JP2010241917A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which has a low shrink on curing and gives a cured film having a high hardness without causing curling and cracking, and an over-coat agent using the same. <P>SOLUTION: The resin composition includes a urethane (meth)acrylate obtained by reacting glycerin (meth)acrylate (a) with an alicyclic polyisocyanate compound or a urethane (meth)acrylate obtained by reacting glycerin (meth)acrylate (a) and a (meth)acrylate (a-1) other than (a) with a polyisocyanate (b), a (meth)acrylate, and a photopolymerization initiator. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition containing urethane (meth) acrylate using glycerin (meth) acrylate as a raw material. Furthermore, the cured film of the resin composition of the present invention is excellent in hardness, adhesion to a base material, scratch resistance, etc., has small curl and less cracking, and is useful as an overcoat for plastic films and small cases It is.

  Currently, plastics that are excellent in various points such as lightness, low cost, and optical properties in addition to processability and transparency are used in the industry. However, since plastics are softer than glass and have defects such as the surface being easily scratched, it is common practice to coat the plastic surface with an overcoat agent. Among the overcoat agents, there are many known hard coat agents for improving the surface hardness, such as thermosetting types such as silicone paints, acrylic paints, and melamine paints. Among them, silicone-based hard coat agents have been mainly used because of their excellent performance and quality, but on the other hand, there are also disadvantages that the curing time is long and expensive.

  Then, the photosensitive acrylic type hard-coat agent which compensates the fault of a silicone type hard-coat agent was developed and came to be utilized (refer patent document 1). The acrylic hard coat agent is immediately cured by irradiation with radiation such as ultraviolet rays, and the processing speed is high. Further, since it is excellent in hardness, scratch resistance and the like and is inexpensive, it has become the mainstream in the hard coat field. It is particularly suitable for continuous processing of films such as polyester.

  Examples of the plastic film include a polyester film, an acrylic film, a polycarbonate film, a vinyl chloride film, a triacetyl cellulose film, and a polyethersulfone film. The polyester film is most widely used because of various excellent characteristics. This polyester film is a glass shatterproof film, or a light shielding film for automobiles, a whiteboard surface film, a system kitchen surface antifouling film, and electronic materials such as CRT flat TV, touch panel, liquid crystal display (LCD), plasma It is widely used as a functional film such as a display (PDP) and an organic EL display, a body and a switch of home appliances, an electronic device casing such as a mobile phone, a personal computer, and an MP3 player. All of these are coated with a hard coat so as not to scratch the surface. In addition to plastic films, polycarbonate and acrylic sheets and substrates that are hard-coated are also used for liquid crystal related members around optical disks and backlights.

For a substrate coated with a hard coat agent in recent years, functionality other than the performance as a hard coat called scratch resistance is required. For example, a display body such as a CRT, LCD, or PDP provided with a film makes it difficult to see the display body screen due to reflection, and the eyes tend to become tired. Therefore, depending on the application, a hard coat treatment having a surface antireflection function is required. (See Patent Document 2).

  While a hard coat imparted with functionality is required, studies have been made to improve the hardness, which is the original purpose of the hard coat. For example, Patent Document 3 attempts to improve hardness by adding polyfunctional urethane acrylate to the resin composition. However, there is a problem that the curing shrinkage of the polyfunctional urethane acrylate being used is large and cracks are observed. Furthermore, the amount of addition or the composition of the whole composition is limited.

  Patent Document 4 and Patent Document 5 describe resin compositions containing urethane (meth) acrylate obtained by reacting glycerin (meth) acrylate (a) and polyisocyanate compound (b). Patent Document 4 describes a resin composition used for a film serving as a protective mask such as a solder resist for printed wiring, in which a polymer having a mass average molecular weight of 10,000 or more and trisacryloyloxyethyl isocyanurate are essential. However, hardness and scratch resistance are not required, and the shrinkage rate is not considered. Patent Document 5 describes a composition for three-dimensional modeling including modified silica fine particles, but does not describe a hard coat.

