JP6481302B2 - Curable resin composition, cured product and laminate - Google Patents

Description

  The present invention relates to a curable resin composition, a cured product obtained by curing the resin composition, and a laminate using the cured product.

  Optical film is generally used as a protective film for optical parts. To prevent scratches on the surface due to handling during production, and to prevent scratches caused by user use when used on the outermost surface. Therefore, a hard coat layer is provided on one side or both sides.

  For example, when a mobile phone such as a smartphone with a display on the front and a metal key are put together in a pocket, the metal key is rubbed against the surface of the display. Is mentioned. In order to prevent such scratches, the hard coat layer has recently been required to have particularly high scratch resistance and pencil hardness.

  Against this background, curable resin compositions have been developed. Patent Documents 1 and 2 describe a curable resin composition made of an organic material for use as a hard coat layer. Patent Documents 3 to 6 disclose organic-inorganic hybrid curable resin compositions using inorganic fillers typified by colloidal silica and dry silica fine particles as curable resin compositions with higher hardness. .

Japanese Patent No. 4003800 JP 2000-191710 A JP2013-108209A JP 2011-012145 A JP 2009-286972 A JP 2008-150484 A

In the case of forming a hard coat layer composed only of an organic substance described in Patent Documents 1 and 2 to increase the hardness, curling of the film on which the hard coat layer is formed due to large curing shrinkage or in an extreme case, the hard coat layer Cracks are likely to occur, and if the curing shrinkage is suppressed, sufficient hardness tends to be hardly exhibited.
Moreover, although the organic-inorganic hybrid type cured resin composition described in Patent Documents 3 to 6 uses an inorganic substance such as silica in order to increase the hardness, characteristics such as processability inherent in the resin are impaired. There is a problem of end.
For example, when a film is to be cut into a predetermined size, fine cracks are generated on the cut surface. This is because the coating film hardened using an inorganic material such as silica has properties close to those of glass.

  The present invention has been made in view of such a situation.

  As a result of intensive studies, the present inventors have found a resin composition that can solve the above problems. That is, the present invention is as follows.

1. Norbornane diisocyanate (a1) and urethane (meth) acrylate (A) and terminal (meth) acryloyl group which are reaction products of compound (a2) having one hydroxyl group and at least one (meth) acryloyl group in one molecule A curable resin composition containing a bifunctional (meth) acrylate monomer (B) having an ethoxy structure introduced therebetween, wherein the proportion of urethane (meth) acrylate (A) in the curable resin composition is cured 40 to 99 parts by mass with respect to 100 parts by mass of the resin composition, and the blending mass ratio of the urethane (meth) acrylate (A) and the (meth) acrylate monomer (B) is A: B = 75: 25 to 95. It was found that the above-mentioned problem was solved by using a curable resin composition that is: 5.

  2. The compound (a2) has one hydroxyl group and 3 to 5 (meth) acryloyl groups in one molecule. The curable resin composition described in 1.

3. The monomer (B) is a polyethylene glycol di (meth) acrylate or ethoxylated bisphenol A di (meth) acrylate, 1. Or 2. It is a resin composition as described in above.

  4). 1-10 mass parts of photoinitiators (C) are contained with respect to 100 mass parts of said resin compositions. ~ 3. The curable resin composition according to any one of the above.

  5. 0.1-100 mass parts of ultraviolet absorbers (D) are contained with respect to 100 mass parts of the resin composition. ~ 4. The curable resin composition according to any one of the above.

  6.1. ~ 5. A cured product obtained by irradiating the curable resin composition according to any one of the above with active energy rays.

  7). 5. The active energy ray is ultraviolet light. Is a cured product.

  8.6. Or 7. It is the laminated body obtained by shape | molding the hardened | cured material as described in on a base material.

  9. 7. The thickness of the cured product is 5 to 200 μm. It is a laminated body as described in above.

  10. 7. The base material is a thermoplastic resin. Or 9. It is a laminated body as described in above.

11. 11. The laminate according to 10, wherein the substrate is polycarbonate, polyethylene terephthalate, or polymethyl methacrylate.

  The laminated body obtained by irradiating an active energy ray, after apply | coating the curable resin composition as described in any one of 12.1-5 on a resin base material.

