JP2009155470A - Active energy ray curing type resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray curing type resin composition capable of obtaining a cured object excellent in tightness with a plastic, metal glass and the like despite high hardness, and to provide a coating agent, an adhesive or a sealant containing the composition. <P>SOLUTION: This active energy ray curing type resin composition contains a phosphate A having two or more of (meth)acryloyl groups in one molecule, and a polyfunctional (meth)acrylate excepting the phosphate A, and a photopolymerization initiator C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable resin composition. More specifically, the present invention relates to an active energy ray-curable resin composition that has excellent adhesion to plastics, metals, glass, and the like and gives a cured product with high hardness.

  An active energy ray-curable resin composition that is polymerized and cured by active energy rays such as ultraviolet rays, visible rays, and electron beams has an advantage of rapid curing (see, for example, Patent Documents 1 and 2), an optical member, Widely used as coating agents for electric / electronic members, paper, plastics, adhesives, sealing agents, etc.

JP 06-87938 A JP-A-10-287718

However, the conventional active energy ray-curable resin composition has excellent adhesion to a substrate such as plastic, metal, glass, etc. when the cured product has a soft pencil hardness of H or less, but it adheres when the pencil hardness is 2H or more. Insufficient performance and warpage of the substrate occurred.
An object of the present invention is to provide an active energy ray-curable resin composition that gives a cured product having excellent adhesion to a substrate such as plastic, metal, glass, etc. even if the pencil hardness is 2H or higher.

  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 relates to a phosphoric ester (A) having two or more (meth) acryloyl groups in one molecule, a polyfunctional (meth) acrylate (B) excluding (A), and a photopolymerization initiator (C). An active energy ray-curable resin composition comprising: a cured product obtained by applying the composition to at least a part of the substrate surface and irradiating and curing the active energy ray; and based on the cured product It is a covering that is provided on at least a part of at least one side of the material.

  The cured product obtained by applying the active energy ray-curable resin composition of the present invention to a base material such as plastic, metal, and glass and curing it can adhere to the base material even if the pencil hardness is H or higher ( Excellent initial adhesion and wet heat resistance).

The phosphate ester (A) in the present invention has 2 or more (preferably 2 to 6) (meth) acryloyl groups in one molecule. When the number of (meth) acryloyl groups is less than 2, the hardness of the cured product is lowered and the scratch resistance is inferior. Here, the (meth) acryloyl group is a notation representing an acryloyl group, a methacryloyl group, or both an acryloyl group and a methacryloyl group, and has the same meaning hereinafter.
The phosphate ester (A) has 9 to 40 carbon atoms (hereinafter abbreviated as C), for example, a reaction product of glycerin di (meth) acrylate and diphosphorus pentoxide, bisphenol A diglycidyl ether (meth) acrylic acid adduct. And poly (meth) acryloyloxyacid phosphate [pentaerythritol (hereinafter abbreviated as PE) tri (meth) acrylate and diphosphorus pentoxide, dipentaerythritol (abbreviated as DPE) penta A reaction product of (meth) acrylate and diphosphorus pentoxide] and a mixture thereof. Among these, a reaction product of PE tri (meth) acrylate and diphosphorus pentoxide, and a reaction product of DPE penta (meth) acrylate and diphosphorus pentoxide are preferable.