Japanese Patent Laid-Open No. 9-48934 JP-A-9-145903 JP 2001-113648 A Japanese Patent Laid-Open No. 62-290705 JP-A-9-87513

  In order to develop a harder overcoat in the tendency for the film of the base material to become thinner, methods such as using a hard material itself, increasing the degree of crosslinking, and setting the film thickness to a thicker are being tried. There are problems such as the occurrence of cracks and the occurrence of curling by increasing the degree of crosslinking with a thick film.

  The present invention provides a resin composition that improves the above-mentioned drawbacks, is capable of thick film coating, is excellent in hardness, gives a cured film free from curling and cracking, and has a low shrinkage during curing. Objective.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that a resin composition having a specific compound and composition can solve the above problems, and have reached the present invention.

That is, the present invention
(1) Contains urethane (meth) acrylate (A), (meth) acrylate (B) and photopolymerization initiator (C) obtained by reacting glycerin (meth) acrylate (a) with an alicyclic polyisocyanate compound. A resin composition,
(2) Urethane (meth) acrylate (A-1) obtained by reacting (meth) acrylate (a-1) other than glycerin (meth) acrylate (a) and (a) with polyisocyanate compound (b) , A resin composition containing (meth) acrylate (B) and a photopolymerization initiator (C),
(3) The resin composition according to (1) or (2), which is for overcoat,
About.

  INDUSTRIAL APPLICABILITY According to the present invention, there are provided a resin composition that gives a cured film having a low shrinkage ratio upon curing, high hardness, and no curling or cracking, and an overcoat agent using the resin composition.

  Hereinafter, the present invention will be described in detail.

  The urethane (meth) acrylate (A) used in the resin composition of the present invention is obtained by reacting glycerin (meth) acrylate (a) with a polyisocyanate compound (b). There is no limitation in particular in the number of (meth) acryloyl groups which glycerin (meth) acrylate (a) has.

  Urethane (meth) acrylate (A-1) used in the resin composition of the present invention is glycerin (meth) acrylate (a) and (meth) acrylate (a-1) other than (a) and polyisocyanate compound (b). Obtained by reacting with. There is no limitation in particular in the number of (meth) acryloyl groups which glycerin (meth) acrylate (a) has.

  Examples of glycerol (meth) acrylate (a) that can be used in the resin composition of the present invention include glycerol diacrylate, glycerol dimethacrylate, glycerol monoacrylate monomethacrylate, diglycerol triacrylate, and diglycerol trimethacrylate. . Among these, glycerol diacrylate, glycerol dimethacrylate, and glycerol monoacrylate monomethacrylate are preferable.

  The (meth) acrylate (a-1) other than (a) that can be used in the resin composition of the present invention is not particularly limited as long as it has an active hydrogen group, and includes a hydroxyl group-containing (meth) acrylate and pentaerythritols. And monofunctional and polyfunctional (meth) acrylates such as methylols and epoxy acrylates.

  Examples of (meth) acrylate (a-1) other than (a) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and cyclohexanedimethanol mono Hydroxyl group-containing (meth) acrylates such as (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate; pentaerythritol tri (meth) acrylate , Pentaerythritol tetraacrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Pentaerythritols such as dipentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, methylols such as trimethylolpropane di (meth) acrylate, and epoxy acrylates such as bisphenol A diepoxy acrylate be able to.

  In addition, you may use (meth) acrylate (a-1) other than these (a) individually or in mixture of 2 or more types.

  As the (meth) acrylate (a-1) other than (a) that can be used in the resin composition of the present invention, a polyfunctional (meth) acrylate is preferable, and a trifunctional or higher (meth) acrylate, particularly pentaerythritol. Triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or mixtures thereof are preferred.

  The polyisocyanate compound (b) that can be used in the resin composition of the present invention is not particularly limited as long as it is a compound containing two or more isocyanate groups in one molecule, and examples thereof include aliphatic polyisocyanate compounds and aromatic compounds. Group polyisocyanate compounds, alicyclic polyisocyanates, trimer or multimer compounds thereof, burette type polyisocyanates, allophanate type polyisocyanates and the like. A trimer or multimeric compound means a compound in which three isocyanate groups form one or more isocyanurate ring structures. Furthermore, you may use a polyisocyanate compound (b) individually or in mixture of 2 or more types.