The curable resin composition of the present invention contains the following two components.
(A): urethane (meth) acrylate (B) which is a reaction product of norbornane diisocyanate (a1) and compound (a2) having one hydroxyl group and at least one (meth) acryloyl group in one molecule: terminal ( A polyfunctional (meth) acrylate monomer having an ethoxy structure introduced between (meth) acryloyl groups.

  The norbornane diisocyanate (a1) used in (A) is a compound having two isocyanate groups bonded to an alicyclic hydrocarbon having a bridge structure, and can be appropriately selected from commercially available products. Examples of such commercially available products include NBDI manufactured by Mitsui Chemicals.

Examples of the compound (a2) used in (A) having one hydroxyl group and at least one (meth) acryloyl group in one molecule include trimethylolpropane di (meth) acrylate and pentaerythritol tri (meth). And poly (meth) acrylates of polyvalent hydroxyl group-containing compounds such as acrylate and dipentaerythritol penta (meth) acrylate. In addition, adducts of these poly (meth) acrylates and ε-caprolactone, adducts of these poly (meth) acrylates and alkylene oxide, epoxy (meth) acrylates, and the like can also be used. These compounds (a2) can be used alone or in combination of two or more.
In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and the same applies to “(meth) acryloyl group” and “(meth) acrylic acid”.

  As the compound (a2), it is preferable to use a compound having 3 to 5 hydroxyl groups from the viewpoint of obtaining a high hardness layer (hard coat). Among them, pentaerythritol tri (meth) acrylate, dipentaerythritol penta It is more preferable to use (meth) acrylate.

  The urethane (meth) acrylate (A) used in the present invention can be obtained by nucleophilic addition reaction of the isocyanate group of the norbornane diisocyanate (a1) and the hydroxyl group of the acrylate compound (a2) having the hydroxyl group. The nucleophilic addition reaction can be performed by appropriately selecting from various known methods.

The use ratio of the compound (a2) in the addition reaction is preferably 0.1 to 50 equivalents as the hydroxyl group equivalent of the compound (a2) with respect to 1 equivalent of the isocyanate group of the norbornane diisocyanate (a1). The equivalent is more preferable, and 0.9 to 1.2 equivalent is more preferable.
Moreover, 30-150 degreeC is preferable and, as for the reaction temperature of the said norbornane diisocyanate (a1) and the said compound (a2), 50-100 degreeC is more preferable. In addition, the end point of reaction can be confirmed by calculating | requiring an isocyanate group content rate by the loss | disappearance of the infrared absorption spectrum of 2250cm < ^-1 > which shows an isocyanate group, or the method as described in JISK7301-1995, for example.
In the addition reaction, a catalyst can be used for the purpose of shortening the reaction time. Examples of the catalyst include basic catalysts (amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, phosphines such as tributylphosphine and triphenylphosphine) and acidic catalysts (copper naphthenate, naphthene). Metal alkoxides such as cobalt acid, zinc naphthenate, tributoxyaluminum, tetrabutoxytrititanium and tetrabutoxyzirconium, Lewis acids such as aluminum chloride, and tin compounds such as dibutyltin dilaurate and dibutyltin diacetate). Among these, acidic catalysts are preferable, and dibutyltin dilaurate which is a tin compound is most preferable.
As the usage-amount of the catalyst in the said addition reaction, it is preferable that it is 0.1-1 mass part normally with respect to 100 mass parts of norbornane diisocyanate (a1).

  In the addition reaction, if necessary, a solvent such as toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or a radical polymerizable monomer having no site that reacts with isocyanate, such as a hydroxyl group or A radically polymerizable monomer having no amino group may be used as a solvent. These solvents and monomers can be used alone or in combination of two or more.

  The ratio of the urethane (meth) acrylate (A) in the curable resin composition is 10 to 99 parts by weight, preferably 20 to 99 parts by weight, and more preferably 40 to 100 parts by weight with respect to 100 parts by weight of the curable resin composition. 99 parts by mass. If it is less than this ratio, the surface hardness becomes low when cured. On the other hand, if the amount is too large, cracks accompanying curing shrinkage and the like are likely to occur.

  The polyfunctional (meth) acrylate monomer (B) having an ethoxy structure introduced between terminal (meth) acryloyl groups used in the curable resin composition of the present invention has two (bifunctional) or more polymerizable functional groups. The polyfunctional (meth) acrylate monomer may be synthesized according to a known method such as a dehydration condensation reaction of (meth) acrylic acid with ethylene glycol and polyfunctional alcohol or phenol, or a commercially available product may be used. .

