average of urethane (meth)acrylate obtained by reacting 1 mol of a compound (Z1) having a meth)acryloyl group and 1 mol of a compound (Z2) having one hydroxyl group and three (meth)acryloyl groups (meth) ) The number of acryloyl groups is 4 (the structure of the obtained urethane (meth)acrylate is schematically shown below).

(Z1)-(Y1)-(X1)-(Y1)-(Z2)

For example, a mixture of 1 mole of 1,3-butanediol, 2 moles of 1,6-hexanediisocyanate, 1 mole of 2-hydroxyethyl (meth)acrylate and 1 mole of pentaerythritol tri(meth)acrylate The above is the case where the reaction is made. In addition, the molar ratio of the monomer is 1:2:1:1.

Further, the urethane (meth)acrylate may be a mixture of two or more of the same or different average number of functional groups. The average number of functional groups in the mixture can also be determined by weighted average. For example, in the case of a mixture of 0.4 mol of urethane (meth)acrylate having an average number of functional groups of 2 and 0.6 mol of urethane (meth)acrylate having an average number of functional groups of 4, the average number of functional groups of urethane (meth)acrylate is: It can be calculated according to the equation, and it becomes 3.2.

(2×0.4+4×0.6)/(0.4+0.6)=3.2

Polyol (X) is a compound having two or more hydroxy groups in a molecule. However, it is assumed that the compound corresponding to the hydroxy group-containing (meth)acrylate (Z) is not contained in the polyol (X). Moreover, polyol (X) may be used individually by 1 type, and may be used in combination of 2 or more types.

As the polyol (X), a compound having two or more hydroxy groups in the molecule may be known or commonly used, and although not particularly limited, for example, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 1,3 -Butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, polyoxyC _2-4 alkylene glycol (polyethylene glycol, polypropylene glycol, poly Oxytetramethylene glycol, etc.), polyesterdiol, polyetherdiol, polycarbonate diol, bisphenol A and its alkylene oxide adduct, bisphenol F and its alkylene oxide adduct, hydrogenated bisphenol A and its alkylene oxide addition Diols such as sieve, hydrogenated bisphenol F and alkylene oxide adducts thereof, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, isosorbide, and xylene glycol; Glycerin, 1,1,1-tris(hydroxymethyl)propane, D-sorbitol, xylitol, D-mannitol, D-mannite, diglycerin, polyglycerin, trimethylolethane, trimethylolpropane, pentaerythritol , Polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, epoxy polyols, natural oil polyols, silicone polyols, fluorine polyols, polyolefin polyols, and other polyols having three or more hydroxyl groups in the molecule.

Commercially available products can be used as the polyol (X). For example, the product name ``TCD alcohol DM'' (Tricyclodecane dimethanol, manufactured by Oxea Corporation), the product name ``Isosorbide'' (Isosorbide, manufactured by Toei Chemical), and the product name `` PEG-400" (polyethylene glycol having a number average molecular weight of 400, manufactured by Sanyo Kasei Kogyo Corporation) is mentioned.

Polyisocyanate (Y) is a compound having two or more isocyanate groups in a molecule. Further, as a raw material for urethane (meth)acrylate, polyisocyanate (Y) may be used singly or in combination of two or more.

As polyisocyanate (Y), for example, aromatic isocyanates, aliphatic isocyanates, cyclic aliphatic isocyanates, alicyclic isocyanates, mixtures thereof, adducts of the isocyanates, modified products of the isocyanates, polymers of the isocyanates, etc. Isocyanates which have been made are mentioned. More specifically, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H12MDI), polyphenylmethane isocyanate compound (crude MDI), modified diphenyl Methane diisocyanate (modified MDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H-XDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI) and norbornene diisocyanate (NDI) are mentioned.

As the polyisocyanate (Y), a commercial item can be used, and for example, the product name ``Smidur N3300'' (a nurate compound derived from 1,6-hexamethylene diisocyanate, manufactured by Sumitomo Bayer Urethane), and the product name ``VESTANAT IPDI'' (isophorone) Diisocyanate, the product made by Evonik) can be mentioned.

