TWI550035B - Active energy ray hardening resin composition and coating agent - Google Patents

Description

Active energy ray curable resin composition and coating agent

The present invention relates to an active energy ray-curable resin composition and a coating agent, and more particularly to an active energy of a coating film which is excellent in smoothness and transparency for forming an appearance of a surface of a coating film or a surface of a coating film. A radiation curable resin composition and a coating agent prepared using the same.

Since the active energy ray-curable resin composition has been hardened by irradiation for a very short time, it has been widely used as a coating agent or an adhesive for various substrates, or an anchor coating agent. )Wait.

When the active energy ray curable resin composition is cured on the surface of the plastic substrate to form a cured coating film, in order to suppress shrinkage during curing and improve adhesion to the plastic substrate, or to increase the surface hardness of the cured coating film, Fine particles such as inorganic fillers may be blended in the active energy ray-curable resin composition.

For example, Patent Document 1 discloses a curable resin composition comprising a reaction of a radiation-curable polyfunctional (meth)acrylate having at least two (meth)acrylonium groups and active hydrogen in a molecule with a polyisocyanate. a polyfunctional urethane acrylate; and a colloidal cerium oxide having a primary particle diameter of 1 to 200 nm, and Patent Document 2 discloses an antistatic hard coating resin composition having at least one molecule in a molecule. In the ultraviolet curable (meth) acrylate of the above (meth) acrylonitrile group, an antistatic hard coat resin composition obtained by dispersing a zinc silicate sol having a primary particle diameter of 0.5 μm or less using a dispersant When the coating film is formed, the haze value is 1.5 or less and is transparent.

On the other hand, the active energy ray-curable resin composition is also useful as an anchor coating agent as described above. For example, Patent Document 3 describes a UV-curable coating material for a metal-evaporated primer coating, comprising: selected from (methyl) An acrylic resin having at least one monomer selected from the group consisting of dicyclopentanyl acrylate, dicyclopentenyl (meth) acrylate and isodecyl (meth) acrylate as a constituent component; having at least two (meth) propylene in the molecule a thiol compound; and a photopolymerization initiator.

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-113649

Patent Document 2: Japanese Laid-Open Patent Publication No. Hei 10-231444

Patent Document 3: Japanese Laid-Open Patent Publication No. 2002-347175

However, in the techniques disclosed in Patent Documents 1 and 2, since fine particles are blended in the active energy ray-curable resin composition, the surface of the cured coating film is likely to be uneven, and the smoothness and transparency of the cured coating film are not Satisfied. Further, in addition to the fine particles, a microgel or the like which is not completely removed by filtration in the coating step, or a fine foreign matter mixed in the coating step, is likely to have irregularities on the surface of the cured coating film, and is easy to be smooth and transparent. Sexuality causes a bad influence.

In addition, in order to prevent clogging of the design portion, it is required to be thinned to 10 μm or less in the case of coating the substrate having a fine design property. However, in the technique disclosed in Patent Document 3, the film thickness of the undercoat film becomes When it is 10 μm or less, there is a problem that the substrate cannot be concealed (refer to paragraph [0054] of the publication of Patent Document 3).

As described above, in recent years, particularly in anchor coating applications, although the thinning of the cured coating film is required, the thinner the thickness of the cured coating film, the more difficult it is to obscure the unevenness caused by the particles or foreign matter contained in the cured coating film. Therefore, it is difficult to achieve both film formation and concavity concealment.

In view of the above, it is an object of the present invention to provide a hardened coating film which is excellent in smoothness and transparency even when the thickness of the cured coating film is small, and it is possible to conceal irregularities caused by fine particles or foreign matter contained in the coating material. An active energy ray curable resin composition and a coating agent using the same.

Therefore, the inventors of the present invention have intensively studied in view of the circumstances, and have found that an active energy ray-curable resin composition contains an active energy ray-curable resin composition containing a urethane (meth) acrylate-based compound. The polysaccharide derivative can increase the viscosity change when the solvent component evaporates, and can suppress the surface of the coating film from floating, so that the unevenness of the surface of the cured coating film can be concealed, and the smoothness or transparency of the smooth substrate can be obtained. The finely designed substrate is obtained by obtaining an active energy ray-curable resin composition for a cured coating film having excellent coating film appearance or transparency.

In other words, the present invention relates to an active energy ray-curable resin composition containing a urethane (meth)acrylate compound (A) and a polysaccharide derivative (B).

Further, the present invention provides a coating agent comprising the active energy ray-curable resin composition, in particular, a coating agent used as a primer for metal vapor deposition.

In the active energy ray-curable resin composition of the present invention, even if the coating film is formed by film coating, the unevenness due to fine particles or foreign matter contained in the coating material can be concealed, and the coating film has excellent appearance, smoothness, and transparency. The effect is, in particular, a substrate having a fine design, which can be coated without clogging the design portion, and can conceal the unevenness caused by the influence of particles or foreign matter contained in the cured coating film, and has a design The effect of excellent followability and transparency is therefore particularly useful as a coating agent, especially a metal vapor deposition primer.

The invention is described in detail below.

The active energy ray-curable resin composition of the present invention contains a urethane (meth) acrylate compound (A) and a polysaccharide derivative (B).

Further, in the present invention, the (meth)acrylic group means an acrylic group or a methacryl group, the (meth)acryloyl group means an acryl group or a methacryl group, and the (meth)acrylate means an acrylic group. Ester or methacrylate.

[Carbamate (meth) acrylate compound (A)]

The urethane (meth) acrylate type compound (A) used in the present invention, for example, a hydroxyl group-containing (meth) acrylate type compound (a1), a polyvalent isocyanate type compound (a2), and a polyol type compound (a3) a urethane (meth) acrylate compound (A1) obtained by the reaction, or an amine group obtained by reacting a hydroxyl group-containing (meth) acrylate compound (a1) and a polyvalent isocyanate compound (a2) The acid ester (meth) acrylate type compound (A2) may be used alone or in combination of two or more.

