JP2018131563A - Curable resin composition and cured product thereof, and coating material, sheet and film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition that makes it possible to obtain a cured product having excellent transparency.SOLUTION: A curable resin composition contains a monofunctional (meth) acrylate (A) having a hydroxy group, a monofunctional (meth) acrylate (B) having an aromatic ring structure other than component (A), a polyfunctional (meth) acrylate (C), a (meth) acrylic polymer (D), a condensed phosphoester compound (E), and a polymerization initiator (F).SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition and a cured product thereof, and a coating material, a sheet, and a film.

  The curable (meth) acrylic resin composition is widely used for transparent members represented by coating materials, sheets, films, and the like because the cured product is excellent in weather resistance and transparency.

  For example, Patent Document 1 discloses a cured product of a thermosetting resin composition containing a (meth) acrylic polymer, a (meth) acrylate having an aromatic ring, a hydroxyalkyl (meth) acrylate, and a thermal polymerization initiator. Since it is excellent in transparency, it is disclosed that it is useful for films and sheets used for optical members.

JP 2012-126896 A

  However, since the cured product of the thermosetting resin composition described in Patent Document 1 has high haze, its transparency is not sufficient.

  The present invention has been made in view of the above circumstances, and includes a curable resin composition from which a cured product excellent in transparency is obtained, a cured product thereof, and a coating material, a sheet and a film using the cured product. The purpose is to provide.

  According to one embodiment of the present invention, a monofunctional (meth) acrylate (A) having a hydroxyl group, a monofunctional (meth) acrylate (B) having an aromatic ring structure other than the component (A), a polyfunctional (meta A curable resin composition containing an acrylate (C), a (meth) acrylic polymer (D), a condensed phosphate ester compound (E), and a polymerization initiator (F) is provided.

  According to the other aspect of this invention, the hardened | cured material formed by hardening | curing said curable resin composition is provided.

  According to the other aspect of this invention, the coating material containing said hardened | cured material is provided.

  According to the other aspect of this invention, the sheet | seat containing said hardened | cured material is provided.

  According to the other aspect of this invention, the film containing said hardened | cured material is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition from which the hardened | cured material excellent in transparency is obtained, its hardened | cured material, and the coating material, sheet | seat, and film using the hardened | cured material can be provided.

Hereinafter, the present invention will be described in detail. In the present invention, “(meth) acryl” is a general term for acrylic and methacrylic. “(Meth) acrylate” is a general term for acrylate and methacrylate. The “(meth) acryloyl group” is a generic name for an acryloyl group and a methacryloyl group, and is represented by CH ₂ ═C (R) —C (═O) — (R represents a hydrogen atom or a methyl group).

[Curable resin composition]
A curable resin composition according to an embodiment of the present invention includes a monofunctional (meth) acrylate (A) having a hydroxyl group, a monofunctional (meth) acrylate (B) having an aromatic ring structure other than the component (A), It contains a functional (meth) acrylate (C), a (meth) acrylic polymer (D), a condensed phosphate ester compound (E), and a polymerization initiator (F).

  Component (A) is 1 to 30% by mass, Component (B) is 10 to 80% by mass, and Component (C) is 5 to 40% with respect to 100% by mass of the total amount of components (A) to (E). The component (D) is 1 to 30% by mass, the component (E) is 1 to 40% by mass, and the component (A) to (E) is 100 parts by mass in total with respect to the component (F). It is preferable to contain 0.1-10 mass parts.

  This curable resin composition can further contain an antistatic agent (G).

(Ingredient (A))
Component (A) is a monofunctional (meth) acrylate having a hydroxyl group, and is a component that improves the transparency of the cured product of the curable resin composition.

  Specific examples of the component (A) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl. Hydroxyalkyl (meth) acrylates such as (meth) acrylate and glycerol mono (meth) acrylate; hydroxyphenyl (meth) acrylate, hydroxycyclohexyl (meth) acrylate, hydroxynorbornyl (meth) acrylate, hydroxyisobornyl (meth) acrylate , Hydroxydicyclopentenyl (meth) acrylate, hydroxydicyclopentanyl (meth) acrylate, hydroxyadamantyl (meth) acrylate, 1,4-cyclohexanedimethano Include hydroxy (meth) acrylates having a cyclic structure, such as mono (meth) acrylate.