Examples of such bifunctional or higher functional (meth) acrylate monomers include polyethylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, ethoxy Glycerol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate , ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated ditrimethylolpropane tetra (meth) acrylate, And ethoxylated dipentaerythritol poly (meth) acrylate. These may be used alone or in combination.

As a commercial item, for example, polyethylene glycol 200 diacrylate (product name A-200) of Shin-Nakamura Chemical Co., Ltd., polyethylene glycol 200 dimethacrylate (product name 4G), polyethylene glycol 400 diacrylate (product name A-400), Polyethylene glycol 400 dimethacrylate (product name 9G), polyethylene glycol 600 diacrylate (product name A-600), polyethylene glycol 600 dimethacrylate (product name 14G), ethoxylated (3 mol) bisphenol A diacrylate (product name) A-BPE-3), ethoxylated (4 mol) bisphenol A diacrylate (product name A-BPE-4), ethoxylated (4 mol) bisphenol A dimethacrylate (product name BPE-200), ethoxylated 10 mol) bisphenol A diacrylate (product name A-BPE-10), ethoxylated (10 mol) bisphenol A dimethacrylate (product name BPE-500), ethoxylated (20 mol) bisphenol A diacrylate (product name A -BPE-20), ethoxylated (20 mol) bisphenol A dimethacrylate (product name BPE-900), ethoxylated (30 mol) bisphenol A diacrylate (product name A-BPE-30), ethoxylated (30 mol) ) Bisphenol A dimethacrylate (product name BPE-1300N), ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate (product name A-9300-1CL), ethoxylated (3 mol) glycerol triacrylate (product) Name A-GLY-3E), Et Silylated (3 mol) glycerin tri (meth) acrylate (product name GLY-3E), ethoxylated (9 mol) glycerin trimethacrylate (product name A-GLY-9E), ethoxylated (9 mol) glycerin trimethacrylate (Product name GLY-9E), ethoxylated (20 mol) glycerol triacrylate (product name A-GLY-20E), ethoxylated (20 mol) glycerin trimethacrylate (product name GLY-20E), ethoxylated (3 mol) ) Trimethylolpropane triacrylate (product name A-TMPT-3EO), ethoxylated (3 mol) trimethylolpropane trimethacrylate (product name TMPT-3EO), ethoxylated (9 mol) trimethylolpropane triacrylate (A-) TMPT-9EO), ethoxylation (9 ) Trimethylolpropane trimethacrylate (TMPT-9EO), ethoxylated (20 mol) trimethylolpropane triacrylate (product name AT-20E), ethoxylated (30 mol) trimethylolpropane triacrylate (product name AT-30E) , Ethoxylated (4 mol) pentaerythritol tri and tetraacrylate (product name ATM-4EL), ethoxylated (4 mol) pentaerythritol tri and tetramethacrylate (product name TM-4EL), ethoxylated (8 mol) pentaerythritol Tri- and tetraacrylate (product name ATM-8EL), ethoxylated (4 mol) pentaerythritol tetraacrylate (product name ATM-4E), ethoxylated (4 mol) pentaerythritol tetramethacrylate (manufactured Name TM-4E), ethoxylated (35 mol) pentaerythritol tetraacrylate (ATM-35E), ethoxylated (35 mol) pentaerythritol tetramethacrylate (TM-35E), ethoxylated (4 mol) ditrimethylolpropane tetraacrylate (Product name AD-TMP-4E), ethoxylated (4 mol) ditrimethylolpropane tetramethacrylate (product name D-TMP-4E), ethoxylated (6) dipentaerythritol polyacrylate (product name A-DPH-6E) ), Ethoxylated (6) dipentaerythritol polymethacrylate (product name M-DPH-6E), ethoxylated (12) dipentaerythritol polyacrylate (product name A-DPH-12E), and ethoxylated (12) di Pentaerythritol And poly (meth) acrylate (product name: M-DPH-12E).
The proportion of the (meth) acrylate monomer (B) in the curable resin composition is 0.1 to 60 parts by mass, preferably 1 to 60 parts by mass with respect to 100 parts by mass of the curable resin composition. . If it is smaller than this ratio, the cured product becomes brittle. On the other hand, if it is large, the surface hardness of the cured product is lowered, which is not preferable.
The blending mass ratio of the urethane (meth) acrylate (A) and the (meth) acrylate monomer (B) is in the range of A: B = 40: 60 to 99: 1. A: B = 50: 50 to 95: 5 is preferable, and A: B = 75: 25 to 90:10 is more preferable. If B is larger than this range, the surface hardness tends to be low, and if B is small, cracks and cure shrinkage tend to increase.