The hydroxy group-containing (meth)acrylate (Z) is a compound having at least one hydroxy group in the molecule and at least one (meth)acryloyl group in the molecule. In addition, as a raw material for urethane (meth)acrylate, the hydroxyl group-containing (meth)acrylate (Z) may be used singly or in combination of two or more.

As a hydroxy group-containing (meth)acrylate (Z), for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2- Monofunctional (meth)acrylate compounds having a hydroxyl group such as hydroxy-3-methoxypropyl (meth)acrylate and these lactone adducts (caprolactone adducts, etc.); Pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, these lactone adducts (caprolactone And polyfunctional (meth)acrylate compounds having a hydroxyl group such as adducts and the like). The hydroxy group-containing (meth)acrylate (Z) may be used singly or in combination of two or more.

As the hydroxy group-containing (meth)acrylate (Z), commercially available products can be used. For example, the product name "BHEA" (2-hydroxyethyl acrylate, manufactured by Nippon Shokubai Co., Ltd.), and the product name "CHDMA" (cyclohexanedimethanol monoacrylic) Rate, Nippon Kasei Co., Ltd.), and a product name "PETRA" (a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, Allnex company make).

As the resin (B) having 5 or more (meth)acryloyl groups, from the viewpoint of abrasion resistance, scratch resistance and surface hardness of the cured product, a low molecular weight having 5 or more (meth)acryloyl groups (for example, a molecular weight of 200 to 800 ) Compounds are preferred, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate are more preferred, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) ) It is particularly preferred to include an acrylate at the same time.

As the resin (B) having 5 or more (meth)acryloyl groups, when simultaneously containing dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, the ratio thereof is not particularly limited. However, for example, the content of dipentaerythritol penta (meth)acrylate relative to the total amount of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate is 1 to 90% by weight It is preferably, more preferably 5 to 80% by weight, still more preferably 8 to 60% by weight, particularly preferably 10 to 50% by weight. When the content of dipentaerythritol penta (meth)acrylate is in the above range, the abrasion resistance, scratch resistance, and surface hardness of the resulting cured product are improved, and the adhesion after drying of the coating film tends to be improved.

As the resin (B) having 5 or more (meth)acryloyl groups, commercially available products can be used, for example, the product name ``KAYATAD DPHA'' (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Nippon Gaya Cousa), the product name "Aronix M-403" (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, the ratio (content) of dipentaerythritol pentaacrylate is 50 to 60% by weight) , Product name "Aronix M-400" (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, the ratio (content) of dipentaerythritol pentaacrylate is 40 to 50% by weight), product name " Aaronix M-402" (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, the ratio (content) of dipentaerythritol pentaacrylate is 30 to 40% by weight), the product name "Aronix M -404" (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, the ratio (content) of dipentaerythritol pentaacrylate is 30 to 40% by weight), product name "Aronix M-406" (The mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, the ratio (content) of dipentaerythritol pentaacrylate is 25 to 35% by weight), product name "Aronix M-405" (Dipenta Product names such as a mixture of erythritol pentaacrylate and dipentaerythritol hexaacrylate and the ratio (content) of dipentaerythritol pentaacrylate is 10 to 20% by weight), etc. Product name "DPHA" (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Allnex), product name "Evecryl (Evecryl) 1360" (silicone hexaacrylate, manufactured by Allnex), product name "KRM8452" (an aliphatic urethane acrylate having a number of functional groups ((meth)acryloyl group) of 10, manufactured by Daicel Allnex Corporation), and the like.

Although the content of the resin (B) having 5 or more (meth)acryloyl groups relative to the total amount of the resin content of the curable resin composition is not particularly limited, it is preferably 58% by weight or less, and more preferably 5 to 56% by weight. %, particularly preferably 10 to 53% by weight, most preferably 20 to 52% by weight. When the resin (B) having 5 or more (meth)acryloyl groups is in the above range, the abrasion resistance, abrasion resistance, and surface hardness of the resulting cured product are improved, and the adhesion after drying the coating film tends to be improved.