  From the viewpoint of the transparency of the cured product, hydroxyalkyl (meth) acrylate is preferred (hydroxyalkyl group preferably has 1 to 6 carbon atoms, more preferably 2 to 5 and even more preferably 2 to 4), 2-hydroxyethyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are particularly preferred.

  A component (A) may be used individually by 1 type, and may use 2 or more types together.

(Ingredient (B))
The component (B) is a monofunctional (meth) acrylate having an aromatic ring structure other than the component (A), dissolves the (meth) acrylic polymer as the component (D), and is used for the curable resin composition. It is a component that improves curability.

  Specific examples of component (B) include phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) ) Acrylate, phenoxypolypropylene glycol (meth) acrylate, biphenyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate, phenoxybenzyl (meth) acrylate, phenylbenzyl (meth) acrylate, naphthyl (meth) acrylate, (1-naphthyl) And methyl (meth) acrylate.

  From the viewpoint of transparency of the cured product, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate are particularly preferable.

  A component (B) may be used individually by 1 type, and may use 2 or more types together.

(Ingredient (C))
Component (C) is a polyfunctional (meth) acrylate and is a component that improves the curability of the curable resin composition.

  Specific examples of the component (C) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9- Polyalkylene glycol di (meth) such as alkylene glycol di (meth) acrylate such as nonanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polybutylene glycol di (meth) acrylate Acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polycarbonate diol di (meth) acrylate, polyester diol di (meth) acrylate Bifunctional (meth) acrylates such as rate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, polyurethane di (meth) acrylate; trimethylolpropane tri (meth) acrylate, ethoxylated isocyanur Trifunctional (meth) acrylates such as acid tri (meth) acrylate and ε-caprolactone-modified tris ((meth) acryloxyethyl) isocyanurate; tetrafunctional (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate; Examples include pentafunctional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; hexafunctional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate.

  From the viewpoint of transparency of the cured product, a bifunctional (meth) acrylate is preferable, and polyalkylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, and propoxylated bisphenol A di (meth) acrylate are particularly preferable. .

  A component (C) may be used individually by 1 type, and may use 2 or more types together.

(Component (D))
Component (D) is a (meth) acrylic polymer and is a component that improves the curability of the curable resin composition.

  The (meth) acrylic polymer is a polymer containing 50% by mass or more of (meth) acrylic monomer units in the composition. The (meth) acrylic monomer means a monomer having a (meth) acryloyl group. “Unit” means a repeating unit constituting a polymer.

  The (meth) acrylic monomer may be a monofunctional monomer or a polyfunctional monomer. From the viewpoint of solubility in the component (A) and the component (B), a monofunctional monomer is preferable.

  Specific examples of the monofunctional monomer include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, hexahydro (Meth) acrylate containing carboxyl group such as 2- (meth) acryloyloxyethyl phthalate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -(Meth) acrylate having a hydroxyl group such as hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) Acrylate i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, Alkyl (meth) acrylates such as n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate; cyclohexyl (meth) acrylate , Dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (Meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (Meth) acrylate, phenylphenyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate, phenoxybenzyl (meth) acrylate, phenylbenzyl (meth) acrylate, naphthyl (meth) acrylate, (1-naphthyl) methyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic (Meth) acrylates having a cyclic structure such as loylmorpholine; alkoxy (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate; 3- (meth) acryloxy Examples include propyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2- (meth) acryloyloxyethyl acid phosphate, trifluoroethyl (meth) acrylate, and heptadecafluorodecyl (meth) acrylate.

  Specific examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonane. Polyalkylene glycol di (meth) acrylates such as alkylene glycol di (meth) acrylates such as diol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polybutylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polycarbonate diol di (meth) acrylate, polyester diol di (meth) Bifunctional such as acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, 9,9-bis (4- (meth) acryloyloxyethoxyphenyl) fluorene, urethane di (meth) acrylate, etc. (Meth) acrylate; trifunctional (meth) acrylate such as trimethylolpropane tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, ε-caprolactone modified tris ((meth) acryloxyethyl) isocyanurate; Tetrafunctional (meth) acrylate such as methylolpropane tetra (meth) acrylate; pentafunctional (meth) acrylate such as dipentaerythritol penta (meth) acrylate; dipentaerythritol hexa (meth) acrylate And polyfunctional monomers such as hexafunctional (meth) acrylates such as cartons.

