JP4415797B2 - Photocurable resin composition - Google Patents

Description

  The present invention relates to a photocurable resin composition, a coating composition, a cured product thereof, and a laminate including these layers.

The photo-curable resin composition and paints using this one-pack type can extend the pot life and shorten the curing time, so it can be used for woodworking, plastic, paper, and metal substrate coating and thermoforming protection When applied to a sheet or the like, an improvement in productivity is expected (Patent Document 1).
Japanese Patent Application Laid-Open No. 11-1000041

  However, most of the photocurable resin compositions are liquid photocurability generically referred to as low molecular weight acrylic ester compounds (epoxy acrylate, urethane acrylate, oligoester acrylate, etc.) and reactive diluent monomers collectively referred to as oligomers. Since the compound is mixed, the coating film until photocured is a liquid or sticky solid, and there is a problem that dust and dust adhere to the coating film during the coating process.

  Such inconvenience has also occurred in the field of thermal transfer printing where a sheet-like composition (laminated body) in which a layer of a photocurable resin composition is previously formed on a film is used.

  Then, the objective of this invention is providing the photocurable resin composition which can make an uncured coating-film surface a non-adhesion state, and can prevent adhesion of refuse and dust.

  In order to achieve the above object, the present invention provides (A) a polymer in which a polymerizable unsaturated bond is formed at the side chain and / or terminal of a (meth) acrylic polymer having a weight average molecular weight of 20,000 or more. (B) a urethane compound having at least three polymerizable unsaturated bonds in one molecule, and (C) a compound having at least four polymerizable unsaturated bonds in one molecule and different from the component (B). A photocurable resin composition (hereinafter referred to as “first photocurable resin composition”) containing a functional (meth) acrylate and (D) a photopolymerization initiator is provided.

  The photocurable resin composition of the present invention may contain a photopolymerizable monomer other than the above. That is, the present invention relates to (A) a polymer having a polymerizable unsaturated bond formed at the side chain and / or terminal of a (meth) acrylic polymer having a weight average molecular weight of 20,000 or more, and (B) 1 A urethane compound having at least three polymerizable unsaturated bonds in the molecule; (C) a polyfunctional (meth) acrylate having at least four polymerizable unsaturated bonds in one molecule and different from the component (B); , (D) a photopolymerization initiator, and (E) a photocurable resin composition having a polymerizable unsaturated bond and a photopolymerizable monomer different from the component (B) and the component (C) ( (Hereinafter referred to as “second photocurable resin composition”).

  In the first and second photocurable resin compositions of the present invention, the surface of the uncured coating film is non-tacky, and it is possible to prevent adhesion of dust and dust. Since there is no adhesion of dust and dust, the dust and dust inspection process and the like can be omitted, so that the efficiency of the process to which the photocurable resin composition is applied is improved. The fact that there is no adhesion of dust and dust also means that dust and dust do not enter the product to which the photocurable resin composition is applied, and the quality of the final product is improved.

  The first and second photocurable resin compositions are effective as components of the coating composition, and are coating compositions containing a resin composition that forms a coating film. The coating composition containing the photocurable resin composition of this can be provided.

  Since the coating composition is applied to the surface of the product, a good surface condition is required. However, since the coating composition of the present invention includes the first and second photocurable resin compositions, The adhesion of dirt and dust is prevented and the beauty of the painted surface can be improved.

  In addition, the hardened | cured material of the 1st and 2nd photocurable resin composition or coating composition exhibits very excellent mechanical strength, surface scratch resistance, and chemical resistance.

  The 1st and 2nd photocurable resin composition and coating composition can be shape | molded in a sheet form. That is, a laminate comprising a layer made of the first or second photocurable resin composition or the coating composition on one side or both sides of a film-like substrate is provided. This laminated body exhibits the above-described characteristics, and can be stacked or rolled up without being covered with a cover sheet or the like.

  According to the present invention, the surface of the uncured coating film can be made non-adhesive, and it is possible not only to prevent adhesion of dust and dust, but also when the sheet is processed into a sheet shape, it is not covered with a cover sheet or the like. It is possible to provide a photocurable resin composition that gives a cured product excellent in mechanical strength, surface scratch resistance and chemical resistance after curing.