The content of the resin (B) having 5 or more (meth)acryloyl groups relative to the total amount of nonvolatile matter of the curable resin composition is not particularly limited, but is preferably 58% by weight or less, and more preferably 5 to 56% by weight. %, particularly preferably 10 to 53% by weight, most preferably 20 to 52% by weight. When the resin (B) having 5 or more (meth)acryloyl groups is in the above range, the abrasion resistance, abrasion resistance, and surface hardness of the resulting cured product are improved, and the adhesion after drying the coating film tends to be improved.

In the curable resin composition, the content of the resin (B) having 5 or more (meth)acryloyl groups relative to the total amount of the thermoplastic resin (A) is, for example, preferably 45 to 90% by weight, more preferably It is 50 to 80% by weight, more preferably 55 to 75% by weight. When the resin (B) having 5 or more (meth)acryloyl groups is in the above range, the abrasion resistance, abrasion resistance, and surface hardness of the resulting cured product are improved, and the adhesion after drying the coating film tends to be improved.

[Photopolymerization initiator (C)]

As a photoinitiator (C), for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl) )-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy) -Phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4 -Benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlor thioxanthone, 2-methyl thioxanthone, 2,4-dimethyl tea Oxanthone, isopropyl thioxanthone, 2,4-dichloro thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine Pin oxide, methylphenyl glyoxylate, benzyl, campoquinone, and the like. These may be used singly or in combination of two or more.

As the photoinitiator (C), a commercial item can be used, and for example, the product name "IRGACURE184" (1-hydroxycyclohexylphenyl ketone, manufactured by BASF) can be mentioned.

The content of the photopolymerization initiator (C) relative to the total amount of the resin content of the curable resin composition is not particularly limited, but, for example, 0.01 to 10% by weight is preferable, more preferably 0.1 to 8% by weight, even more preferably 0.5 to It is 5% by weight.

[Volatile solvent (D)]

The volatile solvent (D) is not particularly limited as long as it is a solvent that volatilizes when a curable resin composition is applied to a substrate and dried. For example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ether Compounds (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (benzene, etc.), halogenated hydrocarbons (dichloromethane, dichloroethane, etc.), esters Compounds (ethyl acetate, etc.), alcohols (ethanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, amides (dimethylformamide, dimethylacetamide, etc.) ). These may be used singly or in combination of two or more.

When the curable resin composition of the present invention contains a solvent, the concentration of the total amount of the resin powder contained in the curable resin composition is, for example, about 10 to 80% by weight, preferably 20 to 70% by weight, particularly preferably It is preferably used in the range of 30 to 60% by weight. By using within the above range, since the viscosity of the curable resin composition exhibits an appropriate value, there is a tendency that it becomes possible to form a coat layer having a desired film thickness.

[Other resin]

The curable resin composition of the present invention may contain resins other than the thermoplastic resin (A) and the resin (B) having 5 or more (meth)acryloyl groups (sometimes referred to as "other resins"). Examples of other resins include resins having 4 or less (meth)acryloyl groups, but the content of other resins relative to the total amount of the resin content of the curable resin composition is preferably, for example, 30% by weight or less. It is preferably 10% by weight or less, more preferably 5% by weight or less, particularly preferably 1% by weight or less, and most preferably 0% by weight (substantially not included).

Examples of the resin having 4 or less (meth)acryloyl groups include compounds having one (meth)acryloyl group, compounds having 2 to 4 (meth)acryloyl groups, and the like. As a compound having one (meth)acryloyl group, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylic (Meth)acrylic acid ester having a linear or branched hydrocarbon group such as rate; (Meth)acrylic acid ester having an alicyclic hydrocarbon group such as cyclohexyl (meth)acrylate; (Meth)acrylic acid ester having an aromatic hydrocarbon group such as benzyl (meth)acrylate; Glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-oxyranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyl Acrylic acid esters having an epoxy group in a molecule, such as oxypropyl (meth)acrylate, glycidyloxyphenyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate, are mentioned. Examples of the compound having 2 to 4 (meth)acryloyl groups include 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate are mentioned.