Among these, the urethane (meth) acrylate compound (A1) is preferred from the viewpoint of imparting adhesion between the plastic substrate and the undercoat layer, the undercoat layer and the metal deposition film, for the purpose of coating When the film is added to the film and the fine particles are added to form a coating agent, the urethane (meth) acrylate compound (A2) is preferable, but it can be appropriately selected in consideration of various physical properties of the intended coating film.

The urethane (meth) acrylate type compound (A) used in the present invention has a weight average molecular weight of preferably from 500 to 50,000, more preferably from 1,000 to 30,000. The weight average If the molecular weight is too small, the cured coating film tends to become brittle. If it is too large, the viscosity becomes high and the handling tends to be difficult.

In addition, the weight average molecular weight is a weight average molecular weight converted from a standard polystyrene molecular weight, and three series connected columns are used in a high-speed liquid chromatograph ("Shodex GPC system-11 type" manufactured by Showa Denko Co., Ltd.): Shodex GPC KF-806L (molecular weight exclusion limit: 2 × 10 ⁷ , separation range: 100~2×10 ⁷ , theoretical number of plates: 10,000 plates / root, filler material: styrene-divinylbenzene copolymer, filler granules Diameter: 10 μm ) for measurement.

The urethane (meth) acrylate compound (A) has a viscosity at 60 ° C of 500 to 150,000 mPa. s is better, especially preferably 500~120,000 mPa. s, and more preferably 1000~100,000 mPa. s. When the viscosity falls outside the above range, the coatability tends to decrease.

Moreover, the viscosity measurement method uses an E-type viscometer.

<Aminoformate (meth) acrylate type compound (A1)>

The hydroxyl group-containing (meth) acrylate compound (a1), for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, Hydroxyalkyl (meth)acrylate such as 4-hydroxybutyl (meth)acrylate or 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethyl acrylate, 2-(methyl) propylene oxide Base ethyl-2-hydroxypropyl phthalate, caprolactone modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth) acrylate, fatty acid modified (meth) acrylate ring Oxypropyl propyl ester, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-(methyl) propylene methoxy propyl (meth) acrylate, glycerin Di(meth)acrylate, 2-hydroxy-3-propenyloxypropyl methacrylate, pentaerythritol tri(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate, oxyethylene Modified pentaerythritol tri(meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, oxyethylene modified dipentaerythritol penta (methyl) ) Acrylate and the like.

Among these, a hydroxy (meth) acrylate type compound having one ethylenically unsaturated group is preferable because it can relax the curing shrinkage at the time of formation of a coating film, and more preferably a 2-hydroxyl (meth) acrylate. Ethyl ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, etc. The hydroxyalkyl acrylate is particularly preferably 2-hydroxyethyl (meth)acrylate, which is preferred from the viewpoint of excellent reactivity and general versatility.

Further, these may be used alone or in combination of two or more.

The polyisocyanate compound (a2), for example, methylphenyl diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylene diisocyanate, tetramethyl amide An aromatic polyisocyanate such as xylene diisocyanate, phenyl diisocyanate or naphthalene diisocyanate; hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diazonic acid diisocyanate, leucine triisocyanate, etc. Aliphatic polyisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane An alicyclic polyisocyanate, or a ternary compound or a polyvalent compound of the polyisocyanate, an allophanate type polyisocyanate, a biuret type polyisocyanate, a water-dispersible polyisocyanate (for example: Japan) "AQUANATE 100", "AQUANATE 110", "AQUANATE 200", "AQUANATE 210", etc., manufactured by Polyurethane Industry Co., Ltd., etc.

Among these, from the viewpoint of less yellowing, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isocyanuric acid diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenation An alicyclic diisocyanate such as xylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate or 1,3-bis(isocyanooxymethyl)cyclohexane is preferred, and the hardening shrinkage is small. In particular, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylene diisocyanate are used, and isophorone diisocyanate can be used from the viewpoint of excellent reactivity and general versatility.

The polyol-based compound (a3) is, for example, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol, a polybutadiene polyol, or a (meth)acrylic polyol. An alcohol, a polyoxyalkylene-based polyol, or the like.

The polyether-based polyol is, for example, a polyether polyol having an alkylene structure such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol or polyhexamethylene glycol. Or a random or block copolymer of such polyolefin diols.

The polyester-based polyol, for example, a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); and a reaction of three components of a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester Things and so on.

The aforementioned polyol, for example: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene glycol, 1,3-tetramethylene glycol, 2- Methyl-1,3-trimethylene glycol, 1,5-pentamethylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, 3-methyl-1,5-five Methylene glycol, 2,4-diethyl-1,5-pentamethylene glycol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediol (1,4 - cyclohexanediol or the like), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol or sorbitol).

The above polycarboxylic acid, for example, malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and the like Dicarboxylic acid; alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, p-phenylene An aromatic dicarboxylic acid such as a carboxylic acid or trimellitic acid.

The above cyclic ester is, for example, propiolactone, β -methyl-δ-valerolactone, ε-caprolactone or the like.

The polycarbonate-based polyol is, for example, a reactant of a polyol and phosgene; a ring-opening polymer of a cyclic carbonate (such as a alkyl carbonate).

The polyhydric alcohol is, for example, a polyhydric alcohol exemplified in the description of the polyester-based polyol, and the above alkylene carbonate, for example, ethyl carbonate, methyltrimethyl carbonate, tetramethylene carbonate, and hexamethylene carbonate. Wait.

Further, the polycarbonate polyol may have a carbonate bond and a terminal having a hydroxyl group in the molecule, and may have both a carbonate bond and an ester bond.

The above polyolefin-based polyol, for example, has a homopolymer or a copolymer of ethylene, propylene, butylene or the like as a saturated hydrocarbon skeleton and has a hydroxyl group at its molecular terminal.

The above polybutadiene-based polyol, for example, a copolymer hydrocarbon having butadiene is used as a skeleton, and its molecular terminal has a hydroxyl group.

The polybutadiene-based polyol may be a hydrogenated polybutadiene polyol obtained by hydrogenating all or a part of the ethylenically unsaturated group contained in the structure.

