JP2009179674A - Active energy ray curable resin composition for hard coat - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray curable resin composition for hard coat, which has excellent low shrinkage during curing and which gives a cured product (hard coat film) excellent in scratch resistance and transparency. <P>SOLUTION: The active energy ray curable resin composition for the hard coat comprises: a polyfunctional monomer (A) having 3 to 10 (meth)acryloyl groups; a monofunctional (meth)acrylate (B) having one (meth)acryloyl group and 1 or 2 benzene rings and having a glass transition point of 15 to 180°C of the homopolymer; and a photopolymerization initiator (C). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable hard coat resin composition. More specifically, the present invention relates to an active energy ray-curable hard coat resin composition that provides a hard coat film having excellent scratch resistance and low cure shrinkage.

Conventionally, polyfunctional (meth) acrylates are widely used as raw materials for various polymer materials such as coating materials, optical materials, electronic materials, and various polymer crosslinking agents.
Among these, the resin composition for hard coats using polyfunctional (meth) acrylate as one of the raw materials is mainly intended to impart scratch resistance to a substrate such as a plastic film. Many studies for improving the performance are still in progress, and the main measure is to increase the crosslink density of the hard coat film (see, for example, Patent Documents 1 and 2).

Japanese Patent Publication No.49-22951 JP-A-56-135526

However, when the thickness of the substrate such as a plastic film is limited, increasing the crosslink density causes volume shrinkage of the hard coat film during curing with active energy rays, resulting in curling of the substrate film, Since problems such as cracks occur in the hard coat film, there is a limit only by increasing the crosslinking density.
An object of the present invention is to provide an active energy ray-curable hard coat resin composition which is excellent in low shrinkage at the time of curing, and the obtained cured product (hard coat film) is excellent in scratch resistance and transparency. is there.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention has a polyfunctional monomer (A) having 3 to 10 (meth) acryloyl groups, 1 (meth) acryloyl group, 1 to 2 benzene rings, and 15 homopolymers. A resin composition for an active energy ray-curable hard coat, comprising a monofunctional (meth) acrylate (B) having a glass transition point of ˜180 ° C. and a photopolymerization initiator (C).

The active energy ray-curable hard coat resin composition of the present invention has the following effects.
(1) Excellent curing low shrinkage.
(2) A cured product (hard coat film) obtained by curing the composition is excellent in scratch resistance and transparency.

(A) in the present invention is a polyfunctional monomer having 3 to 10 (preferably 3 to 6) (meth) acryloyl groups, and the hardness of the hard coat film is less than 3 (meth) acryloyl groups. If it is low and the number exceeds 10, curing shrinkage deteriorates.
(A) includes a polyfunctional (meth) acrylate (A2) having a Mn of 1,000 or less excluding the urethane group-containing polyfunctional (meth) acrylate (A1) and (A1).

  From (A1), from the viewpoint of the reactivity of urethanization and the hardness of the hard coat film, preferably 1 to 3 (more preferably 1 to 2) hydroxyl groups and 2 or more (hard coat film hardness and cure shrinkage) From the viewpoint of the above, those formed from the compound (a1) having 2 to 5 and more preferably 2 to 3) (meth) acryloyl groups and the polyisocyanate (a2) are included.

For (a1), the number of carbon atoms (hereinafter abbreviated as C) is 9 or more and the number average molecular weight [hereinafter abbreviated as Mn, and the measurement is performed by gel permeation chromatography (GPC) method. ] 1,000 or less, for example, glycerin (hereinafter abbreviated as GR) di (meth) acrylate, trimethylolpropane (hereinafter abbreviated as TMP) di (meth) acrylate, ditrimethylolpropane (hereinafter abbreviated as DTMP) di- and tri (Meth) acrylate, pentaerythritol (hereinafter abbreviated as PE) di- and tri (meth) acrylate, dipentaerythritol (hereinafter abbreviated as DPE) tri-, tetra- and penta (meth) acrylate, GR alkylene oxide [C2- 10, hereinafter abbreviated as AO. For example, ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO)] adduct, di (meth) acrylate of PE, AO adduct of tri (meth) acrylate, and the like.
Among these, PE tri (meth) acrylate and DPE penta (meth) acrylate are preferable from the viewpoint of the surface hardness of the cured product.

