JP2019147951A - Active energy ray-curable composition and cured product thereof - Google Patents

Abstract

To provide an active energy ray-curable composition which gives a cured product excellent in scratch resistance, stretchability, and chemical resistance.SOLUTION: The active energy ray-curable composition contains an organic-inorganic composite filler obtained by reacting an inorganic oxide (A), a monomer (b) having one active hydrogen group and at least one (meth)acryloyl group, and a silicon alkoxide (a) having two or more C1-4 alkoxy groups. The weight ratio of (b) to (a) used for the reaction is 1:6-1:1.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable composition and a cured product thereof.

Active energy ray curable resins, coatings on various substrates, hard coat agents, adhesives, pressure-sensitive adhesives, sealants, inks, etc. are expected to be widely used, but the structure of compounds that meet various needs Adjustment of the composition of the composition for design and expected characteristics has not progressed sufficiently, which is a big problem. That is, physical properties such as toughness, extensibility, high hardness, and high adhesion, physical properties such as the speed of curing related to active energy ray curing, surface drying property and surface hardness after curing, scratch resistance, and curing shrinkage It is extremely difficult to balance with
In recent years, there has been an increase in the use of resin for interior materials due to the need for weight reduction of automobiles. In order to give a design to the interior material, a technique is used in which the resin is once stretched and molded by an in-mold method. The use of an active energy ray-curable resin is being considered for this material from the viewpoint of environmental load, but for the reasons described above, when targeting compatibility of stretchability, scratch resistance, and chemical resistance, the required high There is no satisfactory performance.

For this reason, a method of forming a hard coat layer mainly composed of active energy ray-curable resin containing high-hardness silica fine particles as a filler is known, but a sufficient amount is added because the stretchability of the layer decreases. There is a problem that it cannot be done and the scratch resistance is insufficient.
Therefore, a composition containing silyl acrylate modified silica for imparting scratch resistance is known (Patent Document 1). Furthermore, according to Patent Document 2, (A) an organic-inorganic composite obtained by hydrolytic condensation of a resin having an alkoxysilyl group and a (meth) acryloyl group, colloidal silica and / or silicate, and (B) an ultraviolet ray. An active energy ray-curable composition containing an absorber and / or (C) a light stabilizer is disclosed. This composition has (D) two or more (meth) acryloyl groups in the molecule ( It is described that (meth) acrylates may be included.
Patent Document 3 discloses ultraviolet curable silicone obtained by chemically modifying colloidal silica with a radical polymerizable silane compound or a hydrolyzate thereof, [(meth) acryloyloxyalkyl] isocyanurate having a specific structure, and one molecule. A wear-resistant coating-forming composition containing urethane poly (meth) acrylate having at least two (meth) acryloyloxy groups and having an alicyclic skeleton, and a photopolymerization initiator is described.

Japanese Patent No. 4750914 JP 2005-171216 A Japanese Patent No. 3747065

  A cured product of an active energy ray-curable resin composition containing conventional silica fine particles as a filler has a problem of insufficient scratch resistance, stretchability, and chemical resistance.

  Then, an object of this invention is to provide the active energy ray curable composition which gives the hardened | cured material which is excellent in abrasion resistance, stretchability, and chemical resistance.

  As a result of intensive studies, the present inventor has reached the present invention. That is, the present invention relates to a monomer (b) having an inorganic oxide (A), one active hydrogen group and at least one (meth) acryloyl group, and silicon having two or more alkoxy groups having 1 to 4 carbon atoms. An active energy ray-curable composition comprising an organic-inorganic composite filler obtained by reacting an alkoxide (a), wherein the weight ratio of (b) and (a) used in the reaction is 1: 6 to 1: 1. It is a thing.

  The cured product of the active energy ray-curable composition of the present invention has an effect of being excellent in scratch resistance, stretchability and chemical resistance.