  Hereinafter, preferred embodiments of the present invention will be described. In the present invention, (meth) acrylate means acrylate or a corresponding methacrylate. The (meth) acrylic polymer refers to a polymer polymerized using a monomer having a (meth) acryloyl group as an essential component, and the urethane compound refers to a compound having a urethane bond in the molecule. The polymerizable unsaturated bond means a bond that can be polymerized by the photopolymerization initiator (D) of the present invention, and an ethylenically unsaturated bond is representative.

(A) component:
The component (A) is a (meth) acrylic polymer having a polymerizable unsaturated bond and a weight average molecular weight of 20,000 or more. The component (A) first synthesizes a (meth) acrylic polymer having a functional group X in the side chain and a weight average molecular weight of 20,000 or more, and reacts with the (meth) acrylic polymer and the functional group X. It is preferably obtained by reacting a compound having a functional group Y and a polymerizable unsaturated bond. The combination of the functional group X and the functional group Y includes an epoxy group and a hydroxyl group, an epoxy group and a carboxyl group, a group having an active hydrogen (hydroxyl group, mercapto group, carboxyl group, etc.) and an isocyanate group, a hydroxyl group and an acid halide group (or Carboxyl group), alkoxysilyl group and condensed group (hydroxyl group). In each combination, one side may be the functional group X and the other side may be the functional group Y.

  (A) As a 1st aspect of a component, it is obtained by superposing | polymerizing (I) (meth) acrylic-acid glycidyl ester and the monomer which has a polymerizable unsaturated bond of (II) 1, and is different from (I) component. Examples include (meth) acrylic polymers obtained by reacting (III) a carboxylic acid having a polymerizable unsaturated bond with a copolymer having a weight average molecular weight of 20,000 or more. Further, as a second embodiment of the component (A), (i) a (meth) acrylate containing a hydroxyl group and (ii) a monomer having a polymerizable unsaturated bond of 1 and a monomer different from the component (i) are polymerized. (Iii) a (meth) acrylic polymer obtained by reacting a copolymer having an isocyanate group and a polymerizable unsaturated bond with the copolymer having a weight average molecular weight of 20,000 or more is obtained.

  As the component (II) or component (ii), various esters of acrylic acid or methacrylic acid are preferable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl ( Alkyl such as (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate (Meth) acrylate; alkoxyalkyl (meth) acrylate such as ethoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate Hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate; alkoxyalkoxyalkyl (meth) acrylates such as 2-methoxyethoxyethyl (meth) acrylate and 2-ethoxyethoxyethyl (meth) acrylate; methoxy Alkoxy (poly) alkylene glycols (meth) such as diethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, butoxytriethylene glycol (meth) acrylate, and methoxydipropylene glycol (meth) acrylate Acrylate; pyrenoxide adduct (meth) acrylate, octafluoropentyl (meth) acrylate, N, N-dimethylamino ester Le (meth) acrylate, N, 1 kind or a mixture of two or more combinations of such dialkylaminoalkyl (meth) acrylates such as N- diethylaminoethyl (meth) acrylate.

  The copolymer of (I) component and (II) component ((meth) acrylic polymer) can be obtained by carrying out a copolymerization reaction by a known method such as a solution polymerization method in the presence of a radical polymerization initiator. it can. Here, as these compounding ratios, it is preferable that (I) component is 30-50 mass parts with respect to 100 mass parts of total amounts of (I) component and (II) component, and 35-45 masses. More preferably, it is a part. Further, the component (II) is preferably 50 to 70 parts by mass, and more preferably 55 to 65 parts by mass with respect to 100 parts by mass of the total amount of the components (I) and (II).

  The copolymer of component (i) and component (ii) ((meth) acrylic polymer) can also be obtained by a copolymerization reaction by a known method such as a solution polymerization method in the presence of a radical polymerization initiator. Can do. Similarly to the above, the component (i) is preferably 30 to 50 parts by mass and preferably 35 to 45 parts by mass with respect to 100 parts by mass of the total amount of the components (i) and (ii). More preferred. Moreover, it is preferable that it is 50-70 mass parts with respect to 100 mass parts of total amounts of (i) component and (ii) component, and, as for (ii) component, it is more preferable that it is 55-65 mass parts.

  When the component (I) (or (i) component) is less than 30 parts by mass (that is, when the component (II) (or (ii) component) exceeds 70 parts by mass), the photocurable resin is used as a paint. Sometimes the curability of the resulting coating and the performance after curing tend to generally decrease. On the other hand, if (I) component (or (i) component) exceeds 50 parts by mass (that is, (II) component (or (ii) component) is less than 50 parts by mass), volatilization of volatile components such as solvents The surface of the subsequent uncured coating film is sticky, and dust and dust may adhere to the coating film.