Examples of the polyisocyanate (hereinafter sometimes abbreviated as PI) (a2) include the following, and mixtures of two or more thereof.
(1) C (excluding C in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic PI
Diisocyanates (hereinafter abbreviated as DI), such as 1,3- and / or 1,4-phenylene DI, 2,4- and / or 2,6-tolylene DI (TDI), 4, 4′- and / or 2,4′-diphenylmethane DI (MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene DI, and m- and p-isocyanatophenylsulfonyl isocyanate; and trifunctional or higher functional PI (such as triisocyanate), such as crude TDI, crude MDI (polymethylene polyphenyl polyisocyanate) and 4,4 ′, 4 ″ -triphenyl meta Triisocyanate;

(2) C2-18 aliphatic PI
DI, such as ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, nonamethylene DI, decamethylene DI, dodecamethylene DI, 2,2,4- and / or 2,4,4- Trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and Trimethylhexamethylene diisocyanate (TMDI); and trifunctional or higher functional PI (such as triisocyanate), such as 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexa Methyleneto Reisocyanates and lysine ester triisocyanates (phosgenates of reaction products of lysine and alkanolamines, such as 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl-2 , 6-diisocyanatohexanoate);

(3) C4-45 alicyclic PI
DI, for example isophorone DI (IPDI), 2,4- and / or 2,6-methylcyclohexane DI (hydrogenated TDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexyl Silene DI, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- and / or 2,6-norbornane DI, dimer acid DI (DDI); PI (triisocyanate etc.), for example, bicycloheptane triisocyanate (4) C8-15 araliphatic PI
m- and / or p-xylylene DI (XDI), diethylbenzene DI and α, α, α ′, α′-tetramethylxylylene DI (TMXDI)
(5) Nurateated products of the above (1) to (4) Among these PIs, preferred from the viewpoint of light resistance are (2), (3), and (5) of aliphatic PI and alicyclic-containing PI. It is a nurate compound.

The urethane group-containing polyfunctional (meth) acrylate (A1) is obtained by the urethanization reaction of the above (a1) and (a2).
The equivalent ratio of NCO groups to OH groups (NCO / OH) in the reaction is not particularly limited, but is preferably 0.8 / 1 to 1. from the viewpoint of the toughness of the molded product described later and the temporal stability of (A1). 2/1, more preferably 0.9 / 1 to 1.1 / 1.

  In the urethanization reaction, a urethanization catalyst may be used. The catalyst includes metal compounds (organic bismuth compounds, organic tin compounds, organic titanium compounds, etc.), tertiary amines and quaternary ammonium salts.

Among the metal compounds, the organic bismuth compound includes organic bismuth carboxylate, organic bismuth alkoxide, and a chelate compound of a compound having a dicarbonyl group and bismuth.
The organic bismuth carboxylate is represented by the general formula Bi (OCOR) ₃ , where R represents a monovalent hydrocarbon group, such as an aliphatic hydrocarbon group [C1-20, such as alkyl (methyl, ethyl, n- and i -Propyl, n-, i-, sec- and t-butyl, octyl, 2-ethylhexyl, decyl and dodecyl) groups and alkenyl (1-, 2- and i-propenyl, 1-, 2- and 3-butenyl) Group], aromatic (aliphatic) hydrocarbon groups (C6-20, such as phenyl, toluyl, xylenyl, benzyl, phenethyl and hexylphenyl groups) and alicyclic hydrocarbon groups (C3-10, such as cyclopropyl, cyclobutyl, cyclopentyl) , Cyclohexyl and cyclooctyl groups).
Among these R, a C2-12 aliphatic hydrocarbon group and a C5-10 alicyclic hydrocarbon group are preferred from the viewpoint of hydrolysis resistance.
Specific examples of the organic bismuth carboxylate include bismuth tri (2-ethylhexanoate), bismuth tri (decanoate) and the like.

The organic bismuth alkoxide is represented by the general formula Bi (OR) ₃ , R is the same as described above, and preferred from the viewpoint of hydrolysis resistance are the same as described above.
Specific examples of the organic bismuth alkoxide include tri-2-ethylhexyloxybismuth.

  The compound having a dicarbonyl group constituting the chelate compound of a compound having a dicarbonyl group and bismuth includes C4-15, for example, acetylacetone, acetylacetic acid, acetoacetoxyethyl (meth) acrylate, and the chelate compound includes Chelate compounds of these with Bi are included. Specific examples of the chelate compound include bis (acetylacetone) bismuth.

Organotin compounds include divalent tin compounds (stannas octoate, etc.) and tetravalent tin compounds (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate). E.).
The organic titanium compound includes tetraalkyl (C2-12) titanate and titanium (C2-12) dicarboxylate.

Tertiary amines include triethylenediamine, tetraalkyl (C1-3) alkylene (C2-6) diamine (tetramethylethylenediamine, tetramethylhexylenediamine, etc.) and diazabicycloalkene compounds {eg, 1,8-diazabicyclo [5 , 4, 0] undecen-7 [DBU [registered trademark, manufactured by San Apro Co., Ltd.]]} and the like.
The quaternary ammonium salt includes tetraalkyl (C1-4) ammonium bromide, tetraalkyl (C1-4) ammonium perchlorate, and the like.