  Examples of the aliphatic polyisocyanate compound include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-diisocyanate cyclohexane, 1,4- Diisocyanate cyclohexane, dicyclohexylmethane-4,4′-diisocyanate, m-tetramethylxylene diisocyanate, p-tetramethylxylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4-trimethyl Cyclohexane diisocyanate, 2,4,4-trimethylcyclohexane diisocyanate, 2,2,4-trimethylhexamethylene diiso Aneto, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate and the like.

  Examples of the aromatic polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,4-phenylene diisocyanate, 1,6-phenylene diisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include cyclohexane diisocyanate, hydrogenated tolylene diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate, and norbornane diisocyanate.

  In the present invention, the polyisocyanate compound (b) is preferably an aliphatic polyisocyanate compound, more preferably an alicyclic polyisocyanate, still more preferably isophorone diisocyanate and isophorone diisocyanate trimer or multimeric compound. .

  The urethane (meth) acrylate (A) used in the present invention is obtained by reacting glycerin (meth) acrylate (a) and a polyisocyanate compound (b), preferably an alicyclic polyisocyanate compound. (A-1) is obtained by reacting (meth) acrylate (a-1) other than glycerin (meth) acrylate (a) and (a) with the polyisocyanate compound (b). (A) and (A-1) may be used alone or in combination in the resin composition of the present invention. Polyisocyanate compound (b) is usually 0.1 to 0.1 equivalents of isocyanate group equivalent to 1 equivalent of active hydrogen group in (meth) acrylate (a-1) other than glycerin (meth) acrylate (a) and (a). The range is 50 equivalents, preferably 0.1 to 10 equivalents. The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is calculated by a method in which the amount of residual isocyanate is reacted with an excess of n-butylamine and back titrated with 1N hydrochloric acid, and the end when the isocyanate is 0.5% by mass or less.

  A catalyst may be added for the purpose of shortening the reaction time. As this catalyst, either a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphine such as tributylphosphine and triphenylphosphine. Examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, trititanium tetrabutoxide, zirconium tetrabutoxide and the like, Lewis acids such as aluminum chloride, and 2-ethylhexanetin. , Tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. The addition amount of these catalysts is 0.1 mass part or more normally 1 mass part or less with respect to 100 mass parts of polyisocyanate compounds (b).

  Further, during the reaction, a polymerization inhibitor (for example, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5 is used to prevent polymerization during the reaction. -Dihydroxy-p-benzoquinone, phenothiazine, etc.) is preferably used, and the amount of the polymerization inhibitor used is 0.01% by weight or more and 1% by weight or less, preferably 0.05% by weight, based on the reaction mixture. It is 0.5 mass% or less. The reaction temperature is 60 to 150 ° C, preferably 80 to 120 ° C.

  In the resin composition of the present invention, the use amount of the above (A) and / or (A-1) is usually 5% by mass or more and 97% by mass when the solid content of the resin composition of the present invention is 100% by mass. Or less, preferably 21% by mass or more and 80% by mass or less.

  The (meth) acrylate (B) used in the present invention is not particularly limited. Monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or higher (meth) acrylate, polyester (meth) acrylate, urethane ( A meth) acrylate oligomer, a polyester (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, etc. can be mentioned.

  Examples of monofunctional (meth) acrylates include: acryloylmorpholine; hydroxyl-containing (meth) acrylates such as 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; cyclohexane-1,4-dimethanol mono ( Aliphatic (meta) such as (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate ) Acrylate, phenoxyethyl (meth) acrylate, phenyl (poly) ethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate Aromatic (meth) acrylates such as rate, phenylthioethyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, phenylphenol (poly) ethoxy (meth) acrylate, and phenylphenol epoxy (meth) acrylate Can be mentioned.