  The copolymer of the component (I) and the component (II) and the copolymer of the component (i) and the component (ii) have a weight average molecular weight (gel permeation chromatography method, standard polystyrene conversion value) of 20. 1,000 or more are used. The weight average molecular weight is preferably 30,000 to 200,000, and more preferably 50,000 to 150,000. When the weight average molecular weight is less than 20,000, the surface of the uncured coating film after volatilization of volatile components such as solvents has adhesiveness in the coating film obtained when the photocurable resin is used as a paint, And dust will adhere to the coating. On the other hand, when the weight average molecular weight exceeds 200,000, the viscosity of the photocurable resin composition becomes high, and it becomes necessary to dilute with an organic solvent when the photocurable resin is used as a coating material. At this time, the compatibility between the photocurable resin composition and the organic solvent also decreases at the same time. Therefore, when the organic solvent is diluted to an appropriate coating viscosity, the solid content is remarkably decreased and the coating property tends to be decreased.

  The glass transition temperature of the copolymer of component (I) and component (II), and the copolymer of component (i) and component (ii) is preferably 50 ° C or higher, more preferably 50 to 130 ° C, and 60 to 130. More preferred is ° C. When the glass transition temperature is less than 50 ° C., the surface of the uncured coating film after volatilization of volatile components such as a solvent has adhesiveness when the photocurable resin is used as a paint, and the Dust may adhere to the coating film. On the other hand, when the glass transition temperature exceeds 130 ° C., the appearance, curability and paintability of the coating film obtained when the photocurable resin is used as a paint tend to be lowered.

  The copolymer of component (I) and component (II) has an epoxy group at the side chain and / or terminal, and this epoxy group reacts with the carboxyl group of component (III) (addition reaction), A polymerizable unsaturated group is introduced into the copolymer. As the component (III), (meth) acrylic acid and dimers thereof (manufactured by Toagosei Co., Ltd., trade name: Aronix M5600), caprolactone-modified (meth) acrylic acid (ω-carboxy-polycaprolactone monoacrylate, Made by Toagosei Co., Ltd., trade name: Aronix M5300), compound obtained by ring-opening reaction of hydroxyl-containing (meth) acrylate and carboxylic anhydride (monohydroxyethyl hydrogen succinate phthalate, Shin-Nakamura Chemical Co., Ltd.) Product name: NK ester A-SA) and the like.

  In the above addition reaction, the equivalent ratio (epoxy group / carboxyl group) is preferably 1 / 0.8 to 1 / 1.1. When the equivalent ratio is out of the above range, the performance after curing of the coating film obtained when the photocurable resin is used as a coating tends to be generally lowered. The addition reaction can be performed by a known method in the presence of a basic catalyst, a phosphorus catalyst, or the like.

  The copolymer of component (i) and component (ii) has a hydroxyl group at the side chain and / or terminal, and this hydroxyl group reacts with the isocyanate group of component (iii) (polyaddition reaction) to form a urethane bond. And a polymerizable unsaturated group is introduced into the copolymer. (Iii) As component, isocyanate alkyl (meth) acrylate is mentioned, As for carbon number of the alkyl group of the said (meth) acrylate, 1-6 (further 1-3) are preferable.

  The equivalent ratio (hydroxyl group / isocyanate group) in the polyaddition reaction is preferably 1 / 0.8 to 1 / 1.1. When the equivalent ratio is out of the above range, the performance after curing of the coating film obtained when the photocurable resin is used as a coating tends to be generally lowered. The polyaddition reaction can be performed by a known method in the presence of an amine catalyst, a tin catalyst, or the like.

(B) component:
The component (B) is a urethane compound having a polymerizable unsaturated bond obtained by reacting a compound represented by the following general formula (1) with a compound having active hydrogen and a polymerizable unsaturated bond. Is preferred. In the formula, R ¹ is a divalent organic group, and examples of R ¹ include a divalent aliphatic group, a divalent aromatic group, and a divalent alicyclic hydrocarbon group.