The (meth)acrylic polyol, for example, a (meth) acrylate polymer or a copolymer having at least two hydroxyl groups in the molecule, and the (meth) acrylate, for example, methyl (meth)acrylate , ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethyl (meth)acrylate An alkyl (meth)acrylate such as hexyl ester, decyl (meth)acrylate, dodecyl (meth)acrylate or octadecyl (meth)acrylate.

The polyoxyalkylene-based polyol is, for example, a dimethylpolydecane polyol or a methylphenyl polyoxyalkylene polyol.

Among these, a polyester-based polyol or a polyether-based polyol is preferable, and a polyester-based polyol excellent in mechanical properties such as flexibility at the time of curing is particularly preferable.

The weight average molecular weight of the polyol compound (a3) is preferably from 500 to 8,000, more preferably from 550 to 5,000, still more preferably from 600 to 3,000. When the molecular weight of the polyol-based compound (a3) is too large, the mechanical properties such as the coating film hardness at the time of curing tend to be lowered. When the molecular weight is too small, the curing shrinkage tends to be large, and the stability tends to be lowered.

In the method for producing the urethane (meth) acrylate-based compound (A1), the hydroxyl group-containing (meth) acrylate compound (a1), the polyvalent isocyanate compound (a2), and the polyol compound ( A3) The reaction product obtained by reacting the polyol compound (a3) with the polyvalent isocyanate compound (a2) in advance, and adding the hydroxyl group (meth) The reaction of the acrylate-based compound (a1) is useful from the viewpoints of reaction stability or reduction of by-products.

A known reaction method can be used for the reaction of the polyol compound (a3) with the polyvalent isocyanate compound (a2). In this case, for example, the molar ratio of the hydroxyl group in the isocyanate group:polyol compound (a3) in the polyvalent isocyanate compound (a2) is usually about 2n:(2n-2) (n is an integer of 2 or more After obtaining a urethane (meth) acrylate type compound containing a terminal isocyanate group containing an isocyanate group, addition of a hydroxyl group-containing (meth) acrylate type compound (a1) can be carried out. reaction.

The addition reaction between the reaction product obtained by reacting the above polyol compound (a3) with the polyvalent isocyanate compound (a2) and the hydroxyl group-containing (meth) acrylate compound (a1) may also be used. A known reaction method.

a reaction molar ratio of the reaction product to the hydroxyl group-containing (meth) acrylate compound (a1), for example, when the polyisocyanate compound (a2) has two isocyanate groups and a hydroxyl group-containing (meth) acrylate system When the hydroxyl group of the compound (a1) has one, the reaction product: the hydroxyl group-containing (meth) acrylate compound (a1) is about 1:2, and the isocyanate group of the polyisocyanate compound (a2) has three and Hydroxy (meth) acrylate compound When there is one hydroxyl group (a1), the reaction product: hydroxyl group-containing (meth) acrylate type compound (a1) is about 1:3.

In the addition reaction of the reaction product with the hydroxyl group-containing (meth) acrylate-based compound (a1), the reaction is terminated when the residual isocyanate group content of the reaction system is 0.5% by weight or less. An ester (meth) acrylate compound (A1).

The reaction between the polyol-based compound (a3) and the polyvalent isocyanate-based compound (a2), and further, in the reaction of the reaction product with the hydroxyl group-containing (meth) acrylate-based compound (a1), a catalyst is used to promote the reaction. It is also preferred that the catalyst is, for example, an organometallic compound such as dibutyltin dilaurate, trimethyltin hydroxide or tetra-n-butyltin, zinc octenate, tin octenate, cobalt naphthenate or tin chloride. II), a metal salt such as tin (IV) chloride, triethylamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[ 5,4,0]undecene, N,N,N,'N'-tetramethyl-1,3-butanediamine, N-ethyloline and other amine-based catalysts, cerium nitrate, cerium bromide , cesium iodide, strontium sulfide, etc., in addition, an organic hydrazine compound such as dibutyl hydrazine dilaurate or dioctyl bismuth laurate, or bismuth 2-ethylhexanoate, bismuth naphthenate, isodecanoic acid Barium salt, barium neodylinium salt, barium laurate salt, barium salt of maleic acid, barium stearate, barium oleate, linolenic acid, barium acetate, barium dicapcoate, dihydrate Lanthanum sulphate salt, bismuth bismuth citrate salt, etc. And other media, wherein, dibutyl tin dilaurate, 1,8-diazabicyclo [5,4,0] undecene preferred.

Further, in the reaction of the polyol compound (a3) with the polyvalent isocyanate compound (a2), and in the reaction of the reaction product with the hydroxyl group-containing (meth) acrylate compound (a1), it is possible to use no isocyanate group. The organic solvent of the functional group of the reaction is, for example, an ester such as ethyl acetate or butyl acetate; a ketone such as methyl ethyl ketone or methyl isobutyl ketone; or an organic solvent such as aromatics such as toluene or xylene.

Further, the reaction temperature is usually from 30 to 90 ° C, preferably from 40 to 80 ° C, and the reaction time is usually from 2 to 10 hours, preferably from 3 to 8 hours.

The urethane (meth) acrylate type compound (A1) used in the present invention is preferably one having 20 or less ethylenically unsaturated groups from the viewpoint of utilizing the adhesion to the metal deposition layer for structural characteristics. It is especially preferred to have less than 10 ethylenically unsaturated groups, and more preferably 5 or less ethylenically unsaturated groups.

The weight average molecular weight of the obtained urethane (meth) acrylate type compound (A1) is preferably from 500 to 50,000, more preferably from 1,000 to 30,000. If the weight average molecular weight is too small, the cured coating film tends to become brittle. If it is too large, the viscosity tends to be high, and the operation tends to be difficult.

Further, the above weight average molecular weight was measured in the same manner as described above.

The urethane (meth) acrylate compound (A1) has a viscosity of 500 to 150,000 mPa at 60 ° C. s is better, especially preferably 500~120,000 mPa. s, and more preferably 1000~100,000 mPa. s. When the viscosity falls outside the above range, the coatability tends to decrease.

Further, the viscosity measurement method was the same as described above using an E-type viscometer.