The inorganic oxide (A) constituting the organic-inorganic composite filler (C) is not particularly limited, but oxides of silicon, aluminum, zirconium, titanium, zinc, lead, germanium, indium, tin, antimony and cerium, and the like Metal composite oxides are preferable, and specifically, silicon oxide (also referred to as silica), aluminum oxide (also referred to as alumina), silicon-aluminum composite oxide, zirconium oxide (also referred to as zirconia). And oxide of titanium (also referred to as titania), zinc oxide, tin oxide, antimony-doped tin oxide, indium-tin composite oxide (sometimes abbreviated as ITO), cerium oxide, and the like. Of these, silica is preferable.
The shape of the inorganic oxide is not particularly limited as long as it is a shape of a known filler used for coatings, but is in the form of particles (spherical particles, hollow particles, porous particles, amorphous particles, etc.), rod-like, fibrous and plate In particular, the particle shape is preferable, and the spherical shape is particularly preferable.
Among these, when the particulate inorganic oxide (hereinafter, the particulate inorganic oxide is referred to as metal oxide particle) is particulate silica, preferred are dry silica (fumed silica and the like) and wet silica. (Precipitation method silica, gel method silica, colloidal silica and the like).
When the inorganic oxide is inorganic oxide particles, the primary particle diameter is preferably 1 to 100 nm. When the primary particle diameter is less than 1 nm, the effect of improving scratch resistance and hardness is small, and when it is 100 nm or more, secondary aggregation tends to occur and transparency and the like are easily lost. Whether the inorganic oxide particles have undergone secondary aggregation can be confirmed by magnifying the inorganic oxide particles with an electron microscope or the like, and the primary particle size of the secondary aggregated inorganic oxide particles Can be obtained by calculating the number average particle diameter of primary particles projected on the enlarged photo by applying the enlarged photo to an image analyzer or the like, and when the inorganic oxide particles are not secondary aggregated, the inorganic oxide The primary particle diameter of the particles can be measured by a BET method, a dynamic light scattering method, a centrifugal sedimentation method, a laser scattering method, or the like.
Especially, colloidal silica is calculated | required by BET method among the particulate silica which is a preferable inorganic oxide particle.
These inorganic oxide particles can be obtained in a dry state and in a state dispersed in water or an organic solvent.
Of these, colloidal inorganic oxides dispersed in an organic solvent are preferably used as inorganic oxide particles in order to exhibit excellent transparency. Examples of the colloidal inorganic oxide dispersed in an organic solvent include an organic solvent having a hydroxyl group (hereinafter sometimes abbreviated as OH group) (such as methanol and isopropanol) and an organic solvent having a ketone group (methyl isobutyl ketone and methyl ethyl ketone). Etc.) is preferably used. These organosilica sols can also be obtained from the market, and as commercial products, IPA-ST (IPA-dispersed organosilica sol, manufactured by Nissan Chemical Co., Ltd.), MEK-ST (MEK-dispersed organosilica sol, manufactured by Nissan Chemical Co., Ltd.) and MIBK- ST (MIBK-dispersed organosilica sol, manufactured by Nissan Chemical Co., Ltd.). Moreover, the sol which substituted the organic solvent of these origano silica sols with the organic solvent (For example, propylene glycol monomethyl ether) which has another OH group can also be used.

  The organic-inorganic composite filler (C) contained in the active energy ray-curable composition of the present invention is a monomer having an inorganic oxide (A), one active hydrogen group, and at least one (meth) acryloyl group ( b) and an organic-inorganic composite filler obtained by reacting silicon alkoxide (a) having two or more alkoxy groups having 1 to 4 carbon atoms, and the weight of (b) and (a) used in the reaction An active energy ray-curable composition having a ratio of 1: 6 to 1: 1. It is.

  The number formed by condensation of silicon alkoxides (a) is 2 to 10, and preferably 2 to 5 from the viewpoint of stretchability.

In the present invention, “(meth) acryloyl” means methacryloyl or acryloyl.
In the present invention, “(meth) acryl” means methacryl or acryl.

The silicon alkoxide (a) having two or more alkoxy groups having 1 to 4 carbon atoms is a silicon alkoxide having two or more alkoxy groups having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Examples of the silicon alkoxide (a) include tetraethoxysilane (TEOS), tetramethoxysilane, and tetrapropoxysilane.
From the viewpoint of reactivity, tetraethoxysilane and tetramethoxysilane are preferable, and tetraethoxysilane is more preferable.

Examples of the active hydrogen group possessed by the monomer (b) having the one active hydrogen group and at least one (meth) acryloyl group include a hydroxyl group, an amino group, and a thiol group.
Among these, from the viewpoint of reactivity, a hydroxyl group and an amino group are preferable, and a hydroxyl group is more preferable.

  Among the monomers (b) having one active hydrogen group and at least one (meth) acryloyl group, the monomer (b1) having one hydroxyl group and at least one (meth) acryloyl group is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1,4-cyclo Xanthanimethanol monoacrylate, ε-caprolactam adduct of 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane And (meth) acrylates such as di (meth) acrylate and 2,2-bis (4-acryloxydiethoxyphenyl) propane.

  As the monomer (b2) having one amino group and at least one (meth) acryloyl group among the monomers (b) having one active hydrogen group and at least one (meth) acryloyl group, 2-aminoethyl (meth) acrylate, N-propylaminoethyl acrylate, N-ethylaminopropyl (meth) acrylate, N-phenylaminoethyl (meth) acrylate and (meth) acrylic acid N-cyclohexylaminoethyl and the like can be mentioned.

  Among the monomers (b) having one active hydrogen group and at least one (meth) acryloyl group, the monomer (b3) having one thiol group and at least one (meth) acryloyl group N- (2-mercaptoethyl) acrylamide, N- (2-mercapto-1-carboxyethyl) acrylamide, N- (2-mercaptoethyl) methacrylamide, N- (4-mercaptophenyl) acrylamide, N- (7 -Mercaptonaphthyl) acrylamide, maleic acid mono 2-mercaptoethylamide, 2- (meth) acrylic acid (meth) acrylate, 2-mercapto-1-carboxyethyl (meth) acrylate, and the like.

  Of the monomers (b) having one active hydrogen group and at least one (meth) acryloyl group, from the viewpoint of dispersibility and scratch resistance, preferably one hydroxyl group and at least one (meth) acryloyl group are used. Monomer (b1), more preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol Mono (meth) acrylate, ε-caprolactam adduct of 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol pentaacrylate, more preferred Ku is ε- caprolactam adduct of 2-hydroxyethyl (meth) acrylate and dipentaerythritol pentaacrylate.