The urethane compound having a polymerizable unsaturated bond is preferably a trimer obtained by trimerizing a diisocyanate compound of OCN—R ¹ —NCO. Examples of the diisocyanate compound to be trimerized include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated Xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate. In particular, it is preferable to use isophorone diisocyanate, tetramethylxylylene diisocyanate, or hexamethylene diisocyanate.

  As the compound having active hydrogen and a polymerizable unsaturated bond to be reacted with the compound represented by the general formula (1), the active hydrogen is derived from a hydroxyl group, and the polymerizable unsaturated bond is an ethylenically unsaturated bond. What is (especially (meth) acryloyl group) is preferable. Examples of such a compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) ) Acrylates, and hydroxyalkyl (meth) acrylates such as dipentaerythritol penta (meth) acrylate.

(C) component:
The component (C) is a polyfunctional (meth) acrylate compound having at least 4 polymerizable unsaturated bonds in one molecule and different from the component (B). Examples of the component (C) include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

(D) component:
The photopolymerization initiator as component (D) generates radical active species upon irradiation with light (referring to actinic rays such as ultraviolet rays and electron beams), (A) component, (B) component, and (C) component; Or it is a component for making these three components and the (E) component mentioned later carry out radical polymerization reaction. As the component (D), a carbonyl-based photopolymerization initiator; benzophenone, diacetyl, benzyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl Acetone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, p, p'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Sulfides such as [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, methylbenzoylformate, 2,2-diethoxyacetophenone, 4-N, N′-dimethylacetophenones Photopolymerization initiators; quinone photopolymerization initiators such as diphenyl disulfide and dibenzyl sulfide; azo photopolymerization initiators such as benzoquinone and anthraquinone; azobisisobutyronitrile and 2,2′-azobis Sulfochloride photopolymerization initiators such as propane and hydrazine; peroxide photopolymerization initiators such as thioxanthone; photopolymerization initiators such as benzoyl peroxide and di-t-butyl peroxide; o-dimethylaminobenzoic acid Examples include photopolymerization initiators such as isoamyl. These photopolymerization initiators can be used alone or in combination of two or more.

(E) component:
The component (E) is a photopolymerizable monomer having a polymerizable unsaturated bond and different from the components (B) and (C). (E) As a component, a monofunctional or polyfunctional (meth) acrylate compound etc. are mentioned. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, ethyl hexyl acrylate, isodecyl acrylate, n-hexyl acrylate, stearyl acrylate, lauryl acrylate, tridecyl acrylate, ethoxyethyl Acrylate, methoxyethyl acrylate, glycidyl acrylate, butoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol Acryle , Octafluoropentyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, allyl acrylate, 1,3-butanediol acrylate, 1,4-butanediol acrylate, 1,6-hexanediol acrylate , Polyethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate ester neopentyl glycol diacrylate, trimethylolpropane diacrylate, 1,3-bis ( Hydroxyethyl) -5,5-dimethylhydantoin, 3-methylpentanediol acrylate, α, ω-diac Rubisdiethylene glycol phthalate, trimethylolpropane triacrylate, pentaerythritol acrylate, pentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, α, ω-tetraallylbistrimethylolpropane tetrahydrophthalate, 2-hydroxyethylacryloyl phosphate, Trimethylolpropane trimethacrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, neopentyl glycol dimethacrylate, diacryloxyethyl phosphate N- vinylpyrrolidone, acryloyl morphine, N- vinyl caprolactam. In addition, these (E) components can be used individually or in combination of 2 or more types. The component (E) is preferably a polyfunctional photopolymerizable monomer.

  The said compound illustrated as (A) component, (B) component, (C) component, (D) component, and (E) component in 1st photocurable resin composition and 2nd photocurable resin composition May be combined in any way. In addition, each of the (A) component, the (B) component, the (C) component, the (D) component, and the (E) component may be used alone or in combination.

Ratio of each component:
In the 1st photocurable resin composition, the quantity of (A) component which occupies for 100 mass parts of total amounts of (A) component, (B) component, and (C) component is 20-60 mass parts (further. 30 to 50 parts by mass), the amount of component (B) is 10 to 60 parts by mass, the amount of component (C) is 10 to 40 parts by mass (further 15 to 30 parts by mass), component (A), ( It is preferable that the quantity of (D) component with respect to 100 mass parts of total amounts of B) component and (C) component is 0.1-10 mass parts (further 1-10 mass parts).