  The amount of the urethanization catalyst used is usually 1% or less based on the total weight of (a1) and (a2), preferably 0.001 to 0.5%, more preferably 0.8% from the viewpoint of reactivity and transparency. It is 05 to 0.2%.

The conditions for the urethanization reaction are not particularly limited. For example, (a1), (a2) and, if necessary, a urethanization catalyst are mixed, and the reaction temperature is usually 40 to 100 ° C. (reactivity and stability of the product). (A1) can be produced by reacting at a temperature of preferably 60 to 95 ° C. for 2 to 20 hours.
If necessary, the mixture may be reacted in the presence of a solvent (ethyl acetate, methyl ethyl ketone, toluene, etc.). The amount of the solvent used is usually 5,000% or less based on the total weight of (a1) and (a2), and preferably 10 to 1,000% from the viewpoint of the handleability of the mixture and the reaction rate.

  The urethanization reaction can be carried out at normal pressure, reduced pressure or increased pressure. The progress of the urethanization reaction can be determined, for example, by measuring the NCO% of the reaction system.

  Mn in (A1) is preferably 500 to 2,000, more preferably 700 to 1,800, and particularly preferably 800 to 1,500 from the viewpoint of scratch resistance and ease of handling of the cured product.

Among (A), the polyfunctional (meth) acrylate (A2) excluding the above (A1) is preferably 3-6 functional from the viewpoint of the hardness of the hard coat film and curing low shrinkage, and the hardness of the hard coat film. And preferably from C12 or more and Mn 1,000 or less from the viewpoint of curing low shrinkage, such as GR tri (meth) acrylate, MP tri (meth) acrylate, PE tri- and tetra (meth) acrylate, DPE hexa (meth) Examples include acrylate, tri (meth) acrylate of an AO adduct of GR, tri- and tetra (meth) acrylate of an AO adduct of PE, and the like.
Among these, PE tri (meth) acrylate and DPE hexa (meth) acrylate are preferable from the viewpoint of the surface hardness of the cured product.

(B) in the present invention is a monofunctional (meth) acrylate having one (meth) acryloyl group and one or two benzene rings and a homopolymer having a glass transition point of 15 to 180 ° C. .
When the number of (meth) acryloyl groups in (B) exceeds 1, the curing shrinkage increases, and when the number of benzene rings exceeds 2, the toughness deteriorates. Further, when the glass transition point (hereinafter abbreviated as Tg) of the homopolymer (B) is less than 15 ° C., the hardness of the hard coat film is lowered, and when it exceeds 180 ° C., the toughness is deteriorated.

(B) includes C11 or more and Mn 1,000 or less, for example, the following.
(1) Mono (meth) acrylate of AO 1-5 mol adduct of bisphenol compound Each mono (meth) acrylate of EO2 mol and PO1 mol adduct of bisphenol A, -F and -S, etc .;
(2) mono (meth) acrylate of paracumylphenol compound AO 1-5 mol adduct, paracumylphenol EO 1 mol acrylate, etc .;
(3) Benzene ring-containing polyvalent (2-4) carboxylic acid (anhydride) [C8-30, such as isophthalic acid, terephthalic acid, phthalic acid (anhydride) and trimellitic acid (anhydride)] and hydroxyl group-containing mono Mono (meth) acrylate formed from 1 mol of esterified product of (meth) acrylate and 1 mol of isophthalic acid;
(4) Reaction product of phenol and phenylphenol glycidyl ether and hydroxyl group-containing mono (meth) acrylate 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like.
Of these (B), (2), (3) and (4) are preferable from the viewpoint of toughness of the cured product.

The weight ratio of (A) to (B) is preferably 75/25 to 90/10, more preferably 80/20, from the viewpoints of the hardness of the hard coat film and curing low shrinkage.
~ 85/15.

Examples of the photopolymerization initiator (C) include hydroxybenzoyl compounds (2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin alkyl ether, etc.), benzoylformate compounds (methyl) Benzoylformate, etc.), thioxanthone compounds (isopropylthioxanthone, etc.), benzophenones (benzophenone, etc.), phosphate ester compounds (1,3,5-trimethylbenzoyldiphenylphosphine oxide, etc.), benzyldimethyl ketal, and the like.
Among these, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone and 1,3,5-trimethylbenzoyldiphenylphosphine oxide are preferable from the viewpoint of preventing coloring of the cured product. is there.

  The amount of (C) used is preferably 0.1 to 20%, more preferably 0.2 to 10% from the viewpoint of curability and light resistance based on the total weight of (A) and (B).