The organic-inorganic composite filler (C) is obtained by reacting the inorganic oxide (A), the silicon alkoxide (a), and the monomer (b) having one active hydrogen group and at least one (meth) acryloyl group. Can be obtained.
The weight ratio of silicon alkoxide (a) and inorganic oxide (A) used in the reaction is preferably 3: 1 to 10: 1, more preferably 4: 1 to 8: 1.
The weight ratio of monomer (b) to silicon alkoxide (a) is preferably 1: 6 to 1: 1, more preferably 1: 5 to 1: 1.

  The weight ratio of the organic-inorganic composite filler (C) contained in the active energy ray-curable composition of the present invention is preferably 2% by weight based on the total of the active energy ray-curable composition from the viewpoint of scratch resistance and the like. It is 50% by weight, more preferably 5% by weight to 30% by weight.

The organic-inorganic composite filler (C) causes a coupling reaction between silicon alkoxy (a) having two or more alkoxy groups having 1 to 4 carbon atoms and a hydroxyl group present on the surface of the inorganic oxide (A), and further remains. The silicon alkoxide (a) is subjected to a dehydration condensation reaction with respect to the alkoxy group to be formed. Thereafter, the monomer (b) having one more active hydrogen group and at least one (meth) acryloyl group can be added.
For example, the silicon alkoxide (a) in the preferred ratio is dissolved in a colloidal silica sol in which colloidal silica having a primary particle diameter of 10 nm is dispersed in isopropyl alcohol at a concentration of 30% by weight. By stirring for 5 to 5 hours, a hydroxyl group present on the surface of the colloidal silica and the silicon alkoxide (a) undergo a coupling reaction to obtain a reaction product of the colloidal silica and the silicon alkoxide (a). Further, by adding the above-mentioned preferable proportion of the monomer (b) to the reaction product and stirring the reaction at 50 to 80 ° C. for 2 hours, the remaining alkoxide and the active hydrogen group of the monomer (b) are dehydrated and condensed. By doing so, an organic-inorganic composite filler (C) can be obtained. At this time, you may perform the process of distilling off the organic solvent used for reaction.
The organic-inorganic composite filler (C) is a reaction product of the inorganic oxide (A) and the monomer (b) with the silicon alkoxide (a) (the inorganic oxide (A) and the monomer (b) (Bonding via silicon alkoxide (a)) can be confirmed by analyzing the reaction product using TG-DTA and pyrolysis GC-MS.

  The active energy ray-curable composition of the present invention comprises a polyurethane (meth) acrylate (D), a radical polymerizable double bond-containing (meth) acrylic polymer (E), a polyester (meth) acrylate (F), and an epoxy (meth) ) It may contain at least one selected from the group consisting of acrylates (G). From the viewpoint of stretchability and scratch resistance of the curable composition, it is preferable to contain polyurethane (meth) acrylate (D).

  The polyurethane (meth) acrylate (D) that can be contained in the active energy ray-curable composition of the present invention is a monomer having at least one ethylenically unsaturated group and a urethane group, and an organic polyisocyanate. (C) A reactant obtained by reacting a polyhydric alcohol (d) and a (meth) acrylate (e) having a hydroxyl group by a known method (a method described in JP-A-2006-20489) is used. be able to.

Examples of the organic polyisocyanate (c) include aliphatic polyisocyanates having 4 to 20 carbon atoms (c1), alicyclic polyisocyanates having 6 to 17 carbon atoms (c2), and aromatic aliphatic polyisocyanates having 10 to 17 carbon atoms ( c3), aromatic polyisocyanate having 8 to 22 carbon atoms (c4) and the like.
Examples of the aliphatic polyisocyanate (c1) having 4 to 20 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Examples of the alicyclic polyisocyanate (c2) having 6 to 17 carbon atoms include isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene Examples include 1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.
Examples of the araliphatic polyisocyanate (c3) having 10 to 17 carbon atoms include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.
Examples of the aromatic polyisocyanate having 8 to 22 carbon atoms (c4) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4′- or 2,4. '-Diphenylmethane diisocyanate), 1,5-naphthalene diisocyanate, 4,4', 4 ''-triphenylmethane triisocyanate and the like. These may be used alone or in combination of two or more.

  Examples of the polyhydric alcohol (d) include an aliphatic polyhydric alcohol (d1) having 2 to 20 carbon atoms, an alicyclic polyhydric alcohol (d2) having 6 to 20 carbon atoms, and an araliphatic polyvalent having 8 to 16 carbon atoms. A monohydric alcohol (d3), an aromatic polyhydric alcohol (d4) having 6 to 15 carbon atoms, an alcohol (d5) in which an alkylene oxide having 2 to 8 carbon atoms is added to these alcohols in a block form and / or a random form, and the like. Can be mentioned.