  In the 2nd photocurable resin composition, the quantity of (A) component which occupies 100 mass parts of total amounts of (A) component, (B) component, (C) component, and (E) component is 20-60. Parts by mass (further 30-50 parts by mass), the amount of component (B) is 10-60 parts by mass, and the amount of component (C) is 10-40 parts by mass (further 15-30 parts by mass, more preferably 10 To 20 parts by mass), the amount of the component (E) is 30 parts by mass or less (further 5 to 30 parts by mass), and the sum of the components (A), (B), (C) and (E). It is preferable that the quantity of (D) component with respect to 100 mass parts is 0.1-10 mass parts (further 1-10 mass parts).

  In the first and second photocurable resin compositions, if the component (A) is less than 20 parts by mass, the tackiness of the coating film obtained when the photocurable resin is used as a paint tends to be inferior, When the amount exceeds 60 parts by mass, the scratch resistance after curing may be reduced in a coating film obtained when a photocurable resin is used as a coating material.

  In the first and second photocurable resin compositions, if the component (B) is less than 10 parts by mass, the non-tackiness of the coating film obtained when the photocurable resin is used as a paint tends to be inferior, When the amount exceeds 60 parts by mass, the scratch resistance after curing may be reduced in a coating film obtained when a photocurable resin is used as a coating material.

  In the first and second photocurable resin compositions, when the component (C) is less than 10 parts by mass, the scratch resistance after curing is reduced in the coating film obtained when the photocurable resin is used as a paint. When the amount exceeds 60 parts by mass, the non-tackiness of the coating film obtained when the photocurable resin is used as a paint may be inferior.

  In the first and second photocurable resin compositions, if the component (D) is less than 0.1 parts by mass, the curability by light tends to be insufficient, and if it exceeds 10 parts by mass, the photocurable resin is used. There is a tendency that the physical properties of the coating film obtained when using as a paint generally decrease.

  In the second photocurable resin composition, when the component (E) exceeds 30 parts by mass, in the coating film obtained when the photocurable resin is used as a coating material, the surface of the uncured coating film tends to be sticky. .

  The first and second photocurable resin compositions may contain an additive component other than the components (A) to (E). Typical examples of the additive component include organic solvents and fillers. In addition, when the 1st and 2nd photocurable resin composition contains volatile components, such as an organic solvent, the adhesiveness of the uncured photocurable resin composition is in the state from which the volatile component was removed. to decide.

Coating composition:
The coating composition of the present invention is a coating composition including a resin composition that forms a coating film, and includes the first or second photocurable resin composition as the resin composition. It is. The coating composition of the present invention is excellent in curability, mechanical strength, stain resistance, and chemical resistance, and forms a coating film with few appearance defects on the coating film surface due to dust and dust.

  The coating composition may contain the following solvents (1) to (4), fillers, pigments and the like as necessary.

(1) Hydrocarbon organic solvents such as toluene and xylene, ester organic solvents such as ethyl acetate and butyl acetate, and ketone organic solvents such as methyl ketone (hereinafter referred to as “component (1)”).
(2) Unsaturated polyester resin, vinyl ester resin, vinyl urethane resin, vinyl ester urethane resin, solid phenol resin, polyisocyanate, polyepoxide, epoxy-terminated polyoxazolidone, acrylic resins, alkyd resins, urea resins, melamine resins Natural and synthetic oils such as polydiene elastomers, saturated polyesters, saturated polyethers, cellulose derivatives such as nitrocellulose, cellulose acetate butyrate, linseed oil, tung oil, soybean oil, castor oil, epoxidized oil, etc. Molecular substance (hereinafter referred to as “component (2)”).
(3) Various fillers and pigments such as calcium carbonate, talc, mica, clay, silica powder, colloidal silica, barium sulfate, aluminum hydroxide, zinc stearate, zinc white, bengara, azo pigment (hereinafter referred to as “(3) component” ").
(4) Polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, p-t-butylcatechol, 2,6-di-t-butyl-4-methylphenol (hereinafter referred to as “component (4)”).

  (1) 30-80 mass parts is preferable with respect to 100 mass parts of total amounts of (A) component, (B) component, (C) component, (D) component, and (E) component, and 50- 70 parts by mass is more preferable. (1) If the component is less than 30 parts by mass, the viscosity of the photocurable resin tends to be high, and if it exceeds 80 parts by mass, the viscosity of the photocurable resin is low. It tends to be inferior to the paintability at the time.