If necessary, the composition of the present invention may further contain various additives (D) used in the paint as long as the effects of the present invention are not impaired. The (D) includes inorganic or organic filler (D1), organic pigment (D2), dispersant (D3), antifoaming agent (D4), leveling agent (D5), silane coupling agent (D6), thixotropy. A property-imparting agent (thickening agent) (D7), slip agent (D8), antioxidant (D9) and ultraviolet absorber (D10) are included.
The total use amount of (D) is usually 90% or less based on the total weight of the composition of the present invention, and preferably 0.5 to 50% from the viewpoint of the effect of addition and transparency.

  Among the fillers (D1), as inorganic fillers, alumina [aluminum oxide, aluminum hydroxide, alumina white (alumina hydrate), silica alumina (a fused product of alumina and silica, silica coated on the surface of alumina) Zirconia, tungsten carbide, titanium carbide, silicon carbide, boron carbide, diamond, carbon black (channel black, furnace black, thermal black, acetylene black, etc.), silica (finely divided silicic acid, hydrous silicic acid, diatoms) , Colloidal silica, etc.), silicates (fine powdered magnesium silicate, talc, soapstone, stearite, calcium silicate, magnesium aluminosilicate, sodium aluminosilicate, etc.), carbonates (precipitation (active, dry, heavy or Light) calcium carbonate, Magnesium acid etc.], clay (kaolinic clay, sericite clay, vilophyllite clay, montmorillonite clay, bentonite, acid clay, etc.), sulfate [aluminum sulfate (sulfate band, satin white, etc.), barium sulfate ( Barite powder, precipitated barium sulfate, lithopone, etc.), magnesium sulfate, calcium sulfate (stone koji) (anhydrous koji, hemihydrate koji, etc.)], lead white, mica powder, zinc white, titanium oxide, activated calcium fluoride , Cement, lime, calcium sulfite, molybdenum disulfide, asbestos, glass fiber, lock fiber, and microballoon.

Among these, from the viewpoint of scratch resistance of the cured film and composition, and suppression of coloring of the cured product, alumina, silica, silicate, carbonate, sulfate, and titanium oxide are preferable, and silica, calcium carbonate, Barium sulfate and titanium oxide.
Two or more inorganic fillers may be used in combination, or two or more inorganic fillers may be combined (for example, titanium oxide is fused to silica). The shape of the inorganic filler is not particularly limited, and may be, for example, an indefinite shape, a spherical shape, a hollow shape, a porous shape, a petal shape, an aggregated shape, or a granular shape.
The amount of the inorganic filler used is usually 50% or less based on the total weight of the composition of the present invention, preferably from 1 to 30%, more preferably from 3 to 25 from the viewpoint of the effect of addition and the flexibility of the cured product. %.

Among (D1), examples of the organic filler include beads of acrylic, styrene, silicone, polyurethane, acrylic urethane, benzoguanamine, and polyethylene resins. Of these, silicone resin beads are preferred from the viewpoint of heat resistance. Moreover, the number average particle diameter (μm) of the organic filler is preferably 1 to 30, more preferably 3 to 20, from the viewpoints of light transmittance and coatability of the cured product.
The amount of the organic filler used is usually 50% or less based on the total weight of the composition of the present invention, preferably 5 to 40%, more preferably 10 to 35 from the viewpoint of heat resistance and coating properties of the cured product. %.

Examples of the organic pigment (D2) include the following.
(1) Azo pigments Insoluble monoazo pigments (toluidine red, permanent carmine FB, fast yellow G, etc.), insoluble disazo pigments (disazo yellow AAA, disazo orange PMP, etc.), azo lakes (soluble azo pigments) (lake red C, brilliant carmine) 6B etc.), condensed azo pigments, chelate azo pigments, etc. (2) polycyclic pigments phthalocyanine blue, indanthrone blue, quinacridone red, dioxazine violet, etc. (3) dyed lake basic dyes (Victoria Pure Blue BO lake, etc.), (4) Others Azine pigments (aniline black, etc.), daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, etc. (D2) is used in the total weight of the composition. Usually 50% or less, additive effect Preferably a flexible point of view of fine cured product 0.5 to 40%, more preferably 1% to 30% or less.

  Examples of the dispersant (D3) include organic dispersants [polymer dispersants (Mn 2,000 to 500,000) and low molecular dispersants (molecular weight of 100 or more and less than Mn 2,000)] and inorganic dispersants.

  As the polymer dispersing agent, naphthalene sulfonate [alkali metal (Na and K etc.) salt, ammonium salt etc.] formalin condensate, polystyrene sulfonate (same as above), polyacrylate (same as above) , Poly (2-4) carboxylic acid (maleic acid / glycerin / monoallyl ether copolymer etc.) salt (same as above), carboxymethylcellulose (Mn2,000-10,000) and polyvinyl alcohol (Mn2,000-100) , 000) and the like.