[additive]

In addition to the above-described components, the curable resin composition of the present invention includes a leveling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a crystal nucleating agent, a flame retardant, a flame retardant auxiliary agent, a filler, an impact resistance improving agent, a reinforcing agent, a dispersant, an antistatic agent, a foaming agent , An additive such as an antibacterial agent or a colorant may be further included. The content (mixing amount) of these additives is not particularly limited, and can be appropriately set from the amount usually used in the curable resin composition.

<hardener>

The curable resin composition of the present invention can be cured by advancing the polymerization reaction of the resin (B) having 5 or more (meth)acryloyl groups, and thereby a cured product can be formed. The method of curing can be appropriately selected from a known method, and is not particularly limited, but an active energy ray irradiation is mentioned, for example. As the active energy ray, for example, infrared ray, visible ray, ultraviolet ray, X ray, electron ray, α ray, β ray, γ ray, or the like may be used. Among them, ultraviolet rays are preferred from the viewpoint of excellent handling properties.

Conditions when curing the curable resin composition of the present invention by irradiation with active energy rays (irradiation conditions with active energy rays, etc.) can be appropriately adjusted according to the type and energy of the active energy rays to be irradiated, the shape or size of the cured product, etc. Although not limited, in the case of irradiating ultraviolet rays, it is preferably about 1 to 1000 mJ/cm 2, for example. In addition, for the irradiation of the active energy ray, for example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser, or the like can be used. After irradiation of the active energy ray, further heat treatment (annealing, aging) can be performed to further advance the curing reaction.

The curable resin composition of the present invention can be obtained as a coat layer by applying and drying on a substrate to prepare a coating film, and curing the coating film. That is, the curable resin composition of the present invention can be used as a coating agent (coating agent composition).

Although it does not specifically limit as a base material, For example, a plastic base material, a metal base material, a ceramics base material, a semiconductor base material, a glass base material, a paper base material, a wooden base material (wood base material), a base material which is a coating surface, etc. can be used. Can be, and is not particularly limited.

The method of application is not particularly limited, and can be carried out using known or commonly used means such as airless spray, air spray, roll coat, bar coat, gravure coat, and die coat.

The drying temperature of the coating film is preferably 30 to 150°C, more preferably 50 to 120°C, and more preferably 60 to 100°C, for example. The drying time is preferably 0.1 to 10 minutes, more preferably 0.3 to 5 minutes, and more preferably 0.5 to 2 minutes, for example.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited at all by these examples.

(Example 1)

400 parts by weight of Paraloid A-21, 100 parts by weight of Aaronix M-402, and 750 parts by weight of methyl ethyl ketone were mixed, and stirring was continued at 60° C. until the paraloid A-21 was dissolved. To the obtained solution, 6 parts by weight of IRGACURE184 was added to prepare a curable resin composition.

(Examples 2 to 5, Comparative Example 1)

A curable resin composition was prepared in the same manner as in Example 1, except that the compounding amount described in the table was used.

(Examples 6 to 10)

A curable resin composition was prepared in the same manner as in Example 1, except that the components described in the table were blended in a specific amount.

[Assessment Methods]

The base material for evaluation test was produced using the curable resin composition obtained in Examples and Comparative Examples, and based on the measurement method shown below, pencil hardness and the non-adhesive evaluation after coating film drying were performed, and it shows in Table 1.

(Pencil hardness)

The curable resin composition obtained in Examples and Comparative Examples was applied to a PET substrate and dried (temperature: 80° C., time: 10 minutes) so that the cured coating film had a thickness of 10 μm, followed by UV irradiation (high pressure mercury lamp). , 2 kW, line speed: 6 m/min, irradiation frequency: once, accumulated light amount: 224 mJ/cm 2 ), and a substrate for test evaluation having a cured coating film on the surface was prepared. A PET base material having a cured coating film was used on the surface obtained by the above operation, and the pencil hardness was measured according to JIS K-5600, except that the load was 500 g, and judged as follows.