  Examples of the aliphatic polyhydric alcohol (d1) having 2 to 20 carbon atoms include chain aliphatic dihydric alcohols having 2 to 12 carbon atoms [linear diol (ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, etc.) And branched diols (1,2-, 1,3- or 2,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-methyl-1,5-pentanediol and 3-methyl-1,5-pentanediol, etc.]], a C 4-20 tetrahydric alcohol [aliphatic polyol (pe Data erythritol, sorbitol, mannitol, sorbitan, diglycerol and dipentaerythritol), sugars (sucrose, glucose, mannose, fructose, methyl glucoside and derivatives thereof)], and the like.

Examples of the alicyclic polyhydric alcohol (d2) having 6 to 20 carbon atoms include compounds obtained by hydroxyalkylating indene, naphthalene, azulene, anthracene and the like, and alicyclic dihydric alcohols having 6 to 20 carbon atoms {bicyclo [5,3,0] decane dimethanol, bicyclo [4,4,0] decane dimethanol, bicyclo [4,3,0] nonane dimethanol, norbornane dimethanol, tricyclodecane dimethanol, 1,3-adamantane Diol (1,3-dihydroxytricyclo [3,3,1,13,7] decane, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxa Spiro [5,5] undecane, isosorbide, hydrogenated bisphenol A, 1,4-cyclohexanedimethanol, 1,3-cyclohexane Trihydric alcohols [1,3,5-cyclohexane triol] such as methanol, and 1,2-cyclohexanedimethanol} and 3 to 20 carbon atoms and the like.
Of the alicyclic polyhydric alcohol (d2), from the viewpoints of hardness, transparency, weather resistance and curability with active energy rays, tricyclodecane dimethanol, 1,4-cyclohexanedimethanol, 1,3 are preferable. -Cyclohexanedimethanol and 1,2-cyclohexanedimethanol.

  Examples of the araliphatic polyhydric alcohol (d3) having 8 to 16 carbon atoms include dimethylolphenol.

  Examples of the aromatic polyhydric alcohol (d4) having 6 to 15 carbon atoms include catechol, resorcinol, hydroquinone, dihydroxynaphthalene, bisphenol A, bisphenol F, and bisphenol S.

Examples of the alkylene oxide added in alcohol (d5) having 2 to 8 carbon atoms include ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran , 3-methyltetrahydrofuran and styrene oxide.
C2-C12 aliphatic polyhydric alcohol (d1), C6-C20 alicyclic polyhydric alcohol (d2), C7-C16 araliphatic polyhydric alcohol (d3), or C6 It is preferable that the addition mole number of a C2-C8 alkylene oxide added to 1 mol of -15 aromatic polyhydric alcohol (d4) is 1-400 mol from a compatible viewpoint.

  As the polyhydric alcohol (d), one of the above (d1) to (d5) may be used alone, or two or more may be used in combination.

Examples of the (meth) acrylate (e) having a hydroxyl group include the same monomer (b1) having one hydroxyl group and at least one (meth) acryloyl group, 2,3-dihydroxypropyl methacrylate, and the like. It is done. These may be used alone or in combination of two or more.
These may be used alone or in combination of two or more. Among these, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are preferable in that the hydroxyl value of the resulting polyurethane (meth) acrylate (D) is increased. When the hydroxyl value of polyurethane (meth) acrylate (D) is high, the hydroxyl group of the active energy ray-curable composition is also high, and this is preferable because the dispersibility with respect to the organic-inorganic composite filler (C) is improved.

  As the polyurethane (meth) acrylate (D), commercially available products may be used. As a commercially available product, Nippon Synthetic Chemical Industry (trade name: Shibamitsu) UV-1700B (weight average molecular weight: 2,000, Functional group number: 10), UV-6300B (weight average molecular weight: 3,700, functional group number: 7), UV-7550B (weight average molecular weight: 2,400, functional group number: 3) and UV-7600B (weight average molecular weight: 1,400, the number of functional groups: 6) and the like.

  The weight average molecular weight of the polyurethane (meth) acrylate (D) is preferably 1,000 to 20,000, more preferably 2,000 to 10,000, from the viewpoints of stretchability and scratch resistance.

  The number average molecular weight measurement in the present invention uses HLC-8320GPC (manufactured by Tosoh Corp.), THF solvent, TSK standard polystyrene (manufactured by Tosoh Corp.) as a reference substance, measurement temperature: 40 ° C., column: Alliance. (Manufactured by Waters), detector: Measured with a refractive index detector. Moreover, GPC workstation EcoSEC-WS (made by Tosoh Corporation) was used as analysis software.

The radical polymerizable double bond-containing (meth) acrylic polymer (E) which can be contained in the active energy ray-curable composition of the present invention is a monomer composition containing a monomer having a (meth) acryloyl group. It is a polymer having a radical polymerizable double bond composed of a polymer.
(Meth) acrylic acid ester, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, nitrogen-containing (meth) acrylic acid ester as a monomer constituting a monomer composition containing a monomer having a (meth) acryloyl group, (Meth) acrylamide monomer, glycidyl (meth) acrylate, etc. are mentioned.
The radically polymerizable double bond-containing (meth) acrylic polymer (E) is radically polymerizable in the middle of the molecular chain of the polymer of the monomer composition containing a monomer having a (meth) acryloyl group, or at both ends. It can be obtained by adding a compound having a double bond by a known method.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meta ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, n-decyl (meth) acrylate, glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, butylene glycol di (meth) Examples include acrylate and hexane glycol di (meth) acrylate.