The following are mentioned as a low molecular weight dispersing agent.
(1) Polyoxyalkylene type AO (C2-4) of aliphatic alcohol (C4-30), [alkyl (C1-30)] phenol, aliphatic (C4-30) amine and aliphatic (C4-30) amide 1-30 mol adducts As aliphatic alcohols, n-, i-, sec- and t-butanol, octanol, dodecanol etc .; as (alkyl) phenols, phenol, methylphenol and nonylphenol etc .; as aliphatic amines , Laurylamine, methylstearylamine and the like; and aliphatic amides include stearic acid amide and the like.
(2) Polyhydric alcohol type Monoester compound of C4-30 fatty acid (lauric acid, stearic acid, etc.) and polyhydric (2-6 or more) alcohol (eg GR, PE, sorbitol and sorbitan) (3) Carvone Salt type C4-30 fatty acid (same as above) alkali metal (same as above) salt (4) sulfate ester type C4-30 fatty alcohol (same as above) and aliphatic alcohol AO (C2-4) ) 1-30 mol adduct sulfate alkali metal (same as above) salts, etc.

(5) Sulfonate type [Alkyl (C1-30)] Phenol (same as above) sulfonic acid alkali metal salt (same as above) (6) Phosphate ester type C4-30 aliphatic alcohol (same as above) ) And aliphatic alcohol AO (C2-4) 1-30 mol adduct mono- or diphosphate salts [alkali metal (same as above) salts, quaternary ammonium salts, etc.]
(7) C1-30 aliphatic amines [primary (laurylamine, etc.), secondary (dibutylamine, etc.) and tertiary amine (dimethylstearylamine, etc.) hydrochloride, triethanolamine And C4-30 fatty acid (same as above) monoester inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salt (8) quaternary ammonium salt type C4-30 quaternary ammonium (butyltrimethylammonium, diethyl) Inorganic acid (same as above) salts of laurylmethylammonium, dimethyldistearylammonium and the like.

Examples of the inorganic dispersant include alkali metal (same as above) salts of polyphosphoric acid and phosphoric acid-based dispersants (phosphoric acid, monoalkyl phosphoric acid ester, dialkyl phosphoric acid ester and the like).
The amount of (D3) used is usually 10% or less based on the total weight of the composition of the present invention, and preferably 0.05 to 5% from the viewpoints of the effect of addition and coating stability.

Antifoaming agent (D4) includes lower alcohol (C1-6) (methanol, butanol, etc.), higher alcohol (C8-18) (octyl alcohol, hexadecyl alcohol, etc.), higher fatty acid (C10-20) (oleic acid) , Stearic acid, etc.), higher fatty acid esters (C11-30) (glycerol monolaurate, etc.), phosphate esters (tributyl phosphate, etc.), metal soaps (calcium stearate, aluminum stearate, etc.), polyethers [polyethylene glycol (hereinafter referred to as “polyethylene glycol” PEG (abbreviated) (Mn200 to 10,000), polypropylene glycol (hereinafter abbreviated as PPG) (Mn200 to 10,000), etc.], silicone (dimethylsilicone oil, alkyl-modified silicone oil, fluorosilicone oil, etc.) and mineral oil (Silica powder those dispersed in mineral oil) and the like.
The amount of (D4) used is usually 3% or less based on the total weight of the composition of the present invention, and is preferably 0.01 to 2% from the viewpoint of the effect of addition and coating stability.

Examples of the leveling agent (D5) include PEG type nonionic surfactants (nonylphenol EO 1 to 40 mol adducts, stearic acid EO 1 to 40 mol adducts, etc.), polyhydric alcohol type nonionic surfactants (sorbitan palmitic acid monoester) Sorbitan stearic acid monoester, sorbitan stearic acid triester, etc.), fluorosurfactants (perfluoroalkyl EO 1-50 mol adduct, perfluoroalkyl carboxylate, perfluoroalkyl betaine etc.), modified silicone oil [( Other than D4), for example, polyether-modified silicone oil and (meth) acrylate-modified silicone oil].
The amount of (D5) used is usually 3% or less based on the total weight of the composition of the present invention, preferably 0.1 to 2% from the viewpoint of the effect of addition and transparency.