  (2) As for a component, 30 mass parts or less are preferred to the above-mentioned total amount. (2) When a component exceeds 30 mass parts, it exists in the tendency for the sclerosis | hardenability of a photocurable resin to fall.

  (3) As for a component, 0 mass part or less is preferable with respect to the said total amount. (3) If the component exceeds 20 parts by mass, the curability of the photocurable resin and the coating suitability when the photocurable resin is used as a paint tend to be reduced.

  (4) As for a component, 0.5 mass part or less is preferred to the above-mentioned total amount. (4) If the component exceeds 0.5 parts by mass, the curing time of the photocurable resin tends to be long and the workability tends to be reduced. The characteristics tend to be inferior.

  In addition to the above components (1) to (4), a leveling agent and other modifiers can be added to such an extent that the effects of the present invention are not reduced.

  The coating composition of the present invention is an ultraviolet curable coating or the like, a metal material such as iron or aluminum, a calcium silicate board, a pulp cement board, a lightweight concrete board, a lightweight cellular concrete board, an asbestos cement board, an inorganic building material such as mortar, It can be used for wood, paper, plastic substrates and the like. That is, since the coating composition can be cured by irradiating ultraviolet rays or the like, it can be suitably used for the material.

Laminate:
The laminate of the present invention comprises a layer made of the first or second photocurable resin composition or the coating composition on one side or both sides of a film-like substrate. This laminate can be produced by applying the first or second photocurable resin composition or the coating composition (preferably an organic solvent solution) to a film-like substrate. In addition, when the 1st or 2nd photocurable resin composition or the said coating composition contains volatile components, such as an organic solvent, it is preferable to remove this volatile component.

  EXAMPLES Hereinafter, although the suitable Example of this invention is described in detail, this invention is not limited to a following example.

In addition, the following apparatus etc. were used in the measurement of a weight average molecular weight.
Equipment used: Hitachi L6000 type high performance liquid chromatography column: Gelpacks R400, R450 and R400M (manufactured by Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran

(Production Example A1)
1,000 parts by mass of butyl acetate was charged in a reaction vessel and heated to 100 ° C. with stirring in a nitrogen gas atmosphere. Then, 1,000 parts by mass of a polymerizable monomer component (consisting of 370 parts by mass of glycidyl methacrylate, 460 parts by mass of styrene and 170 parts by mass of methyl methacrylate), t-butylperoxy-2-ethylhexanoate (Nippon Yushi Co., Ltd., product name: Perbutyl O) 20 parts by mass was added dropwise over 2 hours. After completion of the dropping, the reaction was further performed at 100 ° C. for 4 hours, and then heated to 110 ° C., and 3 parts by mass of perbutyl O was added dropwise over 1 hour. After completion of the dropwise addition, the reaction was further performed at 110 ° C. for 2 hours, and then heated to 145 ° C., and the reaction was further continued for 2 hours to synthesize a copolymer. The obtained copolymer had a weight average molecular weight of 70,000 and a glass transition temperature of 76 ° C.

  Subsequently, 85 parts by mass of acrylic acid, 5 parts by mass of triphenylphosphine, and 1 part by mass of hydroquinone monomethyl ether were added to 1,000 parts by mass of the copolymer, and the mixture was heated and stirred at 105 ° C. for about 10 hours while blowing air. A polymer (component (A)) having a polymerizable unsaturated bond having a valence of 5 and a solid content of 50 parts by mass was obtained.

( Comparative Production Example A 1 )
1,000 parts by mass of butyl acetate was charged in a reaction vessel and heated to 125 ° C. with stirring in a nitrogen gas atmosphere. Then, 1,000 parts by weight of a polymerizable monomer component (consisting of 370 parts by weight of glycidyl methacrylate, 230 parts by weight of isobutyl methacrylate, 300 parts by weight of methyl methacrylate and 100 parts by weight of styrene) and azobisiso. 15 parts by mass of butyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was further performed at 125 ° C. for 4 hours to synthesize a copolymer. The obtained copolymer had a weight average molecular weight of 20,000 and a glass transition temperature of 70 ° C.

  Subsequently, 85 parts by mass of acrylic acid, 3 parts by mass of triphenylphosphine and 0.5 parts by mass of hydroquinone monomethyl ether were added to 1,000 parts by mass of this copolymer, and the mixture was heated and stirred at 100 ° C. for about 10 hours. And the polymer ((A) component) which has a polymerizable unsaturated bond of 50 mass parts of solid content was obtained.