  Examples of the alkoxyalkyl (meth) acrylate include methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.

  Examples of the hydroxyalkyl (meth) acrylate include (meth) acrylates similar to the (meth) acrylate (e) having a hydroxyl group.

  Nitrogen-containing (meth) acrylic acid esters include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate and N, N- Examples include diethylaminopropyl (meth) acrylate.

  As the (meth) acrylamide monomer, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl ( Examples include meth) acrylamide and N-isopropyl (meth) acrylamide.

  The (meth) acrylic acid ester, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, nitrogen-containing (meth) acrylic acid ester, (meth) acrylamide monomer and glycidyl (meth) acrylate are used in only one kind. Also, two or more kinds may be mixed and used, and another ethylenically unsaturated monomer (such as vinyl ether and vinyl ester) may be used in combination.

  As the radical polymerizable double bond-containing (meth) acrylic polymer (E), commercially available ones can be used, and as a commercial product, 8KX-078 (weight average molecular weight: about 40,000, double bond) Equivalent: 3) and 8KX-089 (weight average molecular weight: about 100,000, double bond equivalent: 930) (manufactured by Taisei Fine Chemical Co., Ltd.).

  The weight average molecular weight of the radically polymerizable double bond-containing (meth) acrylic polymer (E) is preferably 10,000 to 200,000, more preferably 50,000 to 200 from the viewpoints of stretchability and chemical resistance. 150,000.

  The polyester (meth) acrylate (F) is obtained by esterification of a polycarboxylic acid, a polyhydric alcohol, and a compound containing at least one (meth) acryloyl group and at least a hydroxyl group or a carboxyl group in the molecule. Compounds, and polyester acrylates having two or more ester bonds and one or more (meth) acryloyl groups.

  Examples of the polyvalent carboxylic acid include alkane dicarboxylic acids having 2 to 50 carbon atoms (such as oxalic acid, malonic acid, succinic acid, adipic acid, repartic acid, and sebacic acid), and alkenedicarboxylic acids having 4 to 50 carbon atoms ( Alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and glutaconic acid), aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, and Naphthalenedicarboxylic acid and the like), aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid and the like), and aliphatic tricarboxylic acids having 6 to 36 carbon atoms (hexane tricarboxylic acid and the like).

As said polyol, the same thing as the polyhydric alcohol (d) illustrated in the polyurethane (meth) acrylate (D) can be used.
Examples of the compound containing at least one (meth) acryloyl group and at least a hydroxyl group or a carboxyl group in the molecule include (meth) acrylate (e) and (meth) having a hydroxyl group exemplified in polyurethane (meth) acrylate (D). ) Acrylic acid and the like.

  As the polyester (meth) acrylate (F), those available from the market can be used. As commercially available products, EBECRYL450 (weight average molecular weight: 1,600, functional group number: 6) manufactured by Daicel Oltex Co., Ltd., EBECRYL800 (weight average molecular weight: 810, functional group number: 4), EBECRYL810 (weight average molecular weight: 1,000, functional group number: 4), etc. are mentioned.

  The weight average molecular weight of the polyester (meth) acrylate (F) is preferably 1000 to 20,000, more preferably 1500 to 15,000 from the viewpoints of stretchability and chemical resistance.

  Epoxy (meth) acrylate (G) is a reaction product of an epoxy resin and (meth) acrylate. As the epoxy (meth) acrylate (G), commercially available products can be used. As commercial products, BAEA-100 (functional group number: 2), BAEM-100 (functional group number: 2) manufactured by KSM Co., Ltd. ), BAEM-50 (functional group number: 2), and BFEA-50 (functional group number: 2).

  The number average molecular weight of the epoxy (meth) acrylate (G) is preferably 1,000 to 20,000, more preferably 2,000 to 10,000, from the viewpoints of stretchability and chemical resistance.

  Polyurethane (meth) acrylate (D), radical polymerizable double bond-containing (meth) acrylic polymer (E), polyester (meth) acrylate (F) and epoxy (included in the active energy ray-curable composition of the present invention The total weight ratio of the (meth) acrylate (G) is preferably 30% by weight to 90% by weight, more preferably 40% by weight to 80% by weight, based on the total of the curable composition, from the viewpoint of stretchability and the like. It is.

The active energy ray-curable composition of the present invention may further contain a reactive diluent (H).
The reactive diluent (H) is not particularly limited as long as it is a low molecular compound that initiates a radical polymerization reaction with the photopolymerization initiator (I) described later. Preferred reactive diluents (H) include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, long chain aliphatic acrylate, allyl acrylate, cyclohexyl acrylate, 1,6-hexane diacrylate, tetraethylene glycol diacrylate Acrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, isobornyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylacrylamide, diethylacrylamide, N-acryloylmorpholine and tetrachloroterephthalate Examples include dimethyl acid and the like.
These may be used alone or in combination of two or more.
From the viewpoint of chemical resistance, preferred are isobornyl acrylate, dimethyl tetrachloroterephthalate and tricyclodecane dimethanol diacrylate, and more preferred are isobornyl acrylate and tricyclodecane dimethanol diacrylate.