  1 type or 2 types or more may be sufficient as the (meth) acrylic-type monomer unit contained in a component (D). Moreover, the component (D) may contain other monomer units other than the (meth) acrylic monomer unit. Other monomers may be any copolymerizable with (meth) acrylic monomers, for example, aromatic vinyl monomers such as styrene and α-methylstyrene; vinyl cyanide monomers such as acrylonitrile; vinyl acetate and the like And vinyl monomers such as vinyl ester monomers. In component (D), the proportion of (meth) acrylic monomer units is preferably 70% by mass or more, and more preferably 80% by mass or more. The upper limit of the ratio is not particularly limited, and may be 100% by mass.

  Preferred specific examples of the component (D) include polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, a copolymer composed of methyl methacrylate units and n-butyl methacrylate units, and methyl methacrylate units and n-butyl acrylate units. And a copolymer. Among these, from the viewpoint of transparency of the cured product, polymethyl methacrylate, a copolymer composed of a methyl methacrylate unit and an n-butyl methacrylate unit, and a copolymer composed of a methyl methacrylate unit and an n-butyl acrylate unit are preferable.

  The mass average molecular weight of the component (D) is preferably 10,000 to 500,000, and more preferably 30,000 to 200,000. When the mass average molecular weight is 10,000 or more, the curability is improved. The transparency of hardened | cured material becomes it favorable that it is 500,000 or less.

  The polymerization method for obtaining the component (D) is not particularly limited, and for example, the polymerization can be performed by a known method such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or a partial polymerization method. In the present invention, the suspension polymerization method is preferred because it is relatively easy to control the polymerization reaction and to separate the produced polymer.

  A component (D) may be used individually by 1 type, and may use 2 or more types together.

(Ingredient (E))
Component (E) is a condensed phosphate ester compound and is a component that improves the transparency of the cured product.

  Specific examples of the component (E) include, for example, “ADEKA STAB FP-600” (trade name), “ADEKA STAB PFR” (trade name) manufactured by ADEKA, which is commercially available as a flame retardant, Daihachi Chemical Industry Co., Ltd. ) "CR-733S" (product name), "CR-741" (product name), "PX-200" (product name), "DIGUARD-580" (product name), "DIGUARD-880" (product) Non-halogen condensed phosphate such as “TMCPP” (trade name) and “CR-900” (trade name).

  From the viewpoint of the transparency of the cured product, a non-halogen condensed phosphate is preferable.

(Ingredient (F))
Component (F) is a polymerization initiator, and examples thereof include a photopolymerization initiator, a thermal polymerization initiator, and a peroxide used for redox polymerization. The kind of a component (F) can be suitably selected according to a polymerization method.

  The photopolymerization initiator is a radical polymerization initiator used for photopolymerization. Specific examples of the photopolymerization initiator include benzophenone-type compounds such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone; t-butylanthraquinone, 2-ethyl Anthraquinone type compounds such as anthraquinone; 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, Benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methylpropi Nyl) benzyl] phenyl} -2-methylpropan-1-one, etc .; alkylphenone type compounds; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, diethylthioxanthone, isopropylthioxanthone, etc. 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl)- Examples include acylphosphine oxide type compounds such as phenylphosphine oxide; phenylglyoxylate type compounds such as phenylglyoxylic acid methyl ester.

  Among these, an alkylphenone type compound is preferable in that coloring of the cured product can be suppressed, and 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexyl phenyl ketone are more preferable. Moreover, an acyl phosphine oxide type compound is preferable in that it can be sufficiently cured to the inside of the cured product, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide is more preferable in that coloring of the cured product can be suppressed. These photopolymerization initiators may be used alone or in combination of two or more.

  The thermal polymerization initiator is a radical polymerization initiator used for thermal polymerization. Examples of the thermal polymerization initiator include organic peroxides and azo compounds.

  Specific examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide; 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexyl) Peroxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane and the like; 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide Hydroperoxides such as dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; di (4-t-butylcyclohexyl) peroxy Dicarbonate, di ( -Ethylhexyl) peroxydicarbonate such as peroxydicarbonate; t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxybenzoate, 1,1,3,3 -Peroxyesters such as tetramethylbutylperoxy-2-ethylhexanoate.