  As bifunctional (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol (Meth) acrylate, bisphenol A (poly) ethoxy di (meth) acrylate, bisphenol A (poly) propoxy di (meth) acrylate, bisphenol F (poly) ethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, (poly) ethylene Di (meth) acrylate of ε-caprolactone adduct of glycol di (meth) acrylate hydroxybivalate neopentyl glycol (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.) But it can.

  As trifunctional or more polyfunctional (meth) acrylates, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate , Methylols such as trimethylolpropane (poly) propoxytri (meth) acrylate, trimethylolpropane (poly) ethoxy (poly) propoxytri (meth) acrylate; pentaerythritol tri (meth) acrylate, pentaerythritol polyethoxytetra (meta) ) Acrylate, pentaerythritol (poly) propoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol te Erythritols such as la (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; tris [(meth) acryloyloxyethyl] isocyanurate, caprolactone modified tris [(meth) acryloyloxyethyl ] Isocyanurate and the like; and epoxy acrylates such as bisphenol A diepoxy acrylate.

  Examples of the (poly) ester (meth) acrylate include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, polyethylene glycol, and (poly) propylene glycol. 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol , Linear or branched alkyl diols such as 2,4-diethyl-1,5-pentanediol and 2-butyl-2-ethyl-1,3-propanediol, and alicyclic rings such as cyclohexane-1,4-dimethanol Formula Alkyldiols, Bisphe (Poly) ester diol, which is a reaction product of a diol compound such as diol A (poly) ethoxydiol or bisphenol A (poly) propoxydiol and the dibasic acid or anhydride thereof, and (meth) acrylic acid, And the like.

  Examples of the urethane (meth) acrylate oligomer include diol compounds (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6 -Hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5- Pentanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypropoxy Diol etc.) or a reaction product of these diol compounds and dibasic acid or anhydride thereof (for example, succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid or anhydride thereof) Polyester diol and organic polyisocyanate (eg, chain saturated hydrocarbon isocyanate such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate) , Norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diiso Cyclic saturated hydrocarbon isocyanates such as anate, hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate, 6 -Aromatic polyisocyanates such as isopropyl-1,3-phenyl diisocyanate and 1,5-naphthalene diisocyanate) and then a reaction product in which a hydroxyl group-containing (meth) acrylate is added.

  Examples of the (poly) ester (meth) acrylate oligomer include a reaction product of (poly) ester diol and (meth) acrylic acid, which is a reaction product of the above diol compound and the above dibasic acid or its anhydride. Is mentioned.

  In the resin composition of the present invention, the amount of the component (B) used is usually 0% by mass to 94% by mass, preferably 20%, when the solid content of the resin composition of the present invention is 100% by mass. It is at least 79% by mass.

  Examples of the photopolymerization initiator (C) used as necessary in the resin composition of the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2, 2 -Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- Acetophenones such as (methylthio) phenyl] -2-morpholinopropan-1-one; ant such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Quinones; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4 Benzophenones such as 2,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Specifically, from the market, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 907 (2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane manufactured by Ciba Specialty Chemicals, Inc. -1-one), Lucylin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) manufactured by BASF, etc. can be easily obtained. Moreover, you may use these individually or in mixture of 2 or more types.

  In the resin composition of the present invention, the amount of the component (C) used is 0% by mass or more and 10% by mass or less, preferably 1% by mass when the solid content of the resin composition of the present invention is 100% by mass. % To 7% by mass.

  Moreover, said photoinitiator (C) can also be used together with a hardening accelerator (D). Examples of the curing accelerator that can be used in combination include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid isoamino ester, amines such as EPA, 2- And hydrogen donors such as mercaptobenzothiazole. The amount of these curing accelerators used is 0% by mass or more and 5% by mass or less when the solid content of the resin composition of the present invention is 100% by mass.