HB or higher: ○

Less than HB: ×

(Tack-free (1)-touch)

The curable resin composition obtained in Examples and Comparative Examples was applied to a substrate made of PET so that the coating film thickness after drying was 10 µm, and the inner temperature was allowed to stand in an oven heated at 80° C. for 1 minute to prepare a test piece. The tag on the surface of the coating film of the test piece was evaluated by the touch, and judged as follows.

No tag: ○

With tag: ×

(No-adhesion (2)-bonding between coated surfaces)

The curable resin composition obtained in Examples and Comparative Examples was applied to a substrate made of PET so that the coating film thickness after drying was 10 µm, and the inner temperature was allowed to stand in an oven heated at 80° C. for 1 minute to prepare a test piece. It peeled after the applied surfaces of the test piece were butted against each other, and the presence or absence of a coating film defect caused by transfer of one coating film to the other was visually observed, and judged as follows.

No film defect: ○

There is a film defect: ×

Hereinafter, details of the components used in Examples and Comparative Examples will be described.

[Thermoplastic resin (A)]

A-21: Product name "Paraloid A-21", acrylic resin (methyl methacrylate homopolymer), weight average molecular weight 120000, glass transition temperature 105°C

[Resin (B) having 5 or more (meth)acryloyl groups]

M-402: Product name "Aronix M-402", a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (the ratio (content) of dipentaerythritol pentaacrylate is 30 to 40% by weight)

M-400: Product name "Aronix M-400", a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (the ratio (content) of dipentaerythritol pentaacrylate is 40 to 50% by weight)

M-405: Product name "Aronix M-405", a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (the ratio (content) of dipentaerythritol pentaacrylate is 10 to 20% by weight)

KRM8452: Product name "KRM8452", aliphatic urethane acrylate having 10 functional groups (average (meth)acryloyl groups)

EB1360: Product name "Ebecryl 1360", silicone hexaacrylate (average number of (meth)acryloyl groups 6)

[Initiator (C)]

IRG184: Product name "IRGACURE184", 1-hydroxycyclohexylphenylketone

[Solvent (D)]

MEK: methyl ethyl ketone, limited express, manufactured by Wako Junyaku High School

As the above summary, the configuration of the present invention and variations thereof are added below.

[One]

It is a curable resin composition comprising a thermoplastic resin (A) and a resin (B) having 5 or more (meth)acryloyl groups,

A curable resin composition, wherein the content of the thermoplastic resin (A) is 42% by weight or more with respect to the total amount of the resin content of the curable resin composition.

[2]

The curable resin composition according to [1], wherein the lower limit of the glass transition temperature of the thermoplastic resin (A) is -120°C, 60°C, or 100°C, and the upper limit is 200°C, 140°C, or 110°C.

[3]

The curable resin composition according to [1] or [2], wherein the lower limit of the weight average molecular weight of the thermoplastic resin (A) is 1000, 5000, or 10000, and the upper limit is 250000, 140000, or 130000.

[4]

Thermoplastic resin (A) is polyethylene, polypropylene, polyvinyl chloride, polystyrene, AS resin, ABS resin, polyethylene terephthalate, acrylic resin, polyvinyl alcohol, polyvinylidene chloride, polycarbonate resin, urethane resin and polyester The curable resin composition according to any one of [1] to [3], which is at least one selected from the group consisting of resins.

[5]

The curable resin composition according to any one of [1] to [4], wherein the thermoplastic resin (A) is an acrylic resin and/or a polyester resin.

[6]

The curable resin composition according to any one of [1] to [5], wherein the thermoplastic resin (A) is an acrylic resin, and the acrylic resin contains at least an alkyl (meth)acrylate as a monomer unit.

[7]

The curable resin composition according to any one of [1] to [6], wherein the alkyl (meth)acrylate ester is methyl (meth)acrylate.

[8]

[1] to [7], wherein the content of the thermoplastic resin (A) relative to the total amount of the resin content of the curable resin composition is 42% by weight or more, 44 to 95% by weight, 47 to 90% by weight, or 48 to 80% by weight The curable resin composition according to any one.