  Specific examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile). 1,1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate, 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis- (2 -Amidinopropane) dihydrochloride and the like.

  These thermal polymerization initiators may be used alone or in combination of two or more.

  As the thermal polymerization initiator, an organic peroxide is preferable in that air bubbles hardly occur in the cured product. Considering the balance between curing time and pot life of the curable resin composition, the 10-hour half-life temperature of the organic peroxide is preferably 35 to 80 ° C, more preferably 40 to 75 ° C, and still more preferably 45. ~ 70 ° C. When the 10-hour half-life temperature is 35 ° C. or higher, the curable resin composition is hardly gelled at room temperature, and the pot life is improved. On the other hand, if the 10-hour half-life temperature is 80 ° C. or less, the curing time of the curable resin composition can be shortened. Examples of such organic peroxides include 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di (4-t -Butylcyclohexyl) peroxydicarbonate and the like. As a commercially available product of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, for example, Perocta O (trade name, manufactured by NOF Corporation, 10 hour half-life temperature: 65.3 ° C.) Etc. Examples of commercially available products of t-butyl peroxy-2-ethylhexanoate include perbutyl O (trade name, manufactured by NOF Corporation, 10 hour half-life temperature: 72.1 ° C.). Examples of commercially available di (4-t-butylcyclohexyl) peroxydicarbonate include perroyl TCP (trade name, manufactured by NOF Corporation, 10 hour half-life temperature: 40.8 ° C.).

  Examples of the peroxide used for redox polymerization include dibenzoyl peroxide and hydroperoxide. These peroxides may be used alone or in combination of two or more.

  In the redox polymerization, a redox polymerization initiator is usually used. The redox polymerization initiator is a polymerization initiator in which a peroxide and a reducing agent are used in combination. In the case where the above-described peroxide is used as a redox polymerization initiator, an example of a combination with a reducing agent is as follows.

(1) Dibenzoyl peroxide (peroxide) and aromatics such as N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxypropyl) -p-toluidine Combination with tertiary amines (reducing agents).
(2) A combination of hydroperoxide (peroxide) and metal soap (reducing agent).
(3) A combination of hydroperoxide (peroxide) and thioureas (reducing agent).

  These components (F) may be used individually by 1 type, and may use 2 or more types together.

(Ingredient (G))
The curable resin composition by embodiment of this invention may contain the antistatic agent which is a component (G) other than the said components (A)-(F), and, thereby, the surface resistivity of hardened | cured material is made. It can be reduced to prevent dust and dust from adhering.

  Specific examples of the component (G) include a cationic antistatic agent such as “Electro Stripper QN” (trade name) of Kao Corporation, and an anionic charge such as “Electro Stripper ME-2” (trade name). Anti-ionic agents such as anti-static agents, “electrostripper AC” (trade name), non-ionic anti-static agents such as “Rheodor TW-L120” (trade name), “Emazole L-10V” (trade name) Etc.

  An anionic antistatic agent is particularly preferred because of its excellent antistatic performance and transparency.

(Other ingredients)
The curable resin composition according to the embodiment of the present invention may contain other components (H) other than the components (A) to (G) as long as the effects of the present invention are not impaired. Examples of such component (H) include monofunctional vinyl group-containing compounds other than components (A) and (B), antioxidants, rubber, silica particles, zirconia, plasticizers, ultraviolet absorbers, and antifoaming agents. , Thixotropic agents, mold release agents, fillers, phosphors, pigments and the like. These components (H) may be used individually by 1 type, and may use 2 or more types together.

  Specific examples of monofunctional vinyl group-containing compounds other than components (A) and (B) include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl. (Meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (Meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, di Clopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (Meth) acrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 3- (meth) acryloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyl acid phosphate, (Meth) acryloylmorpholine and the like can be mentioned. Specific examples of the vinyl group-containing monomer unit include aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile, and vinyl esters such as vinyl acetate.

(Mixing amount)
The content of the component (A) of the curable resin composition is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, when the total of the components (A) to (E) is 100% by mass. 3-20 mass% is further more preferable. The transparency of hardened | cured material can be made favorable by content of a component (A) being 1-30 mass%.