In the curable resin composition of the present invention, it is preferable to use a photopolymerization initiator (C) in order to facilitate the effect of ultraviolet rays.
As a photoinitiator (C), if used in this industry, it will not specifically limit. For example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2, Examples include 4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, and the like. These can use 1 type (s) or 2 or more types.
The blending mass of the photopolymerization initiator (C) is in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the mixture of urethane (meth) acrylate (A) and (meth) acrylate monomer (B). Preferably, it is 1-7 mass parts, More preferably, it is 3-5 mass parts. When there is more C than this range, it will become easy to generate | occur | produce a crack in the case of hardening. Further, when C is less than this range, curing is insufficient.

In the curable resin composition of this invention, it is preferable to use an ultraviolet absorber (D) from a viewpoint of improving the weather resistance in outdoor use.
The ultraviolet absorber (D) is not particularly limited as long as it is used in the industry. Examples thereof include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and hydroxybenzoate-based ultraviolet absorbers. These can use 1 type (s) or 2 or more types.
Among these, at least one selected from the group consisting of triazine-based UV absorbers, benzophenone-based UV absorbers, and benzotriazole-based UV absorbers is preferable. Are preferably triazine-based ultraviolet absorbers.

  Examples of the triazine ultraviolet absorber include 2,4-bis [hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (2- Hydroxy-4-hydroxymethylphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hydroxymethylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxyethyl) phenyl] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxyethyl) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxyethoxy) pheny ] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [2-hydroxy-4- (3-hydroxypropyl) phenyl] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (3- Hydroxypropyl) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (3-hydroxypropoxy) phenyl] -4,6- Diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (3-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ -Hydroxy-4- (4-hydroxybutyl) phenyl] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (4-hydroxybutyl) phenyl] -4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (4-hydroxybutoxy) phenyl] -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- (4-hydroxybutoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hydroxy Methylphenyl) -4,6-bis (2-hydroxy-4-methylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxyethyl) phenyl] -4,6- Bi (2-hydroxy-4-methylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -4,6-bis (2-hydroxy-4-) Methylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (3-hydroxypropyl) phenyl] -4,6-bis (2-hydroxy-4-methylphenyl) -1,3 5-triazine, 2- [2-hydroxy-4- (3-hydroxypropoxy) phenyl] -4,6-bis (2-hydroxy-4-methylphenyl) -1,3,5-triazine, 2- [4 , 6-Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazine- 2-yl)- -[(Hexyl) oxy] -phenol, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and [(C10-C16, mainly C12-C13 alkyloxy) methyl Reaction product with oxirane, 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid Examples include reaction products with esters.

  Examples of the benzophenone-based ultraviolet absorber include 2,2 "-dihydroxy-4,4" -di (hydroxymethyl) benzophenone, 2,2 "-dihydroxy-4,4" -di (2-hydroxyethyl) benzophenone, 2,2 "-dihydroxy-3,3" -dimethoxy-5,5 "-di (hydroxymethyl) benzophenone, 2,2" -dihydroxy-3,3 "-dimethoxy-5,5" -di (2-hydroxy Ethyl) benzophenone, 2,2 "-dihydroxy-3,3" -di (hydroxymethyl) -5,5 "-dimethoxybenzophenone, 2,2" -dihydroxy-3,3 "-di (2-hydroxyethyl)- 5,5 "-dimethoxybenzophenone, 2,2-dihydroxy-4,4-dimethoxybenzophenone and the like can be mentioned.