Examples of the polyfunctional (bifunctional to hexafunctional or higher) (meth) acrylate (B) excluding the above (A) include the following.
(1) Di (meth) acrylate [C8 or more and number average molecular weight [hereinafter abbreviated as Mn. The measurement is performed by gel permeation chromatography (GPC). ] 1,500 or less]
(1-1) Poly (oxy) alkylene (alkylene group is C2-4) (molecular weight 106 or more and Mn 1,000 or less) di (meth) acrylate polyethylene glycol (hereinafter abbreviated as PEG) (Mn400), polypropylene glycol (hereinafter PPG) Abbreviations) Di (meth) acrylates of (Mn200) and polytetramethylene glycol (hereinafter abbreviated as PTMG) (Mn650), etc .;
(1-2) Alkylene oxide of dihydric phenol compound (hereinafter abbreviated as AO) (2 to 30 mol) adduct di (meth) acrylate Dihydric phenol compound [C6-18, for example, monocyclic (catechol, resorcinol, hydroquinone) ), Condensed polycyclic (dihydroxynaphthalene, etc.), bisphenol compounds (bisphenol A, -F, -S, etc.)] AO adduct [resorcinol ethylene oxide (hereinafter abbreviated as EO) 4 mol adduct di (meth) acrylate , Dihydroxy (meth) acrylate of dihydroxynaphthalene (hereinafter abbreviated as PO) 4 mol adduct, EO 2 mol, and PO 4 mol adducts of bisphenol A, -F and -S, etc.] Acrylate, etc .;
(1-3) Di (meth) acrylate of aliphatic dihydric alcohol (C2-30) of ethylene glycol, neopentyl glycol, 1,6-hexanediol (hereinafter abbreviated as EG, NPG, 1,6-HD, respectively) Each di (meth) acrylate, etc .;
(1-4) Di (meth) acrylate of alicyclic dihydric alcohol (C6-30) di (meth) acrylate of dimethyloltricyclodecane, di (meth) acrylate of cyclohexanedimethanol and dihydrogen bisphenol A (Meth) acrylate, etc.

(2) 3 to 6 functional poly (meth) acrylate C14 or more and Mn 1,000 or less, for example, trimethylolpropane (hereinafter abbreviated as TMP) tri (meth) acrylate, EO3 mol of TMP and PO3 mol adduct tri ( (Meth) acrylate, glycerin (hereinafter abbreviated as GR) tri (meth) acrylate, GR EO3 mol and PO3 mol adduct tri (meth) acrylate, PE tri (meth) acrylate, PE tetra (meth) acrylate, These include tetra (meth) acrylates of PE EO 4 mole adducts, DPE penta (meth) acrylates, hexa (meth) acrylates of DPE, and mixtures thereof.

  Among the above (B), from the viewpoint of the hardness of the cured product, PE tetra (meth) acrylate, PE EO4 mol adduct tetra (meth) acrylate, DPE penta (meth) acrylate and DPE hexa (meth) are preferred. Acrylate.

  Examples of the photopolymerization initiator (C) include benzoin compounds [C14-18, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether]; acetophenone compounds [C8-18, such as acetophenone, 2, 2 -Diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl Ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one]; anthraquinone compound [C14-19, such as 2-ethylanthraquinone, 2-t-butyl Nthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone]; thioxanthone compounds [C13-17, such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone]; ketal compounds [C16-17, such as acetophenone dimethyl ketal , Benzyldimethyl ketal]; benzophenone compounds [C13-21, such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone]; phosphine oxides [C22-28, such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-to Methylbenzoyl) - phenyl phosphine oxide], and mixtures thereof.

  Of the above (C), the acetophenone compound and phosphine oxide are preferable from the viewpoint of light resistance that the cured product after irradiation with active energy rays is not easily yellowed, and 1-hydroxycyclohexyl phenyl ketone, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4 4-Trimethylpentylphosphine oxide, particularly preferred is 1-hydroxycyclohexyl phenyl ketone.

  Each content of (A) to (C) is based on the total weight of (A) to (C), and (A) is preferably 20 to 80% from the viewpoint of adhesiveness and hardness of the cured coating film. More preferably 30 to 60%; (B) is preferably 19 to 79%, more preferably 35 to 65% from the viewpoint of scratch resistance of the cured coating film and warpage of the cured product; and (C) is a composition. From the viewpoint of the active energy ray curability of the product and the light resistance of the coating film, it is preferably 1 to 15%, more preferably 5 to 10%.

  The resin composition of the present invention can contain various additives (D) as necessary within a range not inhibiting the effects of the present invention. (D) includes a filler (D1), an antistatic agent (D2), an organic pigment (D3), a slip agent (D4), a dispersant (D5), a thixotropic agent (thickener) (D6), 1 type or 2 or more types chosen from the group which consists of a silane coupling agent (D7), a leveling agent (D8), an antifoamer (D9), a ultraviolet absorber (D10), and antioxidant (D11) is contained.