<Aminoformate (meth) acrylate type compound (A2)>

In the present invention, the urethane (meth) acrylate compound (A2) is obtained by reacting a hydroxyl group-containing (meth) acrylate compound (a1) and a polyvalent isocyanate compound (a2).

The urethane (meth) acrylate type compound (A2) used in the present invention preferably has three or more ethylenically unsaturated groups from the viewpoint of the hardness of the cured coating film, and more preferably has four or more ethylene groups. a non-saturated base, more preferably having 6 or more ethylenically unsaturated bases, wherein 6 ethylene is obtained by reacting pentaerythritol tri(meth)acrylate with isophorone diisocyanate. Astringent urethane (meth) acrylate is preferred.

Further, the upper limit of the ethylenically unsaturated group contained in the urethane (meth) acrylate type compound (A2) is usually 30, preferably 25 or less.

Further, in order to adjust the number of ethylenically unsaturated groups, a hydroxyl group-containing (meth)acrylate compound (a1) and a polyvalent isocyanate compound (a2) such as a hydroxyl group-containing (meth)acrylate may be suitably selected. When the compound (a1) has three ethylenically unsaturated groups, and the polyisocyanate compound (a2) uses a diisocyanate compound, the ethylenic acid ester of the urethane (meth)acrylate compound (A2) is unsaturated. The base will be six.

The method for producing the urethane (meth) acrylate compound (A2) can be produced according to the method for producing the above urethane (meth) acrylate compound (A1).

Further, the reaction molar ratio of the polyisocyanate compound (a2) to the hydroxyl group-containing (meth)acrylate compound (a1), for example, the isocyanate group of the polyisocyanate compound (a2) has two hydroxyl groups ( When the hydroxyl group of the methyl acrylate-based compound (a1) has one, the polyisocyanate compound (a2): the hydroxyl group-containing (meth) acrylate compound (a1) is about 1:2, and the polyisocyanate compound ( When the number of the isocyanate groups of the a2) and the hydroxyl group-containing (meth)acrylate compound (a1) has one hydroxyl group, the polyisocyanate compound (a2): a hydroxyl group-containing (meth)acrylate compound ( A1) is about 1:3.

In the addition reaction of the polyisocyanate compound (a2) and the hydroxyl group-containing (meth) acrylate compound (a1), the reaction is terminated when the content of the isocyanate group remaining in the reaction system is 0.5% by weight or less. A urethane (meth) acrylate type compound (A2) can be obtained.

The weight average molecular weight of the obtained urethane (meth) acrylate type compound (A2) is preferably from 500 to 50,000, more preferably from 1,000 to 30,000. Weight average molecular weight If it is too small, the hardened coating film tends to become brittle, and if it is too large, the viscosity becomes high and it tends to be difficult to handle.

Further, the above weight average molecular weight was measured in the same manner as described above.

The urethane (meth) acrylate compound (A2) has a viscosity of 500 to 150,000 mPa at 60 ° C. s is better, especially preferably 500~120,000 mPa. s, and more preferably 1000~100,000 mPa. s. When the viscosity falls outside the above range, the coatability tends to decrease.

Further, in the measurement method of the viscosity, an E-type viscometer was used in the same manner as described above.

[polysaccharide derivative (B)]

In the present invention, the polysaccharide refers to a sugar in which a plurality of monosaccharide molecules are bonded by a glycosidic bond, and is a compound in which ten or more monosaccharides are bonded. These available organisms are obtained in the form of raw synthetic products, which may be in the form of raw synthetic products themselves or artificially chemically modified compounds, and are applied to industrial foods, and are more suitable for fibers, paper, cosmetics or toothpaste. A wide range of substances such as daily necessities, adhesives (paste), and medical treatment.

In the present invention, the polysaccharide derivative (B) means all of the polysaccharide compounds derived from the raw product itself and the artificially synthesized product.

The polysaccharide derivative (B) used in the present invention comprises homopolysaccharides and heteropolysaccharides, for example: α -1,4-glucan (amylose, amylopectin), α -1,6-glucan Sugar (glucan), β -1,4-glucan (cellulose), β -1,6-glucan (pustulan), β- 1,3-glucan (for example : α- or β -glucan derived from curdlan, sizofiran, etc., α- 1,3-glucan, β -1,2-glucan (CrownGall polysaccharide) , β -1,4-galactan (galactan), β -1,4-mannan, α -1,6-mannan, β -1,2-fructose (inulin), β -2,6- fructose polysaccharides (bacterial fructan (levan), β -1,4- xylan, β -1,3- xylan, β -1,4- chitosan, β -1,4-N-ethinyl chitosan (chitin), polypulmonium, agar, alginic acid, etc., also containing amylose-containing starch.

Among these, α-glucan or β-glucan is preferred from the viewpoint of compatibility with a urethane (meth) acrylate-based derivative or a solvent, and particularly preferably β-glucan. .

The polysaccharide derivative (B), preferably all or a part of the hydroxyl group of the polysaccharide is substituted with -C(O)R, -C(O)NH(R), -C(O)N(R)(R) and -R Other substituents such as those. Here, R is an aliphatic group having 1 to 3 carbon atoms, an alicyclic group having 3 to 10 carbon atoms or an aromatic or heteroaromatic having 4 to 20 carbon atoms, and R itself may be optionally substituted with a substituent. Other substituents may be substituted by one type or two or more types.

More preferred polysaccharide derivatives (B) are, for example, thiolated polysaccharides. Preferred sulfhydryl groups of the thiolated polysaccharides are, for example, ethyl hydrazino, butyl fluorenyl, benzhydryl, methylbenzhydryl, dimethylbenzimidyl, chlorobenzylidene, dichlorobenzhydryl.

In addition, the polysaccharide derivative (B) has a number average molecular weight (Mn) of preferably 5,000 to 200,000, more preferably 7,500 to 150,000, and more preferably from the viewpoint of concealing irregularities caused by fine particles or foreign matter contained in the coating material. Good is 10,000~100,000. When the number average molecular weight is too small, the floating of the fine particles or the foreign matter to be mixed is suppressed, and the unevenness cannot be concealed. Therefore, the film-hardened coating film having surface smoothness and transparency tends to be difficult to obtain, and if it is too large, it is solvent-soluble. Solubility or miscibility with other ingredients tends to decrease.