  The content of the component (B) of the curable resin composition is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, when the total of the components (A) to (E) is 100% by mass. 20-60 mass% is still more preferable. The transparency of hardened | cured material can be made favorable by content of a component (B) being 10-80 mass%.

  The content of the component (C) of the curable resin composition is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, when the total of the components (A) to (E) is 100% by mass. More preferably, it is 15-30 mass%. By making content of a component (C) into 5-40 mass%, sclerosis | hardenability of curable resin composition and transparency of hardened | cured material can be made favorable.

  The content of the component (D) of the curable resin composition is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, when the total of the components (A) to (E) is 100% by mass. 3-20 mass% is further more preferable. By making content of a component (D) into 1-30 mass%, sclerosis | hardenability of curable resin composition and transparency of hardened | cured material can be made favorable.

  The content of the component (E) of the curable resin composition is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, when the total of the components (A) to (E) is 100% by mass. 3-30 mass% is further more preferable. The transparency of hardened | cured material can be made favorable by content of a component (E) being 1-40 mass%.

  The content of the component (F) of the curable resin composition is preferably 0.1 to 10 parts by mass, and 0.5 to 8 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (E). More preferably, 1-5 mass parts is further more preferable. By making content of a component (F) into 0.1-10 mass parts, sclerosis | hardenability of curable resin composition can be made favorable.

  When curable resin composition contains a component (G), 0.1-10 mass parts is preferable with respect to 100 mass parts of total amounts of a component (A)-(E), and 0.2-5 mass parts is. More preferably, 0.5-3 mass parts is further more preferable. By making content of a component (G) into 0.1-10 mass parts, transparency and antistatic property of hardened | cured material can be made favorable.

  When a monofunctional vinyl group-containing compound other than components (A) and (B) is contained, components (A) to (E) and components (A) and (B) other than components (A) and (B) are preferred in terms of transparency of the cured product. The content of the monofunctional vinyl group-containing compound other than the components (A) and (B) is preferably 30 parts by mass or less, and 20 parts by mass or less with respect to the total amount of 100 parts by mass with the monofunctional vinyl group-containing compound. Is more preferable, and 15 parts by mass or less is more preferable.

(Method for producing curable resin composition)
As a method for producing the curable resin composition, for example, the components (A) to (F) and, if necessary, the component (G) and / or other components (H) are stirred and mixed at room temperature. The method, the method of heating and mixing these, etc. are mentioned.

  When using a thermal polymerization initiator as the component (F), from the viewpoint of the stability of the curable resin composition, a method for obtaining a curable resin composition by mixing at room temperature, or other than the component (F), Examples include a method of cooling after heating and mixing, adding the component (F) at room temperature, stirring and mixing, and obtaining a curable resin composition.

  In the case of producing a curable resin composition by heat mixing, it is preferable to mix under heating at 40 to 100 ° C. from the viewpoint of good compatibility and more uniform mixing. From the same viewpoint, the stirring time during mixing is preferably 0.1 to 5 hours.

(Cured product)
The cured product according to the embodiment of the present invention is obtained by curing the curable resin composition according to the above-described embodiment. As a method for curing the curable resin composition, any of photopolymerization, thermal polymerization, and redox polymerization can be employed depending on the type of the component (F) contained in the curable resin composition.

  In the case of obtaining a cured product by curing the curable resin composition by photopolymerization, the wavelength of light applied to the curable resin composition is not particularly limited, but it is preferable to irradiate ultraviolet rays having a wavelength of 200 to 400 nm. Specific examples of the ultraviolet light source include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, a UV-LED lamp, a chemical lamp, and a black light. After photopolymerization of the curable resin composition, after-curing may be further performed. Thereby, the quantity of the unreacted (meth) acryloyl group which remains in hardened | cured material can be decreased, and the intensity | strength of hardened | cured material can be raised more. The after-curing conditions are preferably 0.01 to 24 hours at 70 to 150 ° C, and more preferably 0.1 to 10 hours at 80 to 130 ° C.

  When the curable resin composition is cured by thermal polymerization to obtain a cured product, the curing conditions are not particularly limited, but the curing temperature is 40 to 200 ° C. from the viewpoint of easily obtaining a resin for optical members in which coloring is suppressed. Preferably, 60-150 degreeC is more preferable. The curing time (heating time) varies depending on the curing temperature, but is preferably 1 to 120 minutes, and more preferably 1 to 60 minutes.