  Examples of the benzotriazole ultraviolet absorber include 2- [2 ″ -hydroxy-5 ″-(hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2 ″ -hydroxy-5 ″-(2-hydroxyethyl). ) Phenyl] -2H-benzotriazole, 2- [2 "-hydroxy-5"-(3-hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2 "-hydroxy-3" -methyl-5 "- (Hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2 "-hydroxy-3" -methyl-5 "-(2-hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2" -hydroxy- 3 "-methyl-5"-(3-hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2 "-hydroxy-3 -T-butyl-5 "-(hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2" -hydroxy-3 "-t-butyl-5"-(2-hydroxyethyl) phenyl] -2H-benzo Triazole, 2- [2 "-hydroxy-3" -t-butyl-5 "-(2-hydroxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2" -hydroxy-3 "-t -Butyl-5 "-(3-hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2" -hydroxy-3 "-t-octyl-5"-(hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2 "-hydroxy-3" -t-octyl-5 "-(2-hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2" -hydroxy 3 "-t-octyl-5"-(3-hydroxypropyl) phenyl] -2H-benzotriazole or the like, or 2,2 "-methylenebis [6- (2H-benzotriazoly-2-yl) -4- (hydroxymethyl) ) Phenol], 2,2 '; -methylenebis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol], 2,2 "-methylenebis [6- (5-chloro-2H) -Benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol], 2,2 "-methylenebis [6- (5-bromo-2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) Phenol], 2,2 "-methylenebis [6- (2H-benzotriazoly-2-yl) -4- (3-hydroxypropyl) phenol], 2 , 2 "-methylenebis [6- (5-chloro-2H-benzotriazoli-2-yl) -4- (3-hydroxypropyl) phenol], 2,2" -methylenebis [6- (5-bromo-2H-benzotriazoli) -2-yl) -4- (3-hydroxypropyl) phenol], 2,2 "-methylenebis [6- (2H-benzotriazoly-2-yl) -4- (4-hydroxybutyl) phenol], 2,2 "-Methylenebis [6- (5-chloro-2H-benzotriazoly-2-yl) -4- (4-hydroxybutyl) phenol], 2,2" -methylenebis [6- (5-bromo-2H-benzotriazoly-2 -Yl) -4- (4-hydroxybutyl) phenol], 3,3- {2,2 "-bis [6- (2H-benzotriazoly-2-yl) -1-hydride Xyl-4- (2-hydroxyethyl) phenyl]} propane, 2,2- {2,2 "-bis [6- (2H-benzotriazoli-2-yl) -1-hydroxy-4- (2-hydroxyethyl) ) Phenyl]} butane, 2,2 "-oxybis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol], 2,2" -bis [6- (2H-benzotriazolyl-) 2-yl) -4- (2-hydroxyethyl) phenol] sulfide, 2,2 "-bis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol] sulfoxide, 2, 2 "-bis [6- (2H-benzotriazoly-2-yl) -4- (2-hydroxyethyl) phenol] sulfone, 2,2" -bis [6- (2H-benzotria Li-2-yl) -4- (2-hydroxyethyl) phenol] amine.

  Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3 ″ -diphenyl acrylate and ethyl-2-cyano-3,3 ″ -diphenyl acrylate.

Hydroxybenzoate UV absorbers include phenyl salicylate, 4-t-butylphenyl salicylate, 2,5-t-butyl-4-hydroxybenzoic acid n-hexadecyl ester, 2,4-di-t -Butylphenyl-3 ', 5-di-t-butyl-4'-hydroxybenzoate and the like.
The blending mass of the ultraviolet absorber (D) is 0.1 to 10 with respect to 100 parts by mass of the urethane (meth) acrylate (A), (meth) acrylate monomer (B), and photopolymerization initiator (C) mixture. Part by mass. Preferably it is 2-7 mass parts, More preferably, it is 3-5 mass parts. When the amount is more than this range, the photopolymerization initiating action of the photopolymerization initiator (C) is inhibited and curing is insufficient. If it is less than this range, yellowing is likely to occur due to sunlight or the like, particularly in outdoor use.

  The curable resin composition of the present invention contains an antioxidant, a light stabilizer, a leveling agent, a pigment, an inorganic filler, an organic filler, an organic solvent, etc., as long as the desired characteristics are not impaired. Can be made.

  The curable resin composition of the present invention includes the urethane (meth) acrylate (A), the (meth) acrylate monomer (B) and, if necessary, a photopolymerization initiator (C), an ultraviolet absorber (D) component and others. Are added at a predetermined composition ratio. When mixing, you may heat and mix as needed. Furthermore, it is preferable to add an organic solvent in order to lower the viscosity and improve the handleability. The organic solvent is not particularly limited as long as it has solubility and volatility, and examples thereof include ketones such as methyl ethyl ketone and methyl isobutyl ketone, and glycol ethers such as methoxypropanol and ethylene glycol monomethyl ether. Since C reacts with light, mixing is preferably performed in a light-shielding environment.