The filler (D1) includes inorganic fillers and organic fillers.
Inorganic fillers include alumina [aluminum oxide, aluminum hydroxide, alumina white (alumina hydrate), silica alumina (alumina-silica fusion, alumina surface coated with silica, etc.]], zirconia, carbonized Tungsten, titanium carbide, silicon carbide, boron carbide, diamond, carbon black (channel black, furnace black, thermal black, acetylene black, etc.), silica (fine powdered silicic acid, hydrous silicic acid, diatom, colloidal silica, etc.), silicic acid Salt (fine powdered magnesium silicate, talc, soapstone, stearite, calcium silicate, magnesium aluminosilicate, sodium aluminosilicate, etc.), carbonate [precipitate (active, dry, heavy or light) calcium carbonate, magnesium carbonate, etc. ], Leh (kaolinic clay, sericite clay, vilophyllite clay, montmorillonite clay, bentonite, acid clay, etc.), sulfate (aluminum sulfate (sulfate band, satin white, etc.), barium sulfate (barite powder, sedimentation) 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, Examples thereof include calcium sulfite, molybdenum disulfide, asbestos, glass fiber, lock fiber, and microballoon (glass microballoon and the like).

Of these, alumina, silica, silicate, carbonate, sulfate, and titanium oxide are preferred from the viewpoint of scratch resistance of the cured product (film) and resin composition, and suppression of coloring of the cured product, and silica is more preferred. , 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.

Examples of the organic filler include beads of acrylic, styrene, silicone, polyurethane, acrylic urethane, benzoguanamine, and polyethylene resins. Among these, silicone resin beads are preferable from the viewpoint of heat resistance.
Moreover, the number average particle diameter (μm) of the organic filler is preferably 0.01 to 30, and more preferably 0.05 to 10 from the viewpoints of light transmittance and coatability of the cured product.

  The total amount of the inorganic and organic fillers is usually 50% or less based on the total weight of the resin composition of the present invention, and preferably 5 to 5 from the viewpoints of heat resistance and flexibility of the cured product and coating properties. 40%, more preferably 10 to 35%.

  Antistatic agents (D2) include cationic, anionic and nonionic antistatic agents.

  Examples of the cationic antistatic agent include amidinium salts, guanidinium salts, and quaternary ammonium salts. Examples of the anion constituting the salt include a methyl carbonate anion and an ethyl carbonate anion. Among these, from the viewpoint of low coloring, amidinium alkyl (C1-3) carbonate and guanidinium alkyl (C1-3) carbonate are preferable, and imidazolinium methyl carbonate and imidazolinium skeleton are more preferable. Is a guanidinium methyl carbonate having

  Anionic antistatic agents include sulfonic acid (polyethylene sulfonic acid, lauryl sulfonic acid, etc.) salt, sulfate ester (lauryl alcohol sulfate, lauryl alcohol EO 3 mol adduct sulfate, etc.) salt, phosphate ester (octyl alcohol phosphate) Ester, lauryl alcohol EO3 mole adduct phosphate ester, etc.) salts and the like. Examples of the cation constituting the salt include alkali metals (sodium, potassium, etc.), amines and the like. Of these, sulfonates are preferable from the viewpoint of antistatic properties.

  Nonionic antistatic agents include EO adducts of higher alcohols (C8-24, such as oleyl alcohol, lauryl alcohol, stearyl alcohol), PEG (Mn 1,000-4,000) fatty acid (C4-28) esters, many Examples thereof include fatty alcohol (C2-6 or more, for example, GR, PE, sorbitol and sorbitan) fatty acid (C4 to 28) esters, and polyhydric alcohol fatty acid esters are preferred from the viewpoint of antistatic properties.

  The amount of (D2) used is usually 30% or less based on the total weight of the resin composition of the present invention, and preferably 10 to 25% from the viewpoint of antistatic properties and light transmittance.

Examples of the organic pigment (D3) include the following (1) to (4).
(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.) Dyes (alkali blue toner, etc.), etc. (4) Others Azine pigments (aniline black, etc.), daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, etc.

  The amount of (D3) used is usually 5% or less based on the total weight of the resin composition of the present invention, preferably 0.5 to 4%, more preferably from the viewpoint of colorability and flexibility of the cured product. 1 to 3%.