  After the curable resin composition is thermally polymerized, after-curing is preferably further performed. As conditions for the after cure, 0.1 to 10 hours are preferable at 50 to 150 ° C, and 0.2 to 5 hours are more preferable at 70 to 130 ° C.

  When a curable resin composition is cured by redox polymerization to obtain a cured product, it can be cured at room temperature of 5 to 40 ° C. by using a redox polymerization initiator. The curing temperature is preferably 15 to 40 ° C. from the viewpoint that the amount of unreacted (meth) acryloyl groups remaining in the obtained optical member resin can be reduced and the strength of the optical member resin can be further increased. .

  In addition, since the curable resin composition is difficult to gel and can be stably handled, there is a method in which a reducing agent is dissolved in the curable resin composition in advance and curing is performed by adding a peroxide thereto. preferable.

  When curing the curable resin composition, it is preferable to cure the curable resin composition in a sealed state in order to suppress the inhibition of curing by oxygen. Examples of the sealing method include a method in which a curable resin composition is sandwiched between glass and a PET film.

(Transparency of cured product)
Regarding the transparency of the cured product according to the embodiment of the present invention, when the thickness of the cured product is 1 mm, the total light transmittance is preferably 88% or more and the haze is 3% or less, and the total light transmittance is 89%. As described above, the haze is more preferably 2.5% or less, the total light transmittance is preferably 90% or more, and the haze is further preferably 2% or less. The total light transmittance and haze are values measured by the method described later.

(Antistatic property of cured product)
Regarding the antistatic property of the cured product, if the surface resistivity of the cured product is lower than 1 × 10 ¹⁴ Ω / □, dust and dust can be prevented from adhering to the surface of the cured product. The surface resistance value is a value measured by a method described later.

[Coating materials, films, sheets]
The curable resin composition according to the embodiment of the present invention can be used as a coating material, a film, or a sheet, because a cured product having excellent transparency can be obtained.

  Specific examples of coating materials include wall coating materials, floor coating materials, roof coating materials, bridge coating materials, plant coating materials, iron structure coating materials, concrete coating materials, etc. Materials: Non-slip coating materials, drainage coating materials, thermal barrier coating materials, road marking coating materials, road coating materials such as floor slab waterproofing coating materials, furniture coating materials, and decorative coatings Materials, coating materials for electronic devices / mobiles, coating materials for home appliances, coating materials for waterproofing, coating materials for automobiles, coating materials for motorcycles, coating materials for heavy machinery, coating materials for railway vehicles, and coating materials for ships.

  Specific examples of films and sheets include light emitting diode modules, mobile phones, smartphones, tablet terminals, personal computers, cameras, organic electroluminescence (organic EL) devices, flat panel displays, touch panels, electronic paper, photodiodes, phototransistors, and the sun. Examples include batteries, projectors, home appliances, automobiles, motorcycles, heavy machinery, railway vehicles, ships, building materials, smoke barriers, smoke curtains, films and sheets used for decorative panels. Moreover, the film and sheet | seat by embodiment of this invention can also be used as FRP in order to provide high elasticity, a flame retardance, and a nonflammability. FRP can be obtained by impregnating a fiber such as glass fiber with a curable resin composition and then curing.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these examples. In the examples and comparative examples, “part” means “part by mass”. Measurement and evaluation in this example were performed according to the following methods.

[Evaluation method]
(Mass average molecular weight)
The mass average molecular weight was obtained by dissolving the polymer in tetrahydrofuran as a solvent and converting the molecular weight measured by gel permeation chromatography into polystyrene.

(Curable)
A curable resin composition is sandwiched between two glass plates of 10 cm × 10 cm with a diameter of about 50 mm × thickness of about 1 mm, irradiated with a chemical lamp (irradiation intensity: 5 mW / cm ² ) for 30 minutes, and 30 ° C. at 30 ° C. The curability when after-curing for a minute was evaluated according to the following criteria.

○: Cured to the end (air contact part).
(Triangle | delta): An edge part (air contact part) is unhardened and a liquid component remains.
X: The sealed central part is uncured and the liquid component remains.

(transparency)
Transparency was evaluated by measuring the haze of a cured product having a diameter of about 50 mm × thickness of about 1 mm using a haze meter (trade name: HM-150, manufactured by Murakami Color Research Laboratory).