The hardened | cured material of this invention is created by irradiating the said curable resin composition by irradiating an active energy ray (an ultraviolet ray, an electron beam, etc.).
When the active energy rays are ultraviolet rays, for example, a high-pressure mercury lamp or a metal halide lamp can be used as an active energy ray supply source.
The irradiation energy of ultraviolet rays is preferably 100 to 2,000 mJ / cm ² .
When the active energy beam is an electron beam, for example, a scanning electron beam irradiation method, a curtain type electron beam irradiation method, or the like can be used as an active energy beam supply source.
The irradiation energy of the electron beam is preferably 10 to 200 kGy.

  The laminate of the present invention is prepared by applying the curable resin composition to a substrate and irradiating an active energy ray to cure the coating film.

  A thermoplastic resin is mentioned as a base material used for the laminated body of this invention. Examples thereof include plastic films made of polypropylene resin, polycarbonate resin, polyethylene resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polymethyl methacrylate resin, polystyrene resin, and the like. In particular, when transparency and rigidity are required, polyethylene terephthalate resin and polymethyl methacrylate resin are preferable, and when transparency and heat resistance are required, polycarbonate resin is preferable. The thickness is usually 10 to 500 μm, preferably 30 to 300 μm, more preferably 50 to 200 μm.

  The method for applying the curable resin composition of the present invention to the substrate is not particularly limited. For example, a gravure coating method, a reverse coating method, a die coating method, a bar coater method, a lip coating method, a blade coating method, a roll coating method, Examples thereof include a roll coating method, a knife coating method, a curtain coating method, a slot orifice method, a spray coating method, and an inkjet method.

  In the laminate of the present invention, the cured product layer obtained by curing the curable resin composition has a thickness of 5 to 200 μm, preferably 5 to 100 μm, more preferably 10 to 50 μm. If it is thinner than this, the surface hardness is difficult to develop, and if it is thicker than this, it is difficult to suppress the occurrence of cracks.

  EXAMPLES Hereinafter, the present invention will be described with specific examples and comparative examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, the part and% in an example are a mass part and the mass%, respectively.

Synthesis example 1
Synthesis of Urethane Acrylate (A) After drying the system in advance by flowing dry air into a five-necked flask equipped with a stirrer, thermometer, cooler, dropping funnel and dry air introduction tube, (a1) 100 parts by mass of norbornene diisocyanate, 561.2% by mass of pentaerythritol triacrylate and 271.2 parts by mass of a mixture of 44% by mass of pentaerythritol tetraacrylate as (a2), and 101.2 parts by mass of 2-butanone as a solvent were added at 60 ° C. Warmed to. Thereafter, 0.08 parts by mass of the polymerization catalyst dibutyltin dilaurate and 0.16 parts by mass of the polymerization inhibitor dibutylhydroxytoluene were added, and the liquid temperature was kept at 80 to 90 ° C. The consumption of isocyanate residues in the reaction product was confirmed by an infrared absorption spectrum using a Fourier transform infrared spectrophotometer, and 2 of urethane acrylate (A), which is an addition reaction product of pentaerythritol triacrylate and norbornane diisocyanate. -506.1 mass parts of butanone solutions (solid content concentration 80 mass%) were obtained.