Examples of the slip agent (D4) include higher fatty acid esters (C4 to 28, for example, butyl stearate), higher fatty acid amides (C4 to 28, for example, ethylenebisstearic acid amide, oleic acid amide), metal soap (C18 to 30, for example, Calcium stearate, aluminum stearate, aluminum oleate), wax [paraffin wax, polyolefin wax (polyethylene wax, polypropylene wax, carboxyl group-containing polyethylene wax, etc.)], silicone oil (eg dimethyl silicone oil, alkyl-modified silicone oil and fluoro) Silicone oil).
The amount of (D4) used is usually 5% or less based on the total weight of the resin composition of the present invention, and preferably 0.01 to 2% from the viewpoint of the addition effect and coating stability.

  The dispersant (D5) includes an organic dispersant [a polymer dispersant (Mn 2,000 to 500,000) and a low molecular dispersant (molecular weight of 100 or more and less than Mn 2,000)] and an inorganic dispersant.

  As the polymer dispersant, naphthalene sulfonate [the cation constituting the salt is an alkali metal (lithium, sodium, potassium, etc.) salt, ammonium salt, etc. same as below. ] Formalin condensate (Mn2,000-100,000), polystyrene sulfonate (Mn2,000-100,000), polyacrylate (Mn2,000-100,000), poly (2-4) carvone Acid (maleic acid / glycerin / monoallyl ether copolymer, etc.) salt (Mn 2,000 to 200,000), carboxymethyl cellulose (Mn 2,000 to 10,000), polyvinyl alcohol (Mn 2,000 to 100,000), etc. Is mentioned.

The following are mentioned as a low molecular weight dispersing agent.
(1) A polyoxyalkylene type aliphatic alcohol (C4-30), [alkyl (C1-30)] phenol, aliphatic amine (C4-30) and aliphatic amide (C4-30) AO 1-30 mol addition As the aliphatic alcohol, n-, i-, sec- and t-butanol, octanol, 2-ethylhexyl alcohol, dodecanol, oleyl alcohol, etc .; (alkyl) phenol as phenol, methylphenol, nonylphenol, etc .; aliphatic Examples of amines include laurylamine and methylstearylamine; and examples of aliphatic amides include stearic acid amide.
(2) Polyhydric alcohol type C4-30 fatty acids (octyl acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, etc.) and polyhydric (divalent to hexavalent or higher) alcohols (for example, GR, PE, sorbitol and sorbitan monoester compounds (3) carboxylate type C4-30 fatty acid (same as above) alkali metal (same as above) salt

(4) Sulfate ester type C4-30 aliphatic alcohols (same as above) and AO (C2-4) 1-30 mol adducts of aliphatic alcohols sulfate alkali metal (same as above) salts, etc. (5) Sulfonate type [alkyl (C1-30)] phenol (same as above) sulfonic acid alkali metal (same as above) salt (6) phosphate ester type C4-30 fatty alcohol (same as above) and fat AO (C2-4) 1-30 mol adducts of aliphatic alcohols, phosphate mono- and diester salts [alkali metal (same as above) salts, quaternary ammonium salts, etc.]
(7) Primary to tertiary amine salt type C4-30 aliphatic amine [primary amine (such as laurylamine), secondary amine (such as dibutylamine) and tertiary amine (such as dimethylstearylamine)] hydrochloride, tri Inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salt of monoester of ethanolamine and C4-30 fatty acid (same as above) (8) Quaternary ammonium salt type C4-30 quaternary ammonium (butyltrimethylammonium , Diethyl lauryl methyl ammonium, dimethyl distearyl ammonium, etc.) and the like (same as above) salts and the like.

Examples of inorganic dispersants include alkali metal salts of polyphosphoric acid (same as above) and phosphoric acid dispersants (such as phosphoric acid, monoalkyl phosphate ester, dialkyl phosphate ester).
The amount of (D5) used is usually 5% or less based on the total weight of the resin composition of the present invention, and preferably 0.05 to 3% from the viewpoints of the effect of addition and coating stability.

Examples of the thixotropic property-imparting agent (D6) include inorganic thixotropic property-imparting agents (such as bentonite, organically treated bentonite, and ultrafine surface-treated calcium carbonate) and organic thixotropic property-imparting agents (hydrogenated castor oil wax, calcium stearate, aluminum oleate, Polymerized linseed oil, etc.).
The amount of (D6) used is usually 5% or less based on the total weight of the composition of the present invention, preferably 0.5 to 3% from the viewpoint of the addition effect and the transparency of the coating film.