The number average molecular weight is a number average molecular weight converted from a standard polystyrene molecular weight, and is connected in series using a high-speed liquid chromatograph (Waters 2695 (main body) and Waters 2414 (detector) manufactured by Waters Corporation, Japan). 3 columns: Shodex GPC KF-806L (molecular weight exclusion limit: 2 × 10 ⁷ , separation range: 100~2×10 ⁷ , theoretical number of plates: 10,000 plates / root, filler material: styrene-divinylbenzene copolymerization The particle size of the material and the filler was measured by 10 μm.

In the present invention, among the above, preferred polysaccharide derivatives (B) are, for example, cellulose acetate alkylate resins such as cellulose acetate butyrate resin and cellulose acetate propionate resin, and fibers. Acetate resin and the like.

In addition, the above-mentioned polysaccharide derivative (B) may be used alone or in combination of two or more.

In the present invention, the content of the polysaccharide derivative (B) is preferably 3 parts by weight or more, more preferably 3 to 1000 parts by weight, per 100 parts by weight of the urethane (meth) acrylate type compound (A). More preferably, it is 5 to 500 parts by weight, particularly 8 to 100 parts by weight. If the content of the polysaccharide derivative (B) is too large, the flatness of the cured coating film may be lowered, or when the primer for metal vapor deposition is used, the adhesion between the cured coating film and the metal deposition layer may be lowered, or the active energy may be The ratio of the radiation curable component is low, and it is difficult to obtain a sufficient surface hardness of the coating film.

On the other hand, if the content of the polysaccharide derivative (B) is too small, the effect of concealing the concavities and convexities caused by fine particles or foreign matter contained in the coating material tends to be lowered.

[Ethylene unsaturated monomer (C)]

The ethylenically unsaturated monomer (C) is an ethylenically unsaturated monomer having one or more ethylenically unsaturated groups in one molecule (excluding the urethane (meth)acrylate compound (A) For example, a monofunctional monomer, a bifunctional monomer, or a trifunctional or higher monomer.

The monofunctional monomer may be any monomer containing one ethylenically unsaturated group, for example, styrene, vinyl toluene, chlorostyrene, α -methylstyrene, methyl (meth)acrylate, ( Ethyl ethyl acrylate, acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (methyl) Phenyloxyethyl acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro(meth)acrylate -2-hydroxypropyl ester, glycerol mono(meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isophthalide (meth)acrylate Ester, tricyclodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (a) Octyl acrylate, decyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, Benzyl (meth) acrylate, phenol Oxyethylene modified methacrylate, nonylphenol oxypropylene modified (meth) acrylate, 2-(methyl) propylene oxy-2-hydroxypropyl phthalate, etc. a half ester (meth) acrylate of a formic acid derivative, decyl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, Allyl (meth) acrylate, propylene sulfhydryl Porphyrin, 2-hydroxyethyl acrylamide, N-methylol (meth) acrylamide, N-vinyl pyrrolidone, 2-vinyl pyridine, 2-(methyl) propylene methoxyethyl acid phosphate Ester monoester and the like.

Further, in addition to the above monofunctional monomer, there are, for example, Michael addition of acrylic acid or monopropenyl 2-propenyloxyethyl dicarboxylate, Michael addition of acrylic acid, such as acrylic acid dimer, methacrylic acid Dimer, acrylic trimer, methacrylic trimer, acrylic tetramer, methacrylic tetramer, and the like. Further, for example, a carboxylic acid having a specific substituent, that is, a 2-propenyloxyethyl dicarboxylic acid monoester, such as 2-propenyloxyethyl succinic acid monoester, 2-methyl propylene oxy ethoxylate B Succinic acid monoester, 2-propenyloxyethyl phthalic acid monoester, 2-methylpropenyloxyethyl phthalate monoester, 2-propenyloxyethyl hexahydroortho Monoester of phthalic acid, 2-methylpropenyloxyethylhexahydrophthalic acid monoester, and the like. Further, for example, an oligoester acrylate.

The bifunctional monomer may be any monomer containing two ethylenically unsaturated groups, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol II. (Meth) acrylate, polyethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate, dipropylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, dibutyl Alcohol di(meth)acrylate, neopentyl glycol di(meth)acrylate, oxyethylene modified bisphenol A di(meth)acrylate, oxypropylene modified bisphenol A di(methyl) Acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol oxyethylene modification Bis(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl di(meth)acrylate, diethylene glycol diepoxy Dipropyl ether di(meth)acrylate, diglycidyl phthalate di(meth) acrylate, hydroxytrimethylacetic acid modified neopentyl glycol di(meth) acrylate, isocyanuric acid Oxyethylene modified diacrylate, 2-(meth)acryloxyethyl acid phosphate diester, and the like.

The monomer having three or more functional groups may be any monomer containing three or more ethylenically unsaturated groups, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol IV (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris(meth) propylene methoxy ethoxy trimethylol propane, glycerol poly epoxide Ether poly (meth) acrylate, isocyanuric acid oxyethylene modified triacrylate, oxyethylene modified dipentaerythritol penta (meth) acrylate, oxyethylene modified dipentaerythritol hexa (meth) acrylate, oxygen Ethylene modified pentaerythritol tri(meth) acrylate, oxyethylene modified pentaerythritol tetra(meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa Acrylate, caprolactone modified pentaerythritol tri(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, and the like.

These ethylenically unsaturated monomers (C) may be used alone or in combination of two or more.

In the above-mentioned ethylenically unsaturated monomer (C), it is preferred to form a mesh structure by crosslinking with active energy rays to improve the durability such as water resistance and heat resistance in the coating film. It is preferably a polyfunctional monomer containing two or more ethylenically unsaturated groups, and a polyfunctional monomer containing three or more ethylenically unsaturated groups is preferred from the viewpoint of forming a high-order network structure.