Example 1
With respect to 125 parts by mass of the 2-butanone solution of urethane acrylate (A) obtained in Synthesis Example 1 (solid content concentration 80% by mass), ethoxylated (10 mol) bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 10 parts by mass of a trade name A-BPE-10) was added as a compound (B), and a photopolymerization initiator 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name TPO, manufactured by BASF) was further added. Mass part (The amount of (A) and (B) was 110 parts by mass when (A) and (B) were described and calculated for the total of 100 parts by mass of (A) and (B)) was mixed to obtain a curable composition.
This curable resin composition was applied to the surface of a 200 μm-thick polycarbonate film (trade name: FE-2000, manufactured by MGC Phil Sheet Co., Ltd.) using a bar coater and dried at 50 ° C. for 1 minute. This curable resin composition was applied, and the polycarbonate film was irradiated with ultraviolet rays using a high-pressure mercury lamp at an integrated light amount of 500 mJ / cm 2 to form a cured product having a thickness of 40 μm on the polycarbonate film surface. A good-appearance coating film with no cracks was formed.
The obtained hard coat film is cut into a 10 cm square, and the four corners are attached to a glass plate with a cellophane tape, and the surface pencil hardness is based on the provisions of JIS K 5600-5-4 (1999 edition). Measurements were made using a scratch tester. The surface pencil hardness was 8H.
The thickness of the cured product was 40 μm by cross-sectional observation. As shown in FIG. 1, no defect due to cracking of the cured product was observed.
Count # 0000, a super fine steel wool, was brought into contact with the surface of a cured product on a horizontally placed polycarbonate film (trade name: FE-2000 manufactured by MGC Phil Sheet Co., Ltd.) at a load of 100 gf / cm 2, 15 times. After reciprocating wear, the amount of change in haze value (cloudiness) before and after wear was determined. There were no scratches before and after the abrasion, and there was no change in the haze value.

Example 2
A curable resin composition was prepared in the same manner as in Example 1, and the polycarbonate film of Example 1 was changed to a polyethylene terephthalate film having a thickness of 250 μm (trade name Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.). And performed in the same manner. The pencil hardness was 9H, the thickness of the cured product was 15 μm, and the haze value was not changed.

Example 3
The acrylate monomer (B) in Example 1 was ethoxylated (8 mol) pentaerythritol tetraacrylate (product name EBECRYL-40, manufactured by Daicel Ornex Co., Ltd.), except that the amount was 10 parts by mass. went. The pencil hardness was 8H, the thickness of the cured product was 40 μm, and the haze value did not change.

Example 4
The curable resin composition prepared in Example 3 was applied to a 250 μm-thick polyethylene terephthalate film (trade name Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) in the same manner as in Example 2. The pencil hardness was 8H, the thickness of the cured product was 15 μm, and the haze value was not changed.

Comparative Example 1
Photopolymerization initiator 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name TPO, manufactured by BASF) for 125 parts by mass of urethane acrylate (A) 2-butanone solution (solid content concentration 80%) 5 parts by mass, that is, 5 parts by mass of photopolymerization initiator 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name TPO manufactured by BASF) was mixed with 100 parts by mass of hexafunctional urethane acrylate oligomer having a solid content. Then, a curable composition was obtained.

This curable resin composition was applied to the surface of a 200 μm-thick polycarbonate film (trade name: FE-2000, manufactured by MGC Phil Sheet Co., Ltd.) using a bar coater and dried at 50 ° C. for 1 minute. This curable resin composition was applied, and the polycarbonate film was irradiated with ultraviolet rays at an integrated light quantity of 500 mJ / cm 2 using a high-pressure mercury lamp to form a cured product on the polycarbonate film surface.
The evaluation was abandoned because cracks occurred in the cured product layer having a thickness of 40 μm on the film surface.

Comparative Example 2
The same procedure as in Example 1 was performed except that the acrylate monomer (B) in Example 1 was changed to 10 parts by mass as pentaerythritol tetraacrylate (trade name EBECRYL-180 manufactured by Daicel Ornex Co., Ltd.). However, since a crack occurred in the cured product layer on the film surface, the evaluation was abandoned.