Examples of the silane coupling agent (D7) include amine compounds (γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-phenylaminopropyltrimethoxysilane, etc.), ureido compounds (ureidopropyltriethoxysilane, etc.). , Vinyl compounds [vinyl ethoxy silane, vinyl methoxy silane, vinyl tris (β-methoxy ethoxy) silane, etc.], methacryloyl group-containing compounds (γ-methacryloxy propyl trimethoxy silane, γ-methacryloxy propyl methyl dimethoxy silane, etc.), epoxides ( γ-glycidoxypropyltrimethoxysilane, etc.), isocyanate compounds (γ-isocyanatopropyltriethoxysilane, etc.), polymer types (polymethoxydimethylsiloxane, polyethoxydimethylsiloxa) And the like, and cation type [N- (N-benzyl-β-aminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, etc.].
The amount of (D7) used is usually 5% or less based on the total weight of the resin composition of the present invention, and preferably 0.5 to 3% from the viewpoint of the addition effect and curability.

Examples of the leveling agent (D8) include PEG-type nonionic surfactants (nonylphenol EO 1 to 40 mol adducts, stearic acid EO 1 to 40 mol adducts), polyhydric alcohol type nonionic surfactants (sorbitan palmitic acid monoester) Sorbitan stearic acid monoester, sorbitan stearic acid triester, etc.), fluorine-containing surfactant (perfluoroalkyl EO 1-50 mol adduct, perfluoroalkyl carboxylate, perfluoroalkyl betaine, etc.), modified silicone oil [poly Ether-modified silicone oil, (meth) acrylate-modified silicone oil, etc.].
The amount of (D8) to be used is usually 3% or less based on the total weight of the resin composition of the present invention, and preferably 0.1 to 2% from the viewpoint of the effect of addition and coating stability.

Antifoaming agents (D9) include lower alcohols (C1-4, such as methanol, butanol), higher alcohols (C68-30, such as octyl alcohol, hexadecyl alcohol), fatty acids (C4-30, such as oleic acid, stearic acid) ), Fatty acid esters (C7-36, eg glycerin monolaurate), phosphate esters (C6-20, eg tributyl phosphate), metal soaps (C18-30, eg calcium stearate, aluminum stearate, aluminum oleate), minerals Examples thereof include oil, polyether (Mn 200 to 5000, such as PEG, PPG), silicone oil [Mn 200 to 10,000, such as dimethyl silicone oil, alkyl-modified silicone oil, fluorosilicone oil] and the like.
The amount of (D9) to be used is usually 3% or less based on the total weight of the resin composition of the present invention, and preferably 0.01 to 2% from the viewpoint of the effect of addition and coating stability.

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) to be used is usually 3% or less based on the total weight of the resin composition of the present invention, and preferably 0.005 to 2% from the viewpoint of the addition effect and curability.

Antioxidants (D11) 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.) and the like.
The amount of (D11) used is usually 3% or less based on the total weight of the resin composition of the present invention, and preferably 0.005 to 2% from the viewpoint of the addition effect and coating stability.

  When the additive is the same and overlaps between (D1) to (D11), the amount of each additive having 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 resin composition of the present invention can be used after being diluted with an organic solvent when applied to a substrate described later. Examples of the organic solvent include alcohols (C1-10, such as methanol, ethanol, n- and i-propanol, n-, sec- and t-butanol, benzyl alcohol, octanol), ketones (C3-8, such as acetone). , Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, dibutyl ketone, cyclohexanone), ester or ether ester (C4-10, such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, EG monomethyl acetate, propylene glycol monomethyl acetate, etc.), Ethers [C4-10, eg EG monomethyl ether (methyl cellosorb), EG monoethyl ether (ethyl cellosorb), diethylene glycol monobutyl ether (butyl cellosolve) , Propylene glycol monomethyl ether], aromatic hydrocarbons (C6-10, such as benzene, toluene, xylene), amides (C3-10, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone), halogenated hydrocarbons (C1- 2, for example, methylene dichloride, ethylene dichloride), petroleum solvents (petroleum ether, petroleum naphtha, etc.). These may be used alone or in combination of two or more.
The amount of the organic solvent used is usually 400% or less based on the total weight of the resin composition of the present invention before adding the organic solvent, preferably 25 to 250 from the viewpoint of ease of handling and coating stability. Preferably it is 40 to 150%.