Examples of the silane coupling agent (D6) include amino group-containing silane coupling agents (γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-phenylaminopropyl trimethoxysilane, etc.), ureido group-containing silane. Coupling agents (ureidopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents [vinylethoxysilane, vinylmethoxysilane, vinyltris (β-methoxyethoxy) silane, etc.], methacrylate groups-containing silane coupling agents (γ-methacrylic) Loxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, etc.), epoxy group-containing silane coupling agents (γ-glycidoxypropyltrimethoxysilane, etc.), isocyanate group-containing silane coupling agents (γ- Isocyanate-propyltriethoxysilane, etc.), polymer-type silane coupling agents (polyethoxydimethylsiloxane, polyethoxydimethylsiloxane, etc.), cationic silane coupling agents [N- (N-benzyl-β-aminoethyl) -γ-amino Propyltrimethoxysilane hydrochloride, etc.].
The amount of (D6) used is usually 10% or less based on the total weight of the composition of the present invention, and preferably 0.5 to 7% from the viewpoint of the effect of addition and transparency.

Thixotropy imparting agent (thickening agent) (D7) includes inorganic thixotropic imparting agents [bentonite, organically treated bentonite (surface wax coating treated bentonite, etc.) and ultrafine surface treated calcium carbonate (colloidal calcium carbonate, etc.)] and Examples include organic thixotropic property-imparting agents (hydrogenated castor oil wax, calcium stearate, aluminum oleate, polymerized linseed oil, etc.).
The amount of (D7) to be used is usually 20% or less based on the total weight of the composition of the present invention, preferably 0.5 to 10% from the viewpoint of the effect of addition and coating stability.

Examples of slip agents (D8) include higher fatty acid esters (such as butyl stearate), higher fatty acid amides (such as ethylene bis stearic acid amide and oleic acid amide), metal soaps (such as calcium stearate and aluminum oleate), and wax [paraffin wax. And polyolefin wax (polyethylene wax, polypropylene wax, carboxyl group-containing polyethylene wax, etc.)] and silicone (for example, dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone oil).
The amount of (D8) used is usually 5% or less based on the total weight of the composition of the present invention, and preferably 0.01 to 2% from the viewpoint of the effect of addition and transparency.

Antioxidants (D9) include hindered phenol compounds [triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis. [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di- t-butyl-4-hydroxybenzylphosphonate diethyl ester] and amine compounds (n-butylamine, triethylamine, diethylaminomethyl methacrylate, etc.).
The amount of (D9) used is usually 3% or less based on the total weight of the composition of the present invention, and preferably 0.005 to 2% from the viewpoint of the effect of addition and prevention of coloring.

Examples of the ultraviolet absorber (D10) include benzotriazole compounds [2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2 -(3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, etc.], triazine compounds [ 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol], benzophenone (such as 2-hydroxy-4-n-octyloxybenzophenone), An oxalic acid anilide compound (2-ethoxy-2'-ethyl oxalic acid bisanilide etc.) is mentioned.
The amount of (D10) used is usually 3% or less based on the total weight of the composition of the present invention, and preferably 0.005 to 2% from the viewpoint of the addition effect and curability.

  When the additives are the same and overlap between (D1) to (D10) above, the amount of each additive exerting the corresponding additive effect is not used regardless of the effect as the other additive, Considering that the effects as other additives can be obtained at the same time, the amount used is adjusted according to the purpose of use.

  The composition of the present invention was formed by blending the above (A), (B), (C), and (D) if necessary, and was formed by applying the composition to a substrate as described below. The cured product (hard coat film) of the present invention can be obtained by irradiating the coating film with an active energy ray to be described later and curing it.

In order to adjust the viscosity of the composition of the present invention to a viscosity suitable for coating, a coating diluted with a solvent as necessary can be used.
The amount of the solvent used is usually 2,000% or less, preferably 10 to 500%, based on the total weight of the composition. Moreover, the viscosity of a coating material is the temperature (usually 5-60 degreeC) at the time of use, and is 5-500,000 mPa * s normally, Preferably it is 50-10,000 mPa * s from a viewpoint of stable coating.

The solvent is not particularly limited as long as it dissolves the resin component in the composition of the present invention. Specifically, aromatic hydrocarbons (C7-10, such as toluene, xylene and ethylbenzene), esters or ether esters (C4-10, such as ethyl acetate, butyl acetate and methoxybutyl acetate), ethers (C4-10, such as Diethyl ether, tetrahydrofuran, monoethyl ether of EG, monobutyl ether of EG, monomethyl ether of propylene glycol (hereinafter abbreviated as PG) and monoethyl ether of diethylene glycol (hereinafter abbreviated as DEG)), ketone (C3-10, for example, acetone, Methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone), alcohol (C1-10 such as methanol, ethanol, n- and i-propanol, n-, i-, sec And t-butanol, 2-ethylhexyl alcohol and benzyl alcohol), amides (C3-6, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), sulfoxides (C2-4, such as dimethylsulfoxide), water, and these Two or more types of mixed solvents are mentioned.
Among these solvents, from the viewpoint of the smoothness of the hard coat film and the efficiency of solvent removal, esters, ketones and alcohols having a boiling point of 70 to 100 ° C. are more preferable, and ethyl acetate, methyl ethyl ketone, i-propanol and these are more preferable. It is a mixture.