Comparative Example 3
With reference to Patent Document 1, 250 parts by mass of glycidyl methacrylate (hereinafter referred to as “GMA”), 1.6 parts by mass of lauryl mercaptan, methyl isobutyl were added to a flask equipped with a stirrer, a gas introduction pipe, a cooling pipe, and a thermometer. While charging 1000 parts by weight of a ketone (hereinafter referred to as “MIBK”) and 7.5 parts by weight of 2,2′-azobisisobutyronitrile (hereinafter referred to as “AIBN”), stirring under a nitrogen stream, The temperature was raised to 90 ° C. over 1 hour and reacted at 90 ° C. for 1 hour.
Next, while stirring at 90 ° C., a mixed solution composed of 750 parts by mass of GMA, 4.4 parts by mass of lauryl mercaptan, and 22.5 parts by mass of AIBN was dropped over 2 hours, and then reacted at 100 ° C. for 3 hours. Thereafter, 10 parts by weight of AIBN was charged, and further reacted at 100 ° C. for 1 hour, then heated to 120 ° C. and reacted for 2 hours. Cool to 60 ° C., replace the nitrogen introduction tube with an air introduction tube, add 507 parts by mass of acrylic acid (hereinafter referred to as “AA”), 2 parts by mass of p-methoxyphenol, and 5.4 parts by mass of triphenylphosphine. After mixing, the reaction solution was bubbled with air, heated to 110 ° C., and reacted for 8 hours. Thereafter, 1.4 parts by mass of p-methoxyphenol was added, and after cooling to room temperature, MIBK was added so that the nonvolatile content was 50% by mass to obtain a polymer (MIBK solution having a nonvolatile content of 50% by mass).
74 parts by mass of this polymer solution, 42.5 parts by mass of the urethane acrylate solution obtained in Synthesis Example 1, 29 parts by mass of a pentaerythritol triacrylate / pentaerythritol tetraacrylate mixture (a mixture with a mass ratio of 75/25), silicon hexa Acryl (0.2 parts by mass of “EBECRYL 1360” manufactured by Daicel UCB Ltd.) and 3 parts by mass of a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone were uniformly mixed to obtain a curable resin composition.
When the obtained resin composition was applied onto a polycarbonate film (trade name FE-2000 manufactured by MGC Phil Sheet Co., Ltd.) in the same manner as in Example 1, the pencil hardness HB, the thickness of the cured product 40 μm, and the post-wool wear scratches were observed. And haze value increased by 0.5%.

Comparative Example 4
When the curable resin composition obtained in Comparative Example 2 was applied to a polyethylene terephthalate film having a thickness of 250 μm (trade name Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) in the same manner as in Example 2, the pencil hardness was 3H and the cured product was The thickness was 15 μm, slight scratches were generated after wearing the stee wool, and the haze value increased by 0.1%.

The results of these Examples, Comparative Examples and Reference Examples are summarized in Table 1.
Comparison between Examples 1 and 3 and Comparative Examples 1 and 2 shows that the curable resin composition of the present invention suppresses the generation of cracks due to curing shrinkage.
As a result of comparison between Examples 1 and 3 and Comparative Example 3 or comparison between Examples 2 and 4 and Comparative Example 4, the curable resin composition of the present invention has a hardness-improving effect as compared with the conventional description represented by Patent Document 6. It can be seen that the effect of imparting scratch resistance is great.

Claims (12)

  Norbornane diisocyanate (a1) and urethane (meth) acrylate (A) and terminal (meth) acryloyl group which are reaction products of compound (a2) having one hydroxyl group and at least one (meth) acryloyl group in one molecule A curable resin composition containing a bifunctional (meth) acrylate monomer (B) having an ethoxy structure introduced therebetween, wherein the proportion of urethane (meth) acrylate (A) in the curable resin composition is cured 40 to 99 parts by mass with respect to 100 parts by mass of the resin composition, and the blending mass ratio of the urethane (meth) acrylate (A) and the (meth) acrylate monomer (B) is A: B = 75: 25 to 95. : A curable resin composition which is 5.   The curable resin composition according to claim 1, wherein the compound (a2) has one hydroxyl group and 3 to 5 (meth) acryloyl groups in one molecule.   The curable resin composition according to claim 1 or 2, wherein the monomer (B) is polyethylene glycol di (meth) acrylate or ethoxylated bisphenol A di (meth) acrylate.   Furthermore, 1-10 mass parts of photoinitiators (C) are contained with respect to 100 mass parts of said resin compositions, The curable resin composition as described in any one of Claims 1-3.   Furthermore, 0.1-10 mass parts of ultraviolet absorbers (D) are contained with respect to 100 mass parts of said resin compositions, The curable resin composition as described in any one of Claims 1-4.   Hardened | cured material obtained by irradiating an active energy ray to the curable resin composition as described in any one of Claims 1-5.   The cured product according to claim 6, wherein the active energy rays are ultraviolet rays.   The laminated body obtained by shape | molding the hardened | cured material of Claim 6 or 7 on a base material.   The laminate according to claim 8, wherein the cured product has a thickness of 5 to 200 μm.   The laminate according to claim 8 or 9, wherein the substrate is a thermoplastic resin. The laminate according to claim 10, wherein the substrate is polycarbonate, polyethylene terephthalate or polymethyl methacrylate.   The laminated body obtained by irradiating an active energy ray after apply | coating the curable resin composition as described in any one of Claims 1-5 on a resin base material.