JP2006342214A - Photocurable resin composition, and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable resin composition capable of forming coating film exhibiting sufficient antistaticity, also excellent in scratch resistance and transparency and suppressed in bleedout, and to provide a laminate having the cured coating film of the above composition on at least part of the surface of its base resin. <P>SOLUTION: The photocurable resin composition comprises (A) a specific amount of a blend of each specific amount of (a-1) a polymerizable compound having in the molecule at least two or more (meth)acryloyloxy groups and (a-2) a compound having one ethylene-based unsaturated bond, (B) a specific amount of a copolymer obtained by copolymerization between each specific amount of (b-1) a quaternary ammonium salt group-bearing specific compound and (b-2) a one unsaturated double bond-bearing compound copolymerizable with the compound(b-1), (C) a specific amount of a photopolymerization initiator, (D) a specific amount of a hindered amine-based compound and (E) a specific amount of dimethylaminoethyl (meth)acrylate. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides a laminate having a film exhibiting sufficient antistatic properties, excellent scratch resistance and transparency, with suppressed bleeding out, and a photocurable resin composition capable of forming such a film Related to things.

  Synthetic resins such as acrylic resins and polycarbonate resins have characteristics such as transparency, impact resistance, and electrical insulation, and are widely used as industrial materials, building materials, and the like. However, since molded products made of these synthetic resins have low surface hardness, there are cases where scratches due to scratching or the like are likely to occur. In addition, since the synthetic resin molded product has a high volume resistivity, charging may occur due to static electricity and dust may be easily attached. In order to suppress these problems, many improvements have been attempted in the past, but no effective means are known.

  As a method for improving the scratch resistance, it is known that a polyfunctional monomer such as polyfunctional (meth) acrylate is used to form a cross-linked film on the substrate surface. In many cases, it did not show any prevention or was insufficient.

  As a method for improving the antistatic property, a polymerizable compound containing at least two acryloyloxy groups and / or methacryloyloxy groups such as ethylene glycol dimethacrylate and a quaternary ammonium salt in the molecule It is known that by forming a film by polymerizing a composition comprising the above, it is excellent in abrasion resistance and solvent resistance, and can improve antistatic properties and surface dyeability (see, for example, Patent Document 1). ).

  However, according to the method described in the publication, since the hygroscopic property of the polymerizable compound containing a quaternary ammonium salt is too high, a lot of moisture is contained in the composition forming the film. In some cases, polymerization curing unevenness, quality unevenness and the like may occur during polymerization. Furthermore, even if it is attempted to remove moisture in the polymerizable compound containing the quaternary ammonium salt, the polymerizable compound containing the quaternary ammonium salt has high polymerizability, so that it is polymerized during the heating and decompression operation, so that it is substantially anhydrous. It was difficult to obtain a polymerizable compound containing a quaternary ammonium salt.

The above-mentioned problems relating to the hygroscopicity of the polymerizable compound containing a quaternary ammonium salt are obtained by replacing the polymerizable compound containing a quaternary ammonium salt with a compound (b ₁ ) having a quaternary ammonium base, and a quaternary ammonium glycol such as polyethylene glycol methacrylate. It is known to be improved by using a copolymer comprising a compound (b ₂ ) having one unsaturated double bond copolymerizable with a compound having a secondary ammonium base (for example, (See Patent Documents 2 and 3).

  However, although the problem relating to hygroscopicity is improved by the method described in the publication, when the obtained film is placed in a high temperature and high humidity environment, the copolymer is hydrolyzed, and the quaternary ammonium produced by the hydrolysis. Sometimes salt bleeded out. And the external appearance of the film may be deteriorated by bleed-out of the quaternary ammonium salt.

  The above-mentioned problem concerning bleedout of quaternary ammonium salt is that one unsaturated divalent copolymerizable with compound (b-1) having a quaternary ammonium base and a compound having a quaternary ammonium base such as polyethylene glycol methacrylate. It is known that the copolymer composed of the compound (b-2) having a heavy bond is improved by including a hindered amine compound (see, for example, Patent Document 4).