  The weight ratio of the reactive diluent (H) contained in the active energy ray-curable composition of the present invention is preferably 5% by weight to 40% based on the total of the curable composition from the viewpoint of scratch resistance and the like. %, And more preferably 10 wt% to 30 wt%.

The active energy ray-curable composition of the present invention may further contain a photopolymerization initiator (I).
As photopolymerization initiator (I), benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzene Nzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 , 4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligo [2-hydroxy-2-methyl-1 [4- (1-methylvinyl) phenyl] propanone], 2,4 , 6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, and the like.
These may be used alone or in combination of two or more.
Of these photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-methyl-1- [4- (methylthio) is preferable from the viewpoint of curability. Phenyl] -2-morpholinopropan-1-one, more preferably 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

  The content of the photopolymerization initiator in the composition is preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight, from the viewpoint of curability, with respect to the total weight of the active energy ray-curable composition. %.

The active energy ray-curable composition of the present invention may further contain a solvent (J).
The solvent (J) is not particularly limited as long as it does not have an active hydrogen group, and a single solvent or a plurality of solvents may be mixed. Specific examples include methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, toluene, cellosolve, ethyl acetate and butyl acetate.
From the viewpoint of the solubility of the resin, propylene glycol monomethyl ether acetate and methyl ethyl ketone are preferable, and propylene glycol monomethyl ether acetate is more preferable.

  The weight ratio of the solvent (J) contained in the active energy ray-curable composition of the present invention is the organic / inorganic composite filler (C) and optionally used (D) and (E) from the viewpoint of coating property and the like. , (F), (G), (H) and (I) based on the total weight, preferably 100 wt% to 500 wt%, more preferably 200 wt% to 400 wt%.

  The active energy ray-curable composition of the present invention includes the organic-inorganic composite filler (C), a polyurethane (meth) acrylate (D) used as necessary, a radical polymerizable double bond-containing (meth) acrylic polymer (E), Known polyester (meth) acrylate (F) and epoxy (meth) acrylate (G), reactive diluent (H) used if necessary, photopolymerization initiator (I) used if necessary, and solvent (J) used if necessary It can be obtained by mixing uniformly with a mixer.

  The cured product of the present invention is a cured product of the active energy ray-curable composition described above, and includes those obtained by reacting and irradiating the active energy ray-curable composition with active energy. .

The cured product of the present invention can be obtained by applying the active energy ray-curable composition to at least a part of at least one side of the substrate, drying it as necessary, and then irradiating the active energy ray to cure. Thus, it is possible to obtain a hard coat coating having a cured film which is a cured product of the present invention.
For coating, known coating machines [bar coater, gravure coater, roll coater (size press roll coater, gate roll coater, etc.), air knife coater, spin coater, blade coater, etc.] can be used.
A coating film thickness is 0.5-300 micrometers as a preferable film thickness after hardening drying. The upper limit is preferably 250 μm from the viewpoints of drying properties and curability, and the lower limit is preferably 1 μm from the viewpoints of wear resistance, solvent resistance and stain resistance.

  As said base material, what consists of resin, such as a methylmethacrylate (co) polymer, a polyethylene terephthalate, a polycarbonate, a polytriacetylcellulose, a polycycloolefin, is mentioned.

When the active energy ray-curable composition contains a solvent, it is preferably dried after coating. Examples of the drying method include a method using a known hot air dryer (dryer or the like).
The drying temperature by a hot air dryer is preferably 10 to 200 ° C. Among them, the more preferable upper limit is 150 ° C. from the viewpoint of the smoothness and appearance of the coating film, and the more preferable lower limit is 30 ° C. from the viewpoint of the drying speed.

  Active energy rays used for curing include ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays. Among these active energy rays, ultraviolet rays and electron beams are preferable from the viewpoint of curability and resin deterioration.

When the active energy ray-curable composition is cured with ultraviolet rays, a known ultraviolet irradiation device [for example, an ultraviolet irradiation device [model number “VPS / I600”, manufactured by Fusion UV Systems Co., Ltd.] can be used.
Examples of the lamp used in the ultraviolet irradiation device include a high-pressure mercury lamp and a metal halide lamp. The dose of ultraviolet rays is preferably a flexible viewpoint of curability and cured product of a composition 10~10,000mJ / cm ^2, more preferably from 100~5,000mJ / cm ^2.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these.