The composition of the present invention is diluted with a solvent if necessary, applied to at least a part of at least one side of the substrate, and dried if necessary, and then an active energy ray (ultraviolet ray, electron beam, X-ray, infrared ray, visible ray). A hard coat coating having a cured product (hard coat film) on at least a part of the front surface and / or back surface of the substrate can be obtained by irradiating and curing the light.
In the coating, a commonly used apparatus such as a coating machine [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. The coating film thickness is usually 0.5 to 300 μm as the film thickness after curing and drying, and the preferable upper limit is 250 μm from the viewpoint of drying property and curability, and the preferable lower limit is from the viewpoint of wear resistance, solvent resistance, and contamination resistance. Is 1 μm.

  When the composition of the present invention is used after being diluted with a solvent, it is preferably dried after coating. Examples of the drying method include hot air drying (such as a dryer). The drying temperature is usually 10 to 200 ° C, the upper limit is preferably 150 ° C from the viewpoint of the smoothness and appearance of the coating film, and the lower limit is preferably 30 ° C from the viewpoint of the drying speed.

Active energy rays include ultraviolet rays, electron beams, X-rays, infrared rays, and visible rays. Of these active energy rays, ultraviolet rays and electron beams are preferable from the viewpoint of curability and suppression of resin deterioration.
When the composition of the present invention is cured by ultraviolet irradiation, a known ultraviolet irradiation device [for example, made by Fusion UV Systems Co., Ltd., hereinafter the same. ] Can be used. The irradiation amount of ultraviolet rays (mJ / cm @ 2) is usually 10 to 10,000, and preferably 100 to 5,000 from the viewpoint of the curability of the composition and the flexibility of the cured product.

  When the composition of the present invention is cured by electron beam irradiation, a known electron beam irradiation apparatus [for example, Electron Beam, manufactured by Iwasaki Electric Co., Ltd.] can be used. The irradiation amount (Mrad) of the electron beam is preferably 0.5 to 20, preferably from the viewpoint of the curability of the composition, the flexibility of the cured product, and avoiding damage to the cured product (coating film) and the substrate. 1-15.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by this. In the following, “part” represents “part by weight”, and “%” represents “% by weight”.

Production Example 1
48.6 parts of PE triacrylate [trade name “Light acrylate PE-3A”, manufactured by Kyoeisha Chemical Co., Ltd.] and 30.0 parts of methyl ethyl ketone are placed in a reaction vessel equipped with a condenser, a stirrer and a thermometer, The mixture was stirred and heated to dissolve uniformly. 21.4 parts of hydrogenated MDI and 0.1 part of bismuth tri (2-ethylhexanoate) solution (2-ethylhexanoic acid 50% solution, the same shall apply hereinafter) were added to this solution and heated at 80 ° C. for 6 hours. Stir to reflux. The mixture was allowed to cool to obtain 100 parts of a resin solution having a solid content of 70% urethane acrylate (A-1).

Production Example 2
Put 55.7 parts of DPE pentaacrylate [trade name “Aronix M-403”, manufactured by Toagosei Co., Ltd.] and 30.0 parts of methyl ethyl ketone in the same reaction vessel as in Production Example 1, and heat and stir at 50 ° C. uniformly. Dissolved. To this solution, 14.3 parts of hydrogenated MDI and 0.1 part of a bismuth tri (2-ethylhexanoate) solution were blended, heated to 80 ° C. for 6 hours with stirring and refluxed. The mixture was allowed to cool to obtain 100 parts of a resin solution of 70% solid content of urethane acrylate (A-2).

Examples 1-5, Comparative Examples 1-3
It mix | blended in the ratio shown in Table 1, and obtained the resin composition (Examples 1-5, Comparative Examples 1-3). The compounding components in Table 1 are as follows.
Multifunctional acrylate (A-3): TMP trimethacrylate [trade name “TMPT”, manufactured by Shin-Nakamura Chemical Co., Ltd.]
Benzene ring-containing monoacrylate (B-1): 2-hydroxy-3-phenoxy
Propyl acrylate (Tg: 15 ° C)
Benzene ring-containing monomethacrylate (B-2): 2-methacryloyloxy
Ethylphthalic acid (Tg: 180 ° C)
Benzene ring-containing monoacrylate (B-3): paracumylphenol EO1
Adduct acrylate [trade name "Aronix M-110", Higashi
[Made by Sakai Synthesis] (Tg: 35 ° C)
Benzene ring-containing monoacrylate (ratio B-1): Phenoxyethyl acrylate
G (Tg: -5 ° C)
Benzene ring-free monoacrylate (ratio B-2): isobornyl acrylate
(Tg: 80 ° C)
Benzene ring-containing diacrylate (ratio B-3): 4 mol EO of bisphenol A
Diacrylate [trade name “Neomer BA-641”, Sanyo Chemical Industries
Made by Co., Ltd.] (Tg: 80 ° C)
Photopolymerization initiator (C-1): [trade name “Irgacure 184”, manufactured by Ciba Specialty Chemicals Co., Ltd., 1-hydroxycyclohexyl phenyl ketone]