[9]

In [1] to [8], wherein the content of the thermoplastic resin (A) relative to the total amount of the nonvolatile matter of the curable resin composition is 42% by weight or more, 44 to 95% by weight, 47 to 90% by weight, or 48 to 80% by weight The curable resin composition according to any one.

[10]

Resin (B) having 5 or more (meth)acryloyl groups is dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripenta Low molecular weight having 5 or more (meth)acryloyl groups such as erythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and tripentaerythritol octa (meth) acrylate (e.g., 200 to 800) compound, a silicone (meth)acrylate having 5 or more (meth)acryloyl groups, and at least one selected from the group consisting of urethane (meth)acrylate having 5 or more (meth)acryloyl groups The curable resin composition according to any one of [1] to [9].

[11]

The resin (B) having 5 or more (meth)acryloyl groups described in any of [1] to [10] containing dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate Curable resin composition.

[12]

As a resin (B) having 5 or more (meth)acryloyl groups, when dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are simultaneously included, dipentaerythritol penta (meth) ) The content of dipentaerythritol penta (meth)acrylate relative to the total amount of acrylate and dipentaerythritol hexa(meth)acrylate is 1 to 90% by weight, 5 to 80% by weight, 8 to 60% by weight Or the curable resin composition in any one of [1]-[11] which is 10-50 weight%.

[13]

The content of the resin (B) having 5 or more (meth)acryloyl groups relative to the total amount of the resin content of the curable resin composition is 58% by weight or less, 5 to 56% by weight, 10 to 53% by weight, or 20 to 52% by weight The curable resin composition according to any one of phosphorus [1] to [12].

[14]

The content of the resin (B) having 5 or more (meth)acryloyl groups relative to the total amount of the nonvolatile matter of the curable resin composition is 58% by weight or less, 5 to 56% by weight, 10 to 53% by weight, or 20 to 52% by weight The curable resin composition according to any one of phosphorus [1] to [13].

[15]

The content of the resin (B) having 5 or more (meth)acryloyl groups relative to the total amount of the thermoplastic resin (A) in the curable resin composition is 45 to 90% by weight, 50 to 80% by weight, or 55 to 75% by weight The curable resin composition in any one of [1] to [14] which is %.

[16]

The curable resin according to any one of [1] to [15], wherein the content of the photopolymerization initiator (C) relative to the total amount of the resin content of the curable resin composition is 0.01 to 10% by weight, 0.1 to 8% by weight, or 0.5 to 5% by weight. Composition.

[17]

The curable resin composition according to any one of [1] to [16] used as a coating agent.

[18]

A cured product of the curable resin composition according to any one of [1] to [17].

[19]

A coating layer which is a cured product according to [18].

In the curable resin composition of the present invention, the obtained cured product not only has good abrasion resistance and scratch resistance, and high surface hardness, but also has low adhesion after drying the coating film. Further, the cured product of the curable resin composition has good abrasion resistance and scratch resistance, and high surface hardness.

Claims (9)

It is a curable resin composition comprising a thermoplastic resin (A) and a resin (B) having 5 or more (meth)acryloyl groups,
The content of the thermoplastic resin (A) is 42% by weight or more with respect to the total amount of the resin content of the curable resin composition. The curable resin composition according to claim 1, wherein the thermoplastic resin (A) has a glass transition temperature of 60 to 140°C. The curable resin composition according to claim 1 or 2, wherein the thermoplastic resin (A) is an acrylic resin and/or a polyester resin. The curable resin composition according to claim 3, wherein the thermoplastic resin (A) is an acrylic resin, and the acrylic resin contains at least an alkyl (meth)acrylate as a monomer unit. The curable resin composition according to claim 4, wherein the alkyl (meth)acrylate ester is methyl (meth)acrylate. The resin (B) having 5 or more (meth)acryloyl groups according to any one of claims 1 to 5 is dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Curable resin composition comprising a. The curable resin composition according to any one of claims 1 to 6, which is used as a coating agent. A cured product of the curable resin composition according to any one of claims 1 to 7. A coating layer which is a cured product according to claim 8.