<Production Example 1>
In a reaction vessel equipped with a stirrer, a cooling tube, a blowing tube and a thermometer, silica particles [trade name: colloidal silica IPA-ST (an isopropyl alcohol dispersion with a colloidal silica concentration of 30% by weight), Nissan Chemical Industries, Ltd. Product] 30 parts by weight and silicon alkoxide tetraethoxysilane (a-1) [trade name: TEOS, manufactured by Tokyo Chemical Industry Co., Ltd.] 35 parts by weight were charged and stirred for 30 minutes, and then 2.36 parts by weight of formic acid was added. The mixture was charged and reacted at 65 ° C. for 2 hours. The reaction vessel was evacuated and topped at 70 ° C. for 2 hours while blowing air to obtain a dispersion of dehydrated condensate of silica and silicon alkoxide.
Furthermore, 20 parts by weight of ε-caprolactam adduct (b-1) [trade name: FA-4DT, manufactured by Daicel Chemical Industries, Ltd.] of 2-hydroxyethyl (meth) acrylate was added and stirred for 30 minutes. 2.36 parts by weight of toluenesulfonic acid was charged and reacted at 65 ° C. for 2 hours. The organic-inorganic composite filler which is a reaction product of silica and 2-hydroxyethyl (meth) acrylate ε-caprolactam adduct and silicon alkoxide is subjected to a condensation reaction at 70 ° C. for 2 hours while reducing the pressure in the reaction vessel and blowing air. A dispersion of (C-1) was obtained.
Isopropyl alcohol was distilled off from the solution obtained by topping the obtained (C-1) at 70 ° C. for 2 hours, and the remaining solid content was analyzed by pyrolysis GC-MS to obtain 2-hydroxyethyl (meth) acrylate. It was confirmed that the ε-caprolactam adduct was an organic-inorganic composite filler bonded to silica particles via a polycondensate of silicon alkoxide. The obtained organic-inorganic composite filler (C-1) had a siloxane bond formed by condensation of three silicon alkoxides (a).

<Production Example 2>
Production Example 1 except that 20 parts by weight of hydroxyethyl acrylamide [trade name: HEAA, KJ Chemicals Co., Ltd.] was used instead of 20 parts by weight of the ε-caprolactam adduct of 2-hydroxyethyl (meth) acrylate. In the same manner as in Example 1, an organic-inorganic composite filler (C-2) in which hydroxyethyl acrylamide was bonded to silica particles through a polycondensate of silicon alkoxide was obtained.

<Production Example 3>
In Production Example 2, instead of 30 parts by weight of silica particles, zirconia particles [trade name: SZR-CMH (methanol dispersion with colloidal zirconia concentration 30% by weight), manufactured by Sakai Chemical Industry Co., Ltd.] 30 parts by weight In the same manner as in Production Example 2, an organic-inorganic composite filler (C-3) in which hydroxyethylacrylamide was bonded to zirconia particles via a polycondensate of silicon alkoxide was obtained.

<Production Example 3 Production Example of Polyurethane Acrylate>
In a glass reaction vessel equipped with a stirrer and a thermometer, 14.9 parts by weight of tricyclodecane dimethanol [trade name: TCD alcohol DM, manufactured by OXEA], the molar ratio of cyclohexane dimethanol and hexanediol is 1: 1 polycarbonate diol [trade name: ETERNACOLL UM-90 (1: 1), Ube Industries, Ltd.] 17.1 parts by weight and propylene glycol 1-monomethyl ether 2-acetate [trade name: propylene glycol monomethyl ether acetate, Sankyo Chemical Co., Ltd.] was charged at 35.0 parts by weight and stirred to obtain a homogeneous solution. Next, dicyclohexylmethane diisocyanate [trade name: Desmodur W, manufactured by Sumika Bayer Urethane Co., Ltd.] 30.3 parts by weight, bismuth tris (2-ethylhexanoate) 50% by weight solution of 2-ethylhexanoic acid as a catalyst [Product name: Neostan U-600, manufactured by Nitto Kasei Co., Ltd.] was added in an amount of 0.1 part by weight, stirred to obtain a homogeneous solution, and then reacted at 80 ° C. for 6 hours.
After confirming that the isocyanate content was 1.65% or less, 2.7 of 2-hydroxyethyl acrylate was added while a mixed gas of nitrogen and oxygen having an oxygen concentration adjusted to 8% by volume was passed through the liquid. Part by weight was added and the reaction was further carried out at 75 ° C. for 2 hours. After confirming that the isocyanate content was 0.01% or less, the mixture was cooled to 60 ° C. to obtain polyurethane acrylate (D-1). Mn of (D-1) was 3,000.

<Example 1>
In a reaction vessel equipped with a stirrer, a condenser tube and a thermometer, 30.0 parts by weight of the organic-inorganic composite (C-1) solution obtained in Production Example 1 and urethane acrylate obtained in Production Example 2 (D -1) 70.0 parts by weight, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (I-2) 3.0 parts by weight, isobornyl acrylate 18 Part by weight was added and mixed and stirred at 65 ° C. until uniform, to obtain an active energy ray-curable composition (X-1).

<Examples 2-6 and Comparative Examples 1-4>
Except according to the number of parts (parts by weight) described in Table 1, the same operation as in Example 1 was performed, and each of the active energy ray-curable compositions (X-2) to (X-6) and (Ratio X-) was performed. 1) to (ratio X-4) were obtained.