  Examples of the diluent (E) used as necessary in the resin composition of the present invention include γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, and ε-caprolactone. Lactones such as dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol Ethers such as dimethyl ether and tetraethylene glycol diethyl ether; ethylene carbonate, propylene carbonate Carbonates such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, etc .; phenols such as phenol, cresol, xylenol; ethyl acetate, butyl acetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Esters such as butyl carbitol acetate and propylene glycol monomethyl ether acetate; Hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane; Halogenated hydrocarbons such as trichloroethane, tetrachloroethane and monochlorobenzene, petroleum ether, petroleum naphtha, etc. Organic solvents such as petroleum solvents, fluorine alcohols such as 2H, 3H-tetrafluoropropanol, perfluorobutyl Chirueteru, hydrofluoroethers such as perfluorobutyl ethyl ether; methyl alcohol, ethyl alcohol, isopropyl alcohol, and n- propyl alcohol; and diacetone alcohol combines ketone and both alcohol performance thereof. You may use these individually or in mixture of 2 or more types.

  In the resin composition of the present invention, the amount of the component (E) used is in the range of 0% by mass to 90% by mass, preferably 0% by mass to 80% by mass with respect to the total amount of the resin composition of the present invention. % Or less.

  Further, the resin composition of the present invention may contain a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, a crosslinking agent, etc. as necessary. It is also possible to add desired functionality to each product. Fluorine compounds, silicone compounds, acrylic compounds, etc. as leveling agents, benzotriazole compounds, benzophenone compounds, triazine compounds, etc. as UV absorbers, hindered amine compounds, benzoate compounds as light stabilizers Compounds, antioxidants such as phenolic compounds, polymerization inhibitors include methoquinone, methylhydroquinone, hydroquinone and the like, and crosslinking agents include the polyisocyanates and melamine compounds.

  The resin composition of the present invention comprises the above component (A), component (A-1), component (B), component (C), and component (D), component (E) and other components as necessary. It can be obtained by mixing in any order.

  The resin composition of the present invention is coated on the substrate so that the film thickness after drying of the resin composition is usually 0.1 μm to 50 μm, preferably 1 μm to 20 μm. It can be obtained by irradiating ultraviolet rays after drying to form a cured film.

  Examples of the base film include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetyl cellulose, polyether sulfone, and cycloolefin polymer. The film to be used may be one provided with a handle or an easy adhesion layer, one subjected to surface treatment such as corona treatment, or one subjected to release treatment.

  Examples of the coating method of the resin composition include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, micro reverse gravure coater, and die coater. Examples include coating, dip coating, spin coating, and spray coating.

Although ultraviolet rays are irradiated for curing, an electron beam or the like can also be used. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp or the like is used as a light source, and the light amount, the arrangement of the light source, etc. are adjusted as necessary. When using a high-pressure mercury lamp, it is preferable to cure at a conveyance speed of 5 to 60 m / min for one lamp having an energy of 80 to 120 W / cm ² . On the other hand, when curing with an electron beam, it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV, and the photopolymerization initiator (C) may not be used.

  The resin composition of the present invention includes ink, metals such as aluminum, iron and copper, plastics such as vinyl chloride, acrylic, polycarbonate, polyethylene terephthalate, polyethylene and polypropylene, ceramics such as glass, wood, paper, printing paper, fibers, etc. The various coating materials are useful for applications such as surface treatment agents, binders, plastic materials, molding materials, laminates, adhesives, and pressure-sensitive adhesives. More specific applications include planographic relief inks, flexographic inks, gravure inks, screen inks and other ink fields, glossy fields, paper coating materials fields, wood coating materials fields, beverage can coating materials or printing ink fields, It is useful for applications such as soft packaging film coating agents, printing inks or adhesives, thermal paper, thermal film coating agents, printing inks, adhesives, adhesives or optical fiber coating agents, and molding processing film coating agents.

  Among the above uses, the resin composition of the present invention has a low shrinkage rate upon curing, high hardness, and no occurrence of curling or cracking. Useful for applications.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples. Moreover, unless otherwise indicated in an Example, a part shows a mass part.