(Antistatic property)
A cured product having a diameter of about 50 mm and a thickness of about 1 mm was stored at 23 ° C. and 50% RH for 24 hours, and then applied with a resistivity meter (trade name: Hiresta UP <MCP-HT450 type>, manufactured by Mitsubishi Chemical Analytech). The surface resistivity at a voltage of 1000 V was measured to evaluate the antistatic property. When the measured value was larger than 1 × 10 ¹⁴ Ω / □, the evaluation result was described as “10 ¹⁴ <”.

[Production Example 1] Production of polymer 1 In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 145 parts of deionized water and polyvinyl alcohol (saponification degree: 80%, polymerization degree: 1) as a dispersion stabilizer. 700) 0.5 part was added and stirred.

  After completely dissolving the polyvinyl alcohol, the stirring was stopped, 93 parts of methyl methacrylate, 7 parts of n-butyl acrylate, 0.1 part of 2,2′-azobisisobutyronitrile, 0.25 part of n-octyl mercaptan Was added and stirred again. Under stirring, the atmosphere in the polymerization apparatus was replaced with nitrogen, and the temperature was raised to 70 ° C. to carry out polymerization. After detecting the peak of the polymerization exotherm, the temperature was raised to 98 ° C., the reaction was further carried out for 0.5 hours, and the mixture was cooled to 40 ° C.

  The obtained aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, and the filtrate was washed with deionized water.

  After dehydration, it was dried at 40 ° C. for 20 hours to obtain a granular (meth) acrylic polymer (hereinafter referred to as “polymer 1”). The weight average molecular weight (Mw) of the polymer 1 was 70,000.

[Production Example 2] Production of polymer 2 In a polymerization apparatus equipped with a stirrer, a cooling pipe and a thermometer, 145 parts of deionized water and polyvinyl alcohol (saponification degree: 80%, polymerization degree: 1) as a dispersion stabilizer. 700) 0.5 part was added and stirred.

  After the polyvinyl alcohol was completely dissolved, stirring was stopped, 100 parts of methyl methacrylate, 0.2 part of 2,2′-azobisisobutyronitrile and 0.9 part of n-dodecyl mercaptan were added and stirred again. Under stirring, the atmosphere in the polymerization apparatus was replaced with nitrogen, and the temperature was raised to 70 ° C. to carry out polymerization. After detecting the peak of the polymerization exotherm, the temperature was raised to 98 ° C., the reaction was further carried out for 0.5 hours, and the mixture was cooled to 40 ° C.

  The obtained aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, and the filtrate was washed with deionized water.

  After dehydration, it was dried at 40 ° C. for 20 hours to obtain a granular (meth) acrylic polymer (hereinafter referred to as “polymer 2”). The weight average molecular weight (Mw) of Polymer 2 was 40,000.

[Example 1]
In a reaction vessel equipped with a cooler, 10 parts of 2-hydroxypropyl methacrylate as component (A), 40 parts of benzyl methacrylate as component (B), 25 parts of New Frontier BPE-4 as component (C), component 20 parts of ADK STAB PFR was added as (E), and 5 parts of polymer 1 produced in Production Example 1 was added as component (D) while stirring these components in the reaction vessel. Next, the solution in the reaction vessel was heated to 70 ° C. and stirred for 1 hour while maintaining the temperature. After confirming that the polymer 1 was completely dissolved, it was cooled to 23 ° C. Further, 3 parts of Irgacure 184 was added as component (F) and stirred for 30 minutes to obtain a curable resin composition.

By sandwiching the curable resin composition in the center of two 10 cm × 10 cm glass plates, irradiating with a chemical lamp (irradiation intensity: 5 mW / cm ² ) for 30 minutes, and further after curing at 100 ° C. for 30 minutes, A cured product of about 50 mm × thickness of about 1 mm was obtained. Each evaluation was performed with respect to the obtained hardened | cured material. The results are shown in Table 1. “Part” of the composition in the table means “part by mass”.

[Examples 2 to 23]
Except for changing the composition as shown in Tables 1 and 2, a curable resin composition and a cured product having a diameter of about 50 mm and a thickness of about 1 mm were prepared and evaluated in the same manner as in Example 1.