(Comparative Production Example A 2 )
1,000 parts by mass of butyl acetate was charged in a reaction vessel and heated to 125 ° C. with stirring in a nitrogen gas atmosphere. Then, 1,000 parts by mass of a polymerizable monomer component (consisting of 370 parts by mass of glycidyl methacrylate, 460 parts by mass of styrene and 170 parts by mass of methyl methacrylate), t-butylperoxy-2-ethylhexanoate 20 parts by mass (Nippon Yushi Co., Ltd., trade name: Perbutyl O) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further performed at 115 ° C. for 2 hours, and then heated to 145 ° C., and the reaction was further continued for 2 hours to synthesize a copolymer. The resulting copolymer had a weight average molecular weight of 15,000 and a glass transition temperature of 76 ° C.

  Subsequently, 85 parts by mass of acrylic acid, 5 parts by mass of triphenylphosphine, and 1 part by mass of hydroquinone monomethyl ether were added to 1,000 parts by mass of the copolymer, and the mixture was heated and stirred at 105 ° C. for about 10 hours while blowing air. A polymer having a polymerizable unsaturated bond having a valence of 5 and a solid content of 50 parts by mass was obtained.

(Production Example B1)
In the reaction solution, 300 parts by mass of butyl acetate, 341 parts by mass of pentaerythritol triacrylate (OH value = 113 mg KOH / g, trade name: Aronix M305), 0.3 part by mass of hydroquinone monomethyl ether, 0.5 part by mass of dibutyltin dilaurate The mixture was charged and heated to 75 ° C. while blowing air. A mixed solution of 246 parts by mass of VESTANATE T1890E represented by the following (1a) at 75 ° C. and 110 parts by mass of butyl acetate was added dropwise over 2 hours. The reaction was carried out at 75 ° C. for 8 hours after completion of the dropwise addition, and when the peak of the isocyanate absorption band (2270 cm ⁻¹ ) disappeared by IR measurement, the synthesis was completed, and in one molecule having a solid content of 50% and a weight average molecular weight of 2,500 The urethane compound (component (B)) having 9 polymerizable unsaturated bonds was obtained.

(Production Example B2)
In the reaction solution, 300 parts by mass of butyl acetate, 245 parts by mass of pentaerythritol triacrylate (OH value = 113 mg KOH / g, trade name: Aronix M305), 65 parts by mass of 2-hydroxyethyl acrylate, 0.3 part by mass of hydroquinone monomethyl ether, 0.5 parts by mass of dibutyltin dilaurate was charged and heated to 75 ° C. while blowing air. At 75 ° C., a mixed solution of 278 parts by mass of VESTANATE T1890E and 110 parts by mass of butyl acetate was added dropwise over 2 hours. The reaction was carried out at 75 ° C. for 8 hours after completion of the dropwise addition, and when the peak of the isocyanate absorption band (2270 cm ⁻¹ ) disappeared by IR measurement, the synthesis was completed, and in one molecule having a solid content of 50% and a weight average molecular weight of 2,500 The urethane compound (component (B)) having 7 polymerizable unsaturated bonds was obtained.

(Examples 1-2 and Comparative Examples 1-4 )
Each component was mixed so that it might become a composition shown in the following Table 1, and the photocurable resin composition was obtained.

(Performance evaluation of photocurable resin composition)
The photocurable resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 to 4 were applied to a glass plate as a substrate using a bar coater so that the dry film thickness was 20 μm, and the temperature was adjusted to 70 ° C. After drying for 5 minutes in a heated hot air dryer, the resulting dried film was evaluated for surface non-stickiness and pencil hardness. Thereafter, the photocurable resin composition was cured by irradiating with ultraviolet rays by placing on a conveyor moving at a speed of 10 m / min equipped with two 80 w / cm high pressure mercury lamps. The resulting cured coating film was evaluated for pencil hardness, scratch resistance, and chemical resistance. The evaluation method is shown below, and the evaluation results are shown in Table 2.