  The resin composition of the present invention can be produced by blending (A) to (C) and, if necessary, (D) and uniformly mixing with a disperser or the like. Used.

As a base material, organic materials, such as a plastics, and inorganic materials, such as a metal and glass, are mentioned. Plastic substrates include various synthetic resins such as acrylonitrile-butadiene-styrene copolymer (ABS) resin, polycarbonate resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polyester resin, polymethyl methacrylate (PMMA). ) Resin, polystyrene (PS) resin, and polyolefin resin.
The metal substrate is not particularly limited. For example, steel plates such as hot-rolled plates and cold-rolled plates, hot-dip galvanized steel plates, electrogalvanized steel plates, tinplate, tin-free steel, and other various plated or alloy-plated steel plates, Metal plates, such as a stainless steel plate and an aluminum plate, are mentioned. Further, it may be subjected to various surface treatments such as phosphate treatment, chromate treatment, organic phosphate treatment, organic chromate treatment, heavy metal substitution treatment such as nickel.

  The resin composition of the present invention is applied to at least a part of at least one surface of the substrate surface, and cured by irradiation with active energy rays to form a cured product (cured film). A coating having at least part of one side can be obtained.

  The active energy rays in the present invention 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 prevention of resin deterioration.

When the resin composition of the present invention is cured by ultraviolet irradiation, various ultraviolet irradiation apparatuses [for example, model number “VPS / I600” manufactured by Fusion UV Systems Co., Ltd.], a light source such as a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, etc. Can be used.
The amount of ultraviolet irradiation (unit: mJ / cm @ 2) is usually 10 to 10,000, preferably 100 to 5,000, more preferably from the viewpoint of the curability of the composition and the flexibility of the cured product (cured film). 300-3,000.

  Moreover, when hardening a resin composition by electron beam irradiation, various electron beam irradiation apparatuses [For example, an electron beam, Iwasaki Electric Co., Ltd. product] can be used. The irradiation amount (Mrad) of the electron beam is preferably 0.5 to 20, and preferably 1 to 15 from the viewpoints of curability of the composition and flexibility of the cured product, and prevention of damage to the substrate.

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

Production Example 1
A reaction vessel equipped with a stirrer and a thermometer was charged with 75.1 parts of 2-hydroxy-3-acryloyloxypropyl methacrylate [trade name “Light Ester G-201P”, manufactured by Kyoeisha Chemical Co., Ltd.] and stirred. 24.9 parts of diphosphorus pentoxide [trade name “phosphorus oxide (5)”, manufactured by Kanto Chemical Co., Ltd.] was added in small portions, heated to 40 ° C., reacted for 4 hours, and one acryloyl per molecule. A phosphate ester (A-1) having a group and one methacryloyl group was obtained.

Production Example 2
In Production Example 1, instead of 2-hydroxy-3-acryloyloxypropyl methacrylate, PE triacrylate [trade name “Light acrylate PE-3A”, manufactured by Kyoeisha Chemical Co., Ltd.] 67.7 parts, and diphosphorus pentoxide A phosphate ester (A-2) having three acryloyl groups in one molecule was obtained in the same manner as in Production Example 1 except that 19.2 parts were used instead of 24.9 parts.

Production Example 3
Instead of 2-hydroxy-3-acryloyloxypropyl methacrylate in Production Example 1, DPE pentaacrylate [trade name “Aronix M-403”, manufactured by Toagosei Co., Ltd.] 88.1 parts, and diphosphorus pentoxide 24. Phosphate ester (A-3) having 5 acryloyl groups in one molecule was obtained in the same manner as in Production Example 1 except that 11.9 parts were used instead of 9 parts.