Specifically, for example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, can be obtained from high formation. The viewpoint of the coating film of the secondary mesh structure is preferable.

In the present invention, the content of the ethylenically unsaturated monomer (C) is preferably from 10 to 500 parts by weight, particularly preferably 20%, based on 100 parts by weight of the urethane (meth)acrylate compound (A). ~300 parts by weight, more preferably 30 to 100 parts by weight. When the content of the ethylenically unsaturated monomer (C) is too large, the adhesion between the undercoat layer and the metal deposition layer tends to decrease when the metal is vapor-deposited, and if it is too small, the high-order mesh structure cannot be formed by crosslinking. The durability of the film tends to decrease.

[Photopolymerization initiator (D)]

In addition to the urethane (meth) acrylate-based compound (A) and the polysaccharide derivative (B), the present invention further preferably comprises a photopolymerization initiator (D) for curing by active energy rays.

Photopolymerization initiator (D), for example: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4-(2) -hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- Oxo (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Acetophenones such as phenylphenyl)butanone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone oligomer; benzoin and benzoin Methyl ether, benzoin ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin; diphenyl ketone, methyl o-benzoyl benzoate, 4-phenyl diphenyl ketone , 4-benzylidene-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone, 2,4,6 -trimethyldiphenyl ketone, 4-benzylidene-N,N-dimethyl-N-[2-(1-o-oxy-2-propenyloxy)ethyl]benzene bromide Diphenylketones such as (Methanaminium), (4-benzylidylbenzyl)trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-di Ethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl Thiophenones such as -9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoate) Mercapto-based fluorenylphosphine oxides such as -2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide; In addition, these photopolymerization initiators (D) may be used alone or in combination of two or more.

Further, these auxiliary agents may also be used in combination, for example, triethanolamine, triisopropanolamine, 4,4'-dimethylaminodiphenyl ketone (milaxone), 4,4'-diethylamino group II. Phenyl ketone, 2-dimethylaminoethyl benzoic acid, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester, 4-dimethylamino benzene Isoamyl formate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone.

Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl benzophenone, benzhydryl isopropyl ether, 4-(2-hydroxyethoxy)-phenyl (2-hydroxy-2-propane) The ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one is preferred.

The content of the photopolymerization initiator (D) is 0.1 part by weight based on 100 parts by weight of the urethane (meth)acrylate compound (A) (when the ethylenically unsaturated monomer (C) is contained). It is preferably 40 parts by weight, more preferably 1 to 20 parts by weight, particularly preferably 2 to 20 parts by weight.

When the content of the photopolymerization initiator (D) is too small, the curing tends to be poor. If the content is too large, the solution stability may be lowered, or the stability of the solution tends to be lowered, or the embrittlement or coloring problem tends to occur.

Therefore, the present invention can provide a urethane (meth) acrylate-based compound (A) and a polysaccharide derivative (B), preferably an ethylenically unsaturated monomer (C), and a photopolymerization initiator. (D) The active energy ray curable resin composition, but a surface conditioner, a leveling agent, a polymerization inhibitor or the like may be added as needed.

The surface conditioning agent is not particularly limited, and examples thereof include alkyd resins and the like.

The alkyd resin has an effect of imparting film forming properties at the time of coating or an effect of improving adhesion to a metal vapor deposition surface.

The coating agent may have a function of imparting a coating liquid to the moisture permeability of the substrate and lowering the surface tension, and a known general coating agent such as an anthrone modified resin, a fluorine-modified resin, or an alkyl group may be used. Modified resin, etc.

Polymerization inhibitors, for example: p-benzylhydrazine, naphthoquinone, formamidine, 2,5-diphenyl-p-benzyl bromide, hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone Monomethyl ether, mono-tert-butylhydroquinone, p-tert-butylcatechol, and the like.

Further, in the active energy ray-curable resin composition of the present invention, an oil, an antioxidant, a flame retardant, an antistatic agent, a filler, a stabilizer, a reinforcing agent, a matting agent, a grinding agent, an organic fine particle, or the like may be blended. Inorganic fine particles, polymer compounds (acrylic resin, polyester resin, epoxy resin, etc.).

Further, the active energy ray-curable resin composition of the present invention may be blended with an organic solvent and adjusted in viscosity as needed. The organic solvent is, for example, an alcohol such as methanol, ethanol, propanol, n-butanol or isobutanol, a ketone such as acetone, methyl isobutyl ketone, methyl ethyl ketone or cyclohexanone, or a cyanobacteria such as ethyl cyanisol. An aromatic hydrocarbon such as toluene or xylene; a glycol ether such as propylene glycol monomethyl ether; an acetate such as methyl acetate, ethyl acetate or butyl acetate; or diacetone alcohol. These organic solvents may be used singly or in combination of two or more.

When two or more kinds are used, a combination of a glycol ether such as propylene glycol monomethyl ether and a ketone such as methyl ethyl ketone or an alcohol such as methanol, or a combination of a ketone such as methyl ethyl ketone or an alcohol such as methanol, or an alcohol such as methanol may be used. In combination, it is preferred from the viewpoint of the appearance of the coating film.

The active energy ray-curable resin composition of the present invention can be usually diluted to 3 to 60% by weight, preferably 5 to 40% by weight, based on the above organic solvent, and applied to a substrate.

Further, when the active energy ray-curable resin composition of the present invention is produced, the urethane (meth) acrylate compound (A), the polysaccharide derivative (B), and the ethylenic unsaturated are not sufficient. The mixing method of the monomer (C) and the photopolymerization initiator (D) is not particularly limited and may be mixed by various methods.

The active energy ray-curable resin composition of the present invention is effective as a curable resin composition for forming a coating film such as a top coating agent or an anchor coating agent for various substrates, and is coated with an active energy ray-curable resin composition. After being coated on the substrate (when the composition diluted with the organic solvent is applied, it is further dried), it is hardened by irradiation with an active energy ray. The coating method is not particularly limited, and examples thereof include wet coating methods such as spray coating, shower coating, dip coating, roll coating, spin coating, and screen printing.