(1) Non-adhesiveness before curing After the organic solvent was volatilized with a warm air dryer, the surface of the coating film was touched with a finger to evaluate the degree of drying of the coating film surface.
(2) Pencil hardness In accordance with the pencil method of JISK5600-5-4 (2003 edition), the maximum pencil hardness that does not leave scratch marks on the coating film surface and the maximum pencil hardness that does not destroy the coating film were measured. .
(3) Scratch resistance The surface of the UV cured coating film was rubbed 10 times with a load of about 200 g using steel wool (Bonster # 0000), and the scratch mark of the coating film was visually determined.
(4) Chemical resistance The surface of the coating film was rubbed 100 times with absorbent cotton soaked with xylene, and the state of the coating film surface was observed.

Claims (12)

(A) a polymer in which a polymerizable unsaturated bond is formed at a side chain and / or a terminal of a (meth) acrylic polymer having a weight average molecular weight of 50,000 or more and a glass transition temperature of 50 ° C. or more ;
(B ) a urethane compound having a polymerizable unsaturated bond obtained by reacting a compound represented by the following general formula (1a) with a compound having active hydrogen and a polymerizable unsaturated bond ;
(C) at least one polyfunctional (meth) acrylate selected from pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate ,
(D) A photopolymerization initiator, a photocurable resin composition containing the photopolymerization initiator.

The amount of the component (A) in the total amount of the component (A), the component (B) and the component (C) of 100 parts by mass is 20 to 60 parts by mass, the amount of the component (B) is 10 to 60 parts by mass, ( C) The amount of the component is 10 to 40 parts by mass,
The photocurable resin composition according to claim 1, wherein the amount of component (D) is 0.1 to 10 parts by mass relative to 100 parts by mass of the total amount of component (A), component (B), and component (C). . (A) a polymer in which a polymerizable unsaturated bond is formed at a side chain and / or a terminal of a (meth) acrylic polymer having a weight average molecular weight of 50,000 or more and a glass transition temperature of 50 ° C. or more ;
(B ) a urethane compound having a polymerizable unsaturated bond obtained by reacting a compound represented by the following general formula (1a) with a compound having a compound having active hydrogen and a polymerizable unsaturated bond ;
(C ) at least one polyfunctional (meth) acrylate selected from pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate ,
(D) a photopolymerization initiator;
(E) a photopolymerizable monomer having a polymerizable unsaturated bond and different from the component (B) and the component (C);
Containing a photocurable resin composition.

(A) component, (B) component, (C) component, and (E) component occupy the total amount of 100 parts by mass, the amount of (A) component is 20 to 60 parts by mass, the amount of (B) component is 10 to 10 parts by mass. 60 parts by mass, the amount of component (C) is 10 to 40 parts by mass, the amount of component (E) is 30 parts by mass or less,
The photocuring of Claim 3 whose quantity of (D) component with respect to 100 mass parts of total amounts of (A) component, (B) component, (C) component, and (E) component is 0.1-10 mass parts. Resin composition. Component (A) has a weight average molecular weight obtained by polymerizing (I) (meth) acrylic acid glycidyl ester and (II) 1 polymerizable unsaturated bond and a monomer different from (I) component. 5. A polymer having a glass transition temperature of 50 ° C. or higher obtained by reacting a carboxylic acid having a polymerizable unsaturated bond with (III) a (meth) acrylic polymer of 50,000 or higher. The photocurable resin composition as described in any one of these. The component (A) is a weight average molecular weight obtained by polymerizing (i) a (meth) acrylate containing a hydroxyl group and (ii) a monomer having a polymerizable unsaturated bond of 1, and a component (i) different from the component. Is a polymer having a glass transition temperature of 50 ° C. or higher , wherein (iii) a compound having an isocyanate group and a polymerizable unsaturated bond is reacted with a (meth) acrylic polymer of 50,000 or higher. Item 5. The photocurable resin composition according to any one of Items 1 to 4. The photocurable resin composition according to any one of claims 1 to 6 , wherein the (meth) acrylic polymer has a polymerization average molecular weight of 50,000 to 70,000. A cured product obtained by curing the photocurable resin composition according to any one of claims 1-7. A coating composition containing a resin composition for forming a coating film,
Wherein the resin composition comprises a photocurable resin composition according to any one of claim 1 to 7 the coating composition. A paint cured product obtained by curing the coating composition according to claim 9 . A laminate comprising a layer made of the photocurable resin composition according to any one of claims 1 to 7 on one side or both sides of a film-like substrate. The laminated body provided with the layer which consists of a coating composition of Claim 9 in the one side or both sides of a film-form base material.