Synthesis example 1
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, 344.35 g (1.54 mol) of glycerol monoacrylate / monomethacrylate, 0.25 g of 4-methoxyphenol as a polymerization inhibitor, urethanization As a reaction catalyst, 0.25 g of dibutyltin dilaurate was added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. Subsequently, 155.65 g (0.70 mol) of isophorone diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and the reaction was carried out at 80 ° C. after the addition, and the reaction was performed when the NCO content was 0.1% or less. The urethane acrylate was obtained.

Synthesis example 2
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller, 262.60 g (1.17 mol) of glycerin monoacrylate / monomethacrylate, 125.00 g of methyl ethyl ketone, 4-methoxyphenol 0 as a polymerization inhibitor .25 g, 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst was added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. Subsequently, 237.40 g (0.36 mol) of T-1890 (isophorone diisocyanate trimer) was added dropwise so that the internal temperature did not exceed 80 ° C., and the reaction was carried out at 80 ° C. after the addition. The resin solution containing 80% of urethane acrylate was obtained with the end point of the reaction as the end point of the reaction.

Synthesis example 3
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller, 187.14 g (0.84 mol) of glycerol monoacrylate / monomethacrylate, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (parts by mass) Mixing ratio: 65/35, hydroxyl equivalent: 458.9 g / Eq) 187.08 g (0.41 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor, 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst The mixture was stirred until uniform, and the internal temperature was adjusted to 50 ° C. Subsequently, 125.78 g (0.57 mol) of isophorone diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and the reaction was carried out at 80 ° C. after the addition, and the reaction was performed when the NCO content was 0.1% or less. The urethane acrylate was obtained.

Synthesis example 4
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, 80.42 g (0.36 mol) of glycerin monoacrylate / monomethacrylate, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (parts by mass) Mixing ratio: 65/35, hydroxyl group equivalent: 458.9 g / Eq) 240.83 g (0.52 mol), methyl ethyl ketone 125.00 g, 4-methoxyphenol 0.25 g as a polymerization inhibitor, dibutyltin dilaurate as a urethanization reaction catalyst 0.25g was added and it stirred until it became uniform, and internal temperature was 50 degreeC. Subsequently, 178.75 g (0.27 mol) of T-1890 (isophorone diisocyanate trimer) was added dropwise so that the internal temperature did not exceed 80 ° C., and the reaction was carried out at 80 ° C. after the addition. The resin solution containing 80% of urethane acrylate was obtained with the end point of the reaction as the end point of the reaction.

Synthesis example 5
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller, 149.51 g (0.67 mol) of glycerol monoacrylate / monomethacrylate, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (parts by mass) Mixing ratio: 65/35, hydroxyl group equivalent: 458.9 g / Eq) 149.50 g (0.33 mol), methyl ethyl ketone 125.00 g, 4-methoxyphenol 0.25 g as a polymerization inhibitor, dibutyltin dilaurate as a urethanization reaction catalyst 0.25g was added and it stirred until it became uniform, and internal temperature was 50 degreeC. Subsequently, 200.99 g (0.30 mol) of T-1890 (isophorone diisocyanate trimer) was added dropwise so that the internal temperature did not exceed 80 ° C., and the reaction was carried out at 80 ° C. after the addition. The resin solution containing 80% of urethane acrylate was obtained with the end point of the reaction as the end point of the reaction.

Synthesis Example 6
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller, 209.60 g (0.94 mol) of glycerin monoacrylate / monomethacrylate, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (parts by mass) Mixing ratio: 65/35, hydroxyl equivalent: 458.9 g / Eq) 70.07 g (0.15 mol), methyl ethyl ketone 125.00 g, 4-methoxyphenol 0.25 g as a polymerization inhibitor, dibutyltin dilaurate as a urethanization reaction catalyst 0.25g was added and it stirred until it became uniform, and internal temperature was 50 degreeC. Subsequently, 220.34 g (0.33 mol) of T-1890 (isophorone diisocyanate trimer) was added dropwise so that the internal temperature did not exceed 80 ° C., the reaction was carried out at 80 ° C. after the addition, and the NCO content was 0.1 The resin solution containing 80% of urethane acrylate was obtained with the end point of the reaction as the end point of the reaction.