The active energy ray can use electromagnetic waves such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, and electromagnetic waves such as X-rays and gamma rays. Further, an electron beam, a proton beam, a neutron beam, or the like can be used, but it is easy to obtain from the curing speed and the irradiation device. From the viewpoints of degree and price, it is advantageous to harden by ultraviolet irradiation. Further, when electron beam irradiation is performed, it can be cured without using a photopolymerization initiator (D).

A method of hardening by ultraviolet irradiation, using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, etc., which emit light in a wavelength region of 150 to 450 nm, is irradiated by about 30 ~3000mJ/cm ² can be.

After the ultraviolet irradiation, heating may be performed as needed to complete the hardening.

The coating film thickness (film thickness after hardening) is usually preferably 1 to 50 μm , more preferably 2 to 30 μm , still more preferably 3 to 25 μm . Among them, in particular, a thin coating is preferably 1 to 15 μm , and a thick coating is preferably 15 to 30 μm , particularly preferably 15 to 25 μm .

In the present invention, even if the coating film is applied by a film, the unevenness caused by the fine particles or foreign matter contained in the coating material or the unevenness of the substrate itself can be concealed, so that it is very thin at the time of thin coating. effective.

A target substrate to which the active energy ray-curable resin composition of the present invention is applied, for example, a polyolefin resin, a polyester resin, a polycarbonate resin, an acrylonitrile butadiene styrene copolymer (ABS), polyphenylene A vinyl-based resin or the like (such as a film, a sheet, a cup, etc.), a metal (aluminum, copper, iron, SUS, zinc, magnesium, an alloy of these, etc.), glass, or the like.

Further, the active energy ray-curable resin composition of the present invention is preferably an anchor coating agent for metal deposition, and specifically, the active energy ray-curable resin composition of the present invention is applied to a surface of a plastic or the like. After the active energy ray is irradiated, the metal is vapor-deposited on the surface of the coating film, and if necessary, a top coat layer is formed thereon to form a multilayer structure.

As the plastic substrate, for example, ABS, polycarbonate, acrylic resin, polyamide resin, a composite substrate such as these, or a composite substrate of the above-mentioned materials obtained by mixing glass fibers or inorganic materials can be used.

The film thickness of the cured coating film of the active energy ray-curable resin composition is preferably from 1 to 30 μm, more preferably from 2 to 15 μm.

Further, the metal to be vapor-deposited is, for example, aluminum (Al), tin (Sn), indium (ln), indium-tin (InSn) or the like.

The active energy ray-curable resin composition containing the urethane (meth)acrylate compound (A) and the polysaccharide derivative (B) of the present invention can be concealed even if the film is applied by film coating. The unevenness caused by fine particles or foreign matter contained in the paint has an effect of being excellent in smoothness of the coating film and transparency. Further, the active energy ray-curable resin composition of the present invention is used as a coating, an adhesive, an adhesive, an adhesive, an ink, a protective coating agent, an anchor coating agent, a magnetic powder coating adhesive, and a sanding coating. Various coating film forming materials such as a film and a plate material are useful. Among them, the anchor coating agent for metal evaporation is very useful.

Example

The present invention will be more specifically described by the following examples, but is not limited to the following examples without departing from the scope of the invention. In addition, in the example, "part" and "%" represent the weight basis.

The urethane (meth) acrylate type compound (A) was prepared as follows.

(A-1): In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 16.1 g (0.07 mol) of isophorone diisocyanate and a bifunctional polyester polyol (hydroxyl weight 54 mgKOH) were added. / g) 75.2 g (0.04 mol), 0.02 g of hydroquinone monomethyl ether as a polymerization inhibitor, 0.02 g of dibutyltin dilaurate as a reaction catalyst, and reacted at 60 ° C for 3 hours to add 2-hydroxy acrylate Ethyl ester 8.6 g (0.07 mol). The reaction was allowed to proceed at 60 ° C for 3 hours, and the reaction was terminated when the residual isocyanate group became 0.3% to obtain a bifunctional urethane acrylate (A-1) (weight average molecular weight: 10,000, viscosity at 60 ° C, 15,000 mPa·s).

The following is prepared as a polysaccharide derivative (B).

(B-1): cellulose acetate butyrate resin (manufactured by Eastman Chemical Japan Co., Ltd., trade name "CAB551-0.01": number average molecular weight 16,000)

(B-2): cellulose acetate butyrate resin (manufactured by Eastman Chemical Japan Co., Ltd., trade name "CAB551-0.2": number average molecular weight 30,000)

(B-3): cellulose acetate butyrate resin (manufactured by Eastman Chemical Japan Co., Ltd., trade name "CAB500-5": number average molecular weight: 57,000)

(B-4): cellulose acetate butyrate resin (manufactured by Eastman Chemical Japan Co., Ltd., trade name "CAB381-20": number average molecular weight 70,000)

(B-5): Cellulose acetate propionate-based resin (manufactured by Eastman Chemical Japan Co., Ltd., trade name "CAB504-0.2": number average molecular weight: 15,000).

The following were prepared as the ethylenically unsaturated monomer (C).

(C-1): pentaerythritol triacrylate

The following materials were prepared as a photopolymerization initiator (D).

(D-1): 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184", manufactured by BASF Japan)

The following materials were prepared as an acrylic resin (B') solution.

(B'-1): To a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, 55 parts of ethyl acetate and 45 parts of toluene were added. The mixture was heated to 90 ° C while stirring, and a solution of 0.05 parts of azobisisobutyronitrile (AIBN) as a polymerization initiator was added dropwise to 100 parts of butyl acrylate for 2 hours. Then, after 1 hour and 2 hours, a polymerization initiator solution in which 0.05 parts of AIBN was dissolved in 10 parts of ethyl acetate was added, and the mixture was reacted under reflux for 7 hours, and diluted with ethyl acetate to obtain an acrylic resin (B). '-1) solution (weight average molecular weight: 180,000, number average molecular weight: 65,000, solid content: 30%).