<Creation of hard coat coating>
To each 50 parts of the resin composition, 100 parts of toluene as a diluted organic solvent was added and stirred with a disperser until uniform, and a cellulose acetate film having a length of 30 cm, a width of 30 cm, and a thickness of 80 μm [trade name “Fujitac “Fuji Photo Film Co., Ltd.” was coated on one side using a bar coater so that the thickness after drying and curing was 5 μm. After drying at 60 ° C. for 3 minutes, the coating film was cured with an ultraviolet irradiation device [manufactured by Fusion UV Systems Co., Ltd.] at an ultraviolet irradiation amount of 200 mJ / cm ² to prepare a hard coat coating. About this coating | covering, performance evaluation was performed about the following item (1)-(3). The results are shown in Table 1.

<Evaluation items>
(1) Scratch resistance Using steel wool # 0000, the surface of the hard coat coating was subjected to 10 reciprocal scratches at a load of 250 g / cm <2>, and the surface appearance was visually evaluated according to the following criteria.

○ No scratches.
Δ: Some scratches are observed.
X Many scratches are observed, and the surface is whitened.

(2) Curing shrinkage The hard coat coating was cut to 10 cm × 10 cm, left in a dryer at 80 ° C. for 1 hour, and then left at room temperature for 1 hour. The coating was placed on a horizontal glass plate with the hard coat surface facing upward, and the height of each of the four raised corners was measured, and the total of four measured values (unit: mm) was taken as cure shrinkage.

○ Less than 120mm △ 120mm or more and less than 150mm × 150mm or more

(3) Transparency Measured according to JIS-K7105 (established in 1981) using a haze meter [haze-gard dual, manufactured by BYK Gardner Co., Ltd.] and evaluated according to the following criteria.

○ Haze is less than 0.5 △ Haze is 0.5 or more and less than 1.5 × Haze is 1.5 or more

<Creation of cured product (hard coat film)>
A spacer frame having a thickness of 500 μm is provided on a glass plate (thickness 3 mm, length 150 mm, width 150 mm) whose surface is treated with a release agent, and is partitioned into squares of 100 mm × 100 mm. After casting the composition shown in Table 1 into the square, another similar glass plate is placed. After irradiating with ultraviolet rays at 1,000 mJ / cm ² with an ultraviolet irradiation device, it was released from the glass plate to obtain a cured product (hard coat film). The cured products were evaluated for the performance of the following items (4) to (5). The results are shown in Table 1.

<Evaluation items>
(4) Compressive modulus After curing the cured product at 25 ° C. and 60% RH for 24 hours, a Vickers hardness meter [Fischer hardness meter, manufactured by Fischer Corporation]. same as below. ], The compression elastic modulus is measured at a load of 1,000 mN. The unit is MPa.
(5) Creep deformation rate The creep deformation rate is measured with a Vickers hardness tester at a load of 1,000 mN. Units%.

  From the results in Table 1, the resin composition of the present invention is superior in curing and low shrinkage compared to the comparative one, and the obtained cured product (hard coat film) has scratch resistance, transparency, compression modulus, creep deformation. It can be seen that the rate is excellent.

  The active energy ray-curable hard coat resin composition of the present invention is excellent in curing low shrinkage at the time of curing, and the resulting cured product (hard coat film) is excellent in scratch resistance, transparency, etc. In an optical film used for a display such as an apparatus, it can be used as a hard coat film for imparting scratch resistance to the surface of the film without impairing its high transparency, which is extremely useful.

Claims (5)

Polyfunctional monomer (A) having 3 to 10 (meth) acryloyl groups (A), 1 (meth) acryloyl group and 1 to 2 benzene rings, and homopolymer having a glass transition of 15 to 180 ° C. An active energy ray-curable hard coat resin composition comprising a monofunctional (meth) acrylate (B) having a point and a photopolymerization initiator (C). The composition according to claim 1, wherein the weight ratio of (A) to (B) is 75/25 to 90/10. A cured product obtained by curing the composition according to claim 1. A hard coat coating comprising the cured product according to claim 3 on at least a part of at least one side of a substrate. A method for producing a hard coat coating, comprising applying the composition according to claim 1 or 2 to at least a part of at least one side of a substrate and irradiating with active energy rays to cure.