However, bleed-out suppression was insufficient when placed in a hot and humid environment for a long time.
Japanese Examined Patent Publication No. 54-15074 JP-A-6-73305 JP-A-8-311366 JP 2001-323029 A

  An object of the present invention is to provide a photocurable resin composition that exhibits sufficient antistatic properties, is excellent in scratch resistance and transparency, and can form a coating in which bleeding out of a quaternary ammonium salt is suppressed. There is. Furthermore, the objective of this invention is providing the laminated body which has the cured film of the said photocurable resin composition on the surface of at least one part of base resin.

In the present invention, 80 to 100% by mass of a polymerizable compound (a-1) having at least two (meth) acryloyloxy groups in the molecule, and one α, β-ethylenically unsaturated bond in the molecule. 100 parts by mass of the mixture (A) composed of 0 to 20% by mass of the compound (a-2) having, and the following general formula (1)

(Wherein R ¹ is a hydrogen atom or a methyl group, R ^{2 to} R ⁴ are alkyl groups that may contain a substituent having 1 to 9 carbon atoms, m is an integer of 1 to 10, and X ⁻ is derived from a quaternizing agent. An anion of the above, Y represents an oxygen atom or NH), and 20 to 99% by mass of the compound (b-1) represented by the compound, and one unsaturated double bond copolymerizable with the compound (b-1). 0.5 to 30 parts by mass of a copolymer (B) obtained by polymerizing 1 to 80% by mass of the compound (b-2) having, 0.1 to 10 parts by mass of a photopolymerization initiator (C), It is a photocurable resin composition comprising 0.01 to 3 parts by mass of a hindered amine compound (D) and 0.3 to 20 parts by mass of dimethylaminoethyl (meth) acrylate.

  Moreover, this invention is a laminated body which has the cured film of the said photocurable resin composition on the surface of at least one part of base resin.

  The photocurable resin composition of the present invention includes a polymerizable compound (a-1) having two or more (meth) acryloyloxy groups and a compound (a-2) having an α, β-ethylenically unsaturated bond. A mixture (A), a copolymer (B) obtained by polymerizing a compound (b-1) having a specific quaternary ammonium base and a compound (b-2) having an unsaturated double bond, and light Since it contains a polymerization initiator (C), a hindered amine compound (D), and dimethylaminoethyl (meth) acrylate in a predetermined mass ratio, a film obtained by photocuring this photocurable resin composition The laminate having a sufficient antistatic property and excellent scratch resistance and transparency, and bleed-out of the quaternary ammonium salt is suppressed.

  The photocurable resin composition of the present invention comprises a polymerizable compound (a-1) having two or more (meth) acryloyloxy groups and a compound having one α, β-ethylenically unsaturated bond in the molecule. A mixture (A-2) comprising (a-2), a compound (b-1) having quaternary ammonium and a compound (b-2) having one unsaturated double bond copolymerizable with (b-1) ), A photopolymerization initiator (C), a hindered amine compound (D), and dimethylaminoethyl (meth) acrylate in a predetermined mass ratio.

  The polymerizable compound (a-1) used in the present invention is a cross-linking reactive compound having at least two (meth) acryloyloxy groups in the molecule, and is a residue that binds each (meth) acryloyloxy group. Is a hydrocarbon or a derivative thereof, and may include an ether bond, a thioether bond, an ester bond, an amide bond, a urethane bond, or the like in the molecule.

  The main examples of these compounds are esterified products obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or derivatives thereof; polyhydric alcohol and polyhydric carboxylic acid or anhydride thereof. And a linear esterified product having two or more (meth) acryloyloxy groups in one molecule, obtained from a product and (meth) acrylic acid or a derivative thereof. In addition, (meth) acryl means an acryl and / or a methacryl.

Examples of esterified products obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Polyethylene glycol di (meth) acrylate such as acrylate; 1,4-butanediol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylol Propane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin (Meth) acrylate, the following general formula (3)

[Wherein, n is an integer of 1 to 4, and at least three of X ^{1 to} X ⁶ are (meth) acryloyl groups, and the other represents a hydroxyl group. ], For example, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) Examples thereof include acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and the like.