Examples 1-5, Comparative Examples 1-2
It compounded according to Table 1 and obtained the resin composition (Examples 1-5, Comparative Examples 1-2). The blending components are as follows.
Ratio A-1: 2-Methacryloyloxyethyl acid phosphate [trade name “Light Ester P-1M”, manufactured by Kyoeisha Chemical Co., Ltd.]
B-1: DPE hexaacrylate [trade name “Neomer DA-600”, manufactured by Sanyo Chemical Industries, Ltd.]
B-2: PE triacrylate [trade name “light acrylate PE3A”,
Kyoeisha Chemical Co., Ltd.]
B-3: DPE pentaacrylate [trade name “Aronix M-403”,
Toagosei Co., Ltd.]
C-1: 1-hydroxycyclohexyl phenyl ketone [trade name “Irgacure 184”, manufactured by Ciba Specialty Chemicals Co., Ltd.]

  About the said resin composition, performance evaluation was performed in accordance with the following method. The results are shown in Table 1.

<Performance evaluation method>
(1) Adhesion (1-1) Initial adhesion After applying the resin composition to each of the following substrates using a # 10 bar coater (thickness immediately after application is 25 μm), an ultraviolet irradiation device [model number “ Using VPS / I600 ", manufactured by Fusion UV Systems Co., Ltd.], an ultraviolet ray of 1,000 mJ / cm <2> was irradiated to cure the coating film to obtain a coated specimen. In accordance with JIS K5400, evaluation was performed according to the following criteria by a cross-cut test (gap spacing 1 mm).

○ The remaining squares are 90-100
△ 50-89 remaining squares
× The number of remaining squares is 0 to 49

(Base material)
(1) Silicate glass plate [Nippon Test Panel Co., Ltd., Size 1.0 mm (thickness)
× 7cm × 15cm]
(2) PET film [trade name “Cosmo Shine A4300”, Toyobo Co., Ltd.
Manufactured, size 100 μm (thickness) × 10 cm × 10 cm]
(3) Aluminum vapor-deposited ABS plate [size 50 nm (thickness) × 10 cm × 10 cm]

(1-2) Moisture and heat-resistant adhesion After leaving the test piece similar to (1-1) above for 72 hours under the conditions of 65 ° C. and 95% RH, it is further 24 hours under the conditions of 23 ° C. and humidity 50% RH After leaving still, according to JIS K5600, it evaluated by the following reference | standard by the cross cut test (gap space | interval 1mm).

○ The number of grids remaining is 90-100.
Δ The number of grids remaining is 50-89.
X The number of remaining squares is 0 to 49.

(2) Pencil hardness It measured by scratch hardness (pencil method) based on JIS K5600.

  From the results of Table 1, it can be seen that the cured product of the present invention is extremely excellent in adhesiveness (initial adhesiveness and wet heat resistant adhesiveness) with various substrates, although the pencil hardness is 2H or more.

  In the active energy ray-curable resin composition of the present invention, a cured product (film) obtained by curing the resin composition has high adhesiveness (initial adhesion and adhesion) with a substrate such as plastic, metal, or glass. Adhesive for bonding optical films (electrical / electrical components, paper, plastics, etc.) and optical films (antireflection film, hard coating film, light diffusion sheet, etc.) It is useful as an adhesive for bonding optical disks, a sealing agent for display panels (liquid crystal, organic EL, etc.), an adhesive for optical members, or a sealing agent.

Claims (6)

Activity comprising a phosphate ester (A) having two or more (meth) acryloyl groups in one molecule, a polyfunctional (meth) acrylate (B) excluding (A) and a photopolymerization initiator (C) Energy ray curable resin composition. The ratio based on the total weight of (A), (B), and (C) is 20 to 80% for (A), 19 to 79% for (B), and 1 to 15% for (C). The composition as described. Further, a group consisting of a filler, an antistatic agent, an organic pigment, a slip agent, a dispersant, a thixotropic agent (thickener), a silane coupling agent, a leveling agent, an antifoaming agent, an ultraviolet absorber and an antioxidant. The composition according to claim 1 or 2, comprising an additive (D) selected from: The coating agent, adhesive agent, or sealing agent formed by containing the composition in any one of Claims 1-3. Hardened | cured material formed by apply | coating the composition in any one of Claims 1-3 to at least one part of at least one side of a base material surface, and irradiating an active energy ray and hardening. A coating comprising the cured product according to claim 5 on at least a part of at least one side of a substrate.