The raw materials used in Table 1 are as follows.
(C′-1): Alkylsilane coupling agent-modified silica fine particles [trade name “Colloidal silica MEK-ST” primary particle size 10-15 nm MEK 40 wt% solution, manufactured by Nissan Chemical Industries, Ltd.]
(C′-2): Acrylate-containing silane coupling agent-modified silica fine particles [trade name “MEK-AC-2140Z” primary particle size 10-15 nm MEK 46 wt% solution, surface modified grade (for acrylic composite) Nissan Chemical Industries ( Made by Co., Ltd.]
(E-1): UV curable high molecular weight acrylate polymer (weight average molecular weight: about 100,000, double bond equivalent: 930) [trade name “8KX-089” manufactured by Taisei Fine Chemical Co., Ltd.]
(H-1) Isobornyl acrylate: [trade name “Light acrylate IBX-A”, manufactured by Kyoeisha Chemical Co., Ltd.]
(H-2) Tricyclodecane dimethanol diacrylate: [trade name “A-DCP”, manufactured by Shin-Nakamura Kogyo Co., Ltd.]
(I-1): 2,4,6-trimethylbenzoyldiphenylphosphine oxide [trade name “Lucirin TPO”, manufactured by BASF Corporation]
(I-2): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one [trade name “Irgacure 907”, manufactured by BASF Corporation]
(I-3): 1-hydroxycyclohexyl phenyl ketone [trade name “Irgacure 184”, manufactured by BASF Corporation]
(J-1): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (I-2) [trade name “Irgacure 907”, manufactured by BASF Corporation]

  Below, the method of performance evaluation of haze, a total light transmittance, and pencil hardness is demonstrated.

<Curing method for cured film>
The active energy ray-curable compositions (X-1) to (X-4) and (Ratio X-1) to (Ratio X-4) were each diluted with methyl ethyl ketone using a disperser to obtain a nonvolatile content of 30% by weight. Prepare.
PET film with a thickness of 100 μm [trade name “Cosmo Shine A4300”, manufactured by Toyobo Co., Ltd.] Using a bar coater on one side of the base material, it was applied so that the film thickness after drying and curing was 5 μm, and at 80 ° C. After drying for 1 minute, an ultraviolet irradiation device [model number “VPS / I600”, manufactured by Fusion UV Systems Co., Ltd. same as below. ] Was irradiated with ultraviolet rays at 300 mJ / cm ² to create a film having a cured film on the surface of the base film.
Performance evaluation was performed by the following method about the obtained film. The evaluation results are shown in Table 1.

[Measurement of haze]
In accordance with JIS-K7105, a total light transmittance measuring device [trade name “haze-gard
haze was measured using “dual” BYK Gardner Co., Ltd.].

[Measurement of total light transmittance (transparency of film)]
Based on JIS-K7105, the said test piece measured the total light transmittance (%) using the total light transmittance measuring apparatus [Brand name "haze-garddual" by BYK gardner Co., Ltd.].

[Measurement of scratch resistance]
About the created cured film, a load was applied to steel wool [trade name “BON STAR No. 0000” manufactured by Nippon Steel Wool Co., Ltd.] to be 1 N / cm ^2, and the cured film surface was set to 10 using a Gakushin abrasion tester. The difference between the haze value (H2) measured immediately after reciprocating rubbing and the haze value (H1) measured before the test was determined. The haze value was measured with the above-described total light transmittance measuring device.

[Measurement of stretchability]
The test piece was pulled by an autograph at 130 ° C. and a speed of 10 mm / min, and the elongation at the time of breaking was measured.

[Measurement of chemical resistance]
An SPF45 sunscreen cream was applied on the test piece, and the state after wiping off the cream after 4 hours at 80 ° C. was observed.
1: Occurrence of film peeling 2: Muddy white film 3: Slight trace remaining on film 4: No change in film

From the results of Table 1, the cured films obtained by curing the active energy ray-curable compositions of Examples 1 to 6 of the present invention are not impaired in transparency even if they contain a large amount of inorganic oxide fine particles. In addition, it can be seen that it has an excellent effect on scratch resistance. In addition, since the reactive group is directly bonded to the inorganic oxide, the chemical resistance is excellent.
On the other hand, Comparative Example 1 and Comparative Example 3 using an inorganic oxide having no reactive group are inferior in scratch resistance and chemical resistance as compared with Examples. In addition, Comparative Examples 2 and 4 using an inorganic oxide provided with a reactive group on the particle surface are inferior in scratch resistance and stretchability.
As a result, commercially available modified silica fine particles not produced by the method of the present invention cannot achieve both transparency, scratch resistance and chemical resistance.

A film having a coating film obtained by curing the active energy ray-curable composition of the present invention is excellent in stretchability, scratch resistance, and chemical resistance, and therefore is used for a decorative film by an in-mold method. Ideal for materials and other applications.

Claims (5)

  A monomer (b) having an inorganic oxide (A), one active hydrogen group and at least one (meth) acryloyl group, and a silicon alkoxide (a) having two or more alkoxy groups having 1 to 4 carbon atoms; An active energy ray-curable composition, comprising an organic-inorganic composite filler obtained by reacting, wherein the weight ratio of (b) and (a) used in the reaction is 1: 6 to 1: 1.   The active energy ray-curable composition according to claim 1, further comprising a polyurethane (meth) acrylate (D) and / or a radically polymerizable double bond-containing (meth) acrylic polymer (E).   The active energy ray-curable composition according to claim 2, wherein the number average molecular weight of the (D) is 1,000 to 20,000.   The active energy ray-curable composition according to any one of claims 1 to 3, wherein the inorganic oxide (A) is silica.   Hardened | cured material of the active energy ray curable composition in any one of Claims 1-4.