Synthesis example 7
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, 197.71 g (0.88 mol) of glycerol monoacrylate / monomethacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ( Mass part mixing ratio: 40/60, hydroxyl group equivalent: 1311.2 g / Eq) 197.69 g (0.15 mol), 4-methoxyphenol 0.25 g as a polymerization inhibitor, dibutyltin dilaurate 0.25 g as a urethanization reaction catalyst Was added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. Subsequently, 104.60 g (0.47 mol) of isophorone diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and the reaction was carried out at 80 ° C. after the addition, and the reaction was performed when the NCO content was 0.1% or less. The urethane acrylate was obtained.

Synthesis example 8
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller, 163.51 g (0.73 mol) of glycerol monoacrylate / monomethacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ( Mass part mixing ratio: 40/60, hydroxyl group equivalent: 1311.2 g / Eq) 163.49 g (0.36 mol), methyl ethyl ketone 125.00 g, 4-methoxyphenol 0.25 g as a polymerization inhibitor, urethanization reaction catalyst 0.25 g of dibutyltin dilaurate was added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. Subsequently, 173.01 g (0.26 mol) of T-1890 (isophorone diisocyanate trimer) was added dropwise so that the internal temperature did not exceed 80 ° C., and the reaction was carried out at 80 ° C. after the addition. The resin solution containing 80% of urethane acrylate was obtained with the end point of the reaction as the end point of the reaction.

Comparative Synthesis Example 1
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, 372.58 g (1.67 mol) of glycerol monoacrylate / monomethacrylate, 0.25 g of 4-methoxyphenol as a polymerization inhibitor, urethanization As a reaction catalyst, 0.25 g of dibutyltin dilaurate was added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. Subsequently, 127.42 g (0.76 mol) of hexamethylene diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and the mixture was reacted at 80 ° C. after the addition, so that the NCO content was 0.1% or less. This was the end point of the reaction, and urethane acrylate was obtained.

Comparative Synthesis Example 2
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (mass part mixing ratio: 65/35, hydroxyl group equivalent: 458.9 g / Eq) 409.77 g (0.89 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform, and the internal temperature was adjusted to 50 ° C. Subsequently, 90.23 g (0.41 mol) of isophorone diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and the mixture was reacted at 80 ° C. after the addition, and the NCO content was 0.1% or less. Was used as the end point of the reaction to obtain urethane acrylate.

Comparative Synthesis Example 3
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (parts by mass mixing ratio: 40/60, hydroxyl group equivalent: 1311.2 g / Eq) 464.23 g (0.35 mol), 0.25 g of 4-methoxyphenol as a polymerization inhibitor and 0.25 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform, and the internal temperature was 50 ° C. did. Subsequently, 35.77 g (0.16 mol) of isophorone diisocyanate was added dropwise so that the internal temperature did not exceed 80 ° C., and the mixture was reacted at 80 ° C. after the addition, and the NCO content was 0.1% or less. Was used as the end point of the reaction to obtain urethane acrylate.

Examples 1-10 and Comparative Examples 1-5
A resin composition containing the materials shown in Table 1 and Table 2 was applied onto a readily adhesive-treated PET film (film thickness 125 μm) with a bar coater, dried at about 80 to 100 ° C., and then irradiated with an ultraviolet irradiator (JAPAN STORE). BATTERY CO, LTD .: CS30L-1-1) High-pressure mercury lamp: 120 W / cm; lamp height: 10 cm; conveyor speed: 10 m / min (energy: about 300 mW / cm ² , about 200 mJ / cm ² ) A hard coat film having a thickness of about 5 μm was obtained by curing. In Tables 1 and 2, the unit represents “part”.