[Comparative Examples 1-2]
In Comparative Examples 1 and 2, except that the composition was changed as shown in Table 1 and Table 2, a curable resin composition and a cured product having a diameter of about 50 mm and a thickness of about 1 mm were prepared in the same manner as in Example 1. Each evaluation was performed.

Each component described in the table is as follows.
2-Hydroxypropyl methacrylate (trade name: Acryester HP, manufactured by Mitsubishi Rayon Co., Ltd.).
2-hydroxyethyl methacrylate (trade name: Acryester HO, manufactured by Mitsubishi Rayon Co., Ltd.).
-Benzyl methacrylate (trade name: Acryester BZ, manufactured by Mitsubishi Rayon Co., Ltd.).
Orthophenylphenoxyethyl acrylate (trade name: NK ester A-LEN-10, manufactured by Shin-Nakamura Chemical Co., Ltd.)
New frontier BPE-4: ethoxylated bisphenol A diacrylate (trade name: New Frontier BPE-4, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Blemmer PDP-400N: Polypropylene glycol dimethacrylate (trade name: Blemmer PDP-400N, manufactured by NOF Corporation).
Polymer 1: (meth) acrylic polymer produced in Production Example 1 (MMA / nBA = 93/7, Mw = 70,000).
Polymer 2: (Meth) acrylic polymer produced in Production Example 2 (PMMA, Mw = 40,000).
Adeka Stub PFR: Non-halogen condensed phosphate (trade name: Adeka Stub PFR, manufactured by ADEKA).
Adekastab FP-600: non-halogen condensed phosphate (trade name: Adekastab FP-600, manufactured by ADEKA).
Irgacure 184: 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by BASF, photopolymerization initiator).
Tetrahydrofurfuryl methacrylate (trade name: acrylate ester THF, manufactured by Mitsubishi Rayon Co.).
I-Butyl methacrylate (trade name: Acryester IB, manufactured by Mitsubishi Rayon Co., Ltd.)
Electro stripper ME-2: Anionic surfactant (trade name: Electro stripper ME-2, manufactured by Kao Corporation).
Electro stripper AC: amphoteric antistatic agent (trade name: Electro stripper AC, manufactured by Kao Corporation)
Electro stripper QN: a cationic antistatic agent (trade name: Electro stripper QN, manufactured by Kao Corporation).
-Reodol TW-L120: nonionic antistatic agent (trade name: Rheodor TW-L120, manufactured by Kao Corporation).

  From Table 1 and Table 2, it turns out that the hardened | cured material of the curable resin composition obtained by each Example has high transparency. Moreover, it turns out that Examples 18-23 which mix | blended the antistatic agent have high transparency and antistatic property. On the other hand, Comparative Example 1 and Comparative Example 2 in which component (E) was not blended resulted in low transparency.

Claims (8)

  Monofunctional (meth) acrylate (A) having a hydroxyl group, monofunctional (meth) acrylate (B) having an aromatic ring structure other than component (A), polyfunctional (meth) acrylate (C), (meth) A curable resin composition containing an acrylic polymer (D), a condensed phosphate ester compound (E), and a polymerization initiator (F). Component (A) is 1 to 30 mass%, Component (B) is 10 to 80 mass%, and Component (C) is 5 to 40 mass% with respect to 100 mass% of the total amount of components (A) to (E) The component (D) is 1 to 30% by mass and the component (E) is 1 to 40% by mass,
The curable resin composition of Claim 1 which contains 0.1-10 mass parts of components (F) with respect to 100 mass parts of total amounts of components (A)-(E). Component (A) is a hydroxyalkyl (meth) acrylate,
Component (B) is at least one selected from phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate,
Component (C) is at least one selected from polyalkylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate,
Component (D) is at least one selected from polymethyl methacrylate, a copolymer composed of methyl methacrylate units and n-butyl methacrylate units, and a copolymer composed of methyl methacrylate units and n-butyl acrylate units,
The curable resin composition according to claim 1 or 2, wherein the component (E) is a non-halogen condensed phosphate ester.   Furthermore, the curable resin composition in any one of Claims 1-3 containing an antistatic agent (G).   Hardened | cured material formed by hardening | curing the curable resin composition in any one of Claims 1-4.   A coating material comprising the cured product according to claim 5.   A sheet comprising the cured product according to claim 5.   A film comprising the cured product according to claim 5.