[Examples 1 to 11]

The urethane (meth) acrylate compound (A), the polysaccharide derivative (B), the ethylenically unsaturated monomer (C), and the photopolymerization initiator (D) are calculated in terms of solid content. After blending at a ratio shown in Table 1, the solid content of the photopolymerization initiator was 30%, and the active energy ray-curable resin composition was obtained by diluting with ethyl acetate.

(Comparative Example 1)

100 parts of the urethane (meth)acrylate compound (A), 42.9 parts of the ethylenically unsaturated monomer (C), and 5.7 parts of the photopolymerization initiator (D) were blended in terms of solid content. The solid content of the photopolymerization initiator (D) was 30%, and the active energy ray-curable resin composition was obtained by diluting with ethyl acetate.

(Comparative Example 2)

An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that the polysaccharide derivative (B-1) in Example 1 was changed to the acrylic resin (B'-1).

The obtained active energy ray-curable resin composition was evaluated according to the following conditions: The evaluation results are shown in Table 1.

<Formation of hardened coating film for evaluation>

In the active energy ray-curable resin composition obtained above, fine particles (acrylic beads: average particle diameter: 5 μm , neo-Nippon oil) are blended with respect to 100 parts of the component from which the solvent is removed from the active energy ray-curable resin composition. 0.1 part of the company "NMB-0520"), coated with a polyethylene terephthalate film substrate (thickness 125 μm ) with an easy-adhesion layer by a bar coater to make a hard coating film 4 to 5 μ m, after drying at 60 ° C for 5 minutes, using a high-pressure mercury lamp bulb 80 W, 1 lamp, 2 times of ultraviolet irradiation from a height of 18 cm at a conveyor speed of 3.4 m / min (accumulated irradiation amount 800 mJ / cm ² ) , obtaining a hardened coating film.

Further, the active energy ray-curable resin composition of the present invention contains a urethane (meth)acrylate compound (A) and a polysaccharide derivative (B), and the blending of the fine particles is for evaluating unevenness. The shape is concealed and deliberately blended.

<Smoothness (surface roughness)>

For the hardened coating film obtained on the surface of the coating film for the above evaluation, a surface roughness meter ("SURFCOM 480A" manufactured by Tokyo Seimitsu Co., Ltd.) was used, and the filter type: Gaussian, λs filter: cutoff ratio 300, calculation specification : JIS '01, a measurement length of 10 mm, a measurement speed of 0.3 mm/s, and a cutoff value of 0.8 mm were measured, and the surface roughness Ra value was measured.

[Evaluation]

◎: Ra value is less than 0.050

○: Ra value is 0.050 or more and less than 0.100

△: Ra value is 0.100 or more and less than 0.120

×: Ra value is 0.120 or more

<Transparency>

For the hardened coating film obtained on the surface of the coating film for the above evaluation, the haze value was measured using a haze meter ("NDH 2000" manufactured by Nippon Denshoku Industries Co., Ltd.).

[Evaluation]

○: Haze value is lower than 0.9

×: The haze value is 0.9 or more

<adhesion>

The obtained hardened coating film was formed on the surface of the coating film for the above evaluation, and the substrate adhesion was evaluated by a checkerboard tape method in accordance with JIS K5400 (1990 edition).

[Evaluation]

○: 100/100 (completely closed)

×: 99/100~0/100 (partial peeling ~ complete peeling)

[Table 1]

From the above evaluation results, it was found that the hardening of Examples 1 to 11 obtained from the active energy ray curable resin composition containing the urethane (meth) acrylate compound (A) and the polysaccharide derivative (B) The coating film, although containing fine particles, can obtain a cured coating film which is excellent in smoothness and excellent in transparency.

On the other hand, the cured coating film of Comparative Example 1 obtained from the active energy ray-curable resin composition containing no polysaccharide derivative (B) was inferior in surface smoothness and transparency.

In addition, the cured coating film of Comparative Example 2 obtained from the active energy ray-curable resin composition containing the acrylic resin (B') in place of the polysaccharide derivative (B) is excellent in transparency, but has poor smoothness and does not have concealing unevenness. effect.

Further, the above embodiments have shown the specific embodiments of the present invention, but the above embodiments are merely illustrative and not limiting. Various modifications apparent to those skilled in the art are within the scope of the invention.

[Industry Utilization]

The active energy ray-curable resin composition containing the urethane (meth)acrylate compound (A) and the polysaccharide derivative (B) of the present invention can be concealed even if a coating film is formed by film coating. The unevenness due to fine particles or foreign matter contained in the paint has an effect of being excellent in smoothness of the coating film and transparency. Further, the active energy ray-curable resin composition of the present invention is used as a coating, an adhesive, an adhesive, an adhesive, an ink, a protective coating agent, an anchor coating agent, a magnetic powder coating adhesive, and a coating film for sanding. Various coating film forming materials such as a plate material are useful. Among them, the anchor coating agent for metal evaporation is very useful.

Claims (8)

An active energy ray curable resin composition comprising a urethane (meth) acrylate compound (A) and a polysaccharide derivative (B); characterized in that the urethane (methyl) The acrylate-based compound (A) is a urethane obtained by reacting a hydroxyl group-containing (meth) acrylate compound (a1), a polyvalent isocyanate compound (a2), and a polyol compound (a3). The acrylate-based compound (A1) and the polyol-based compound (a3) are polyester-based polyols. The active energy ray-curable resin composition according to claim 1, wherein the polysaccharide derivative (B) is a cellulose derivative. The active energy ray-curable resin composition according to claim 1 or 2, wherein the polysaccharide derivative (B) has a number average molecular weight of 10,000 to 100,000. The active energy ray curable resin composition according to claim 1 or 2, wherein the content of the polysaccharide derivative (B) is 100% by weight based on the urethane (meth) acrylate compound (A). The serving is 3 parts by weight or more. An active energy ray-curable resin composition according to claim 1 or 2, which contains an ethylenically unsaturated monomer (C). The active energy ray-curable resin composition of claim 1 or 2 further comprises a photopolymerization initiator (D). A coating agent comprising the active energy ray-curable resin composition according to any one of claims 1 to 6. The coating agent of claim 7 is used as a primer for metal evaporation.