(note)
* 1: KAYARAD DPHA (dipentaerythritol pentaacrylate / hexaacrylate mixture) manufactured by Nippon Kayaku Co., Ltd.
* 2: Methyl ethyl ketone * 3: 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals

  The following items were evaluated for the hard coat films obtained in Examples 1 to 10 and Comparative Examples 1 to 5, and the results are shown in Table 3.

(Pencil hardness)
According to JIS K 5600-5-4, the pencil hardness of the coating film having the above composition was measured using a pencil scratch tester. Specifically, on the polyester film having the cured film to be measured, the pencil is applied with a load of 750 g from the top at a 45 degree angle, and is scratched for about 5 mm. expressed.
(Adhesion)
The film surface after the light resistance test was scratched on the cloth with a cutter, and a cellophane tape was affixed thereon and peeled at an angle of 90 degrees.
○: No peeling ×: Peeling occurred

(Abrasion resistance)
Steel wool # 0000 was reciprocated 10 times with a load of 200 g / cm ² , and the condition of the scratch was visually confirmed.
○: No scratch ×: Scratch occurred

(curl)
A polyester film having a cured film to be measured was cut into 5 cm × 5 cm, left in an oven at 80 ° C. for 1 hour, and then returned to room temperature. The height of each of the four sides that floated on a horizontal table was measured, and the sum of the four sides was taken as the measured value (unit: mm). At this time, the curl of the base material itself was 0 mm.

(Tackiness)
A resin composition containing the materials shown in Table 1 and Table 2 is applied onto a PET film (film thickness 125 μm) that has been subjected to an easy adhesion treatment with a bar coater, and the absorbent cotton is rubbed onto the coating film after drying at about 80 to 100 ° C. The tackiness of the film was evaluated.
Evaluation ○: Absorbent cotton is not attached.
X: Absorbent cotton lint sticks to the coating film.

(appearance)
Surface cracks, whitening, cloudiness, etc. were judged visually.
Evaluation ○: Good ×: Significant crack occurrence

(Curing shrinkage)
To the compounds obtained in Synthesis Examples 1-8 and Comparative Synthesis Examples 1-3, Irg. 3% by mass of 184 was added, applied onto a glass substrate using a bar coater, and irradiated with ultraviolet rays using an ultraviolet irradiator to obtain a cured product having a thickness of about 200 μm. However, for the compounds of Synthesis Example 2, Synthesis Examples 4 to 6, and Synthesis Example 8, MEK as a solvent was evaporated from a resin solution containing urethane acrylate. The cure shrinkage was calculated from the following formula (1) from the liquid specific gravity before curing at 25 ° C. and the liquid specific gravity of the cured product, and the results are shown in Table 4.

Formula (1)
Curing shrinkage = (film specific gravity−liquid specific gravity) / film specific gravity × 100

  As is apparent from the results in Table 3, the film having the cured film of the resin composition of the present invention has good hardness, adhesion, and scratch resistance, small curl, and no occurrence of cracks. Furthermore, in Examples 2, 5, 6, 9, and 10 containing urethane (meth) acrylate composed of trimer alicyclic polyisocyanate, tackiness is good. Further, as is clear from the results in Table 4, the urethane (meth) acrylate contained in the resin composition of the present invention has a small shrinkage rate upon curing, and is therefore effective in suppressing the occurrence of curls and cracks. is there.

  The hard coat film obtained with the resin composition of the present invention has good hardness, adhesion, and scratch resistance, has a small shrinkage ratio upon curing, and does not cause curling or cracking. Therefore, the resin composition of the present invention is useful as an overcoat for a plastic film or a small casing.

Claims (3)

Resin composition containing urethane (meth) acrylate (A), (meth) acrylate (B) and photopolymerization initiator (C) obtained by reacting glycerin (meth) acrylate (a) with an alicyclic polyisocyanate compound object. Urethane (meth) acrylate (A-1) and (meth) obtained by reacting (meth) acrylate (a-1) other than glycerin (meth) acrylate (a) and (a) with polyisocyanate (b). A resin composition containing an acrylate (B) and a photopolymerization initiator (C). The resin composition according to claim 1 or 2, which is used for overcoat.