  In a linear esterified product having two or more (meth) acryloyloxy groups in one molecule obtained from a polyhydric alcohol and a polycarboxylic acid or anhydride thereof and (meth) acrylic acid, Preferred combinations of polycarboxylic acids or anhydrides thereof and (meth) acrylic acid include malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, malonic acid / Glycerin / (meth) acrylic acid, malonic acid / pentaerythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (meth) acrylic acid, succinic acid / Glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / (meth) acrylic acid, azimuth Acid / trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolpropane / (meth) acrylic acid, adipic acid / glycerin / (meth) acrylic acid, adipic acid / pentaerythritol / (meth) acrylic acid, glutar Acid / trimethylolethane / (meth) acrylic acid, glutaric acid / trimethylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (meth) acrylic acid, glutaric acid / pentaerythritol / (meth) acrylic acid, sebacic acid / Trimethylolethane / (meth) acrylic acid, sebacic acid / trimethylolpropane / (meth) acrylic acid, sebacic acid / glycerin / (meth) acrylic acid, sebacic acid / pentaerythritol / (meth) acrylic acid, fumaric acid / Trimethylolethane / (meth) acryl Acid, fumaric acid / trimethylolpropane / (meth) acrylic acid, fumaric acid / glycerin / (meth) acrylic acid, fumaric acid / pentaerythritol / (meth) acrylic acid, itaconic acid / trimethylolethane / (meth) acrylic acid , Itaconic acid / trimethylolpropane / (meth) acrylic acid, itaconic acid / glycerin / (meth) acrylic acid, itaconic acid / pentaerythritol / (meth) acrylic acid, maleic anhydride / trimethylolethane / (meth) acrylic acid And maleic anhydride / trimethylolpropane / (meth) acrylic acid, maleic anhydride / glycerin / (meth) acrylic acid, maleic anhydride / pentaerythritol / (meth) acrylic acid, and the like.

Other examples of the polymerizable compound (a-1) include trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, trimethyl. A polyisocyanate represented by the following general formula (4) obtained by trimerization of hexamethylene diisocyanate and the like;

(In the formula, R represents a divalent hydrocarbon group having 1 to 12 carbon atoms which may contain a substituent.) Acrylic monomer having active hydrogen, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, 1,2,3-propanetriol-1,3-di ( Urethane (meth) acrylate obtained by reacting 3 moles or more per mole of isocyanate with meth) acrylate, 3-acryloyloxy-2-hydroxypropyl (meth) acrylate, etc .; of tris (2-hydroxyethyl) isocyanuric acid Poly (di (meth) acrylate, tri (meth) acrylate, etc. Meth) acryloyloxyethyl] isocyanurate; known epoxy polyacrylates; can be mentioned known urethane polyacrylate.

  In addition, as content of a polymeric compound (a-1), in order to implement | achieve sufficient abrasion resistance of a film, it is 80 to 100 mass% with respect to the whole mixture (A). It is preferable that it is 85 mass% or more. In addition, even if it consists of a single polymeric compound (a-1), it is called "mixture (A)" for convenience.

  Examples of the compound (a-2) used in the present invention include monomers having one α, β-ethylenically unsaturated bond in the molecule other than dimethylaminoethyl (meth) acrylate. . In particular, a compound having compatibility with both the polymerizable compound (a-1) and the copolymer (B) and having a polar group in the molecule is preferable.

  Specifically, it is appropriately selected depending on the kind and amount of the polymerizable compound (a-1) and the copolymer (B), but in general, acrylic acid, methacrylic acid, and their amides, amide methylolated products. 2-hydroxyethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like are preferable.

  In addition, as content of a compound (a-2), in order to implement | achieve sufficient abrasion resistance of a film, it is set as 0 mass% or more and 20 mass% or less with respect to the whole mixture (A). It is preferable that it is 15 mass% or less.

  The compound (b-1) used in the present invention is a compound having a quaternary ammonium base. For example, (meth) acrylates or (meth) acrylamides having an amino group are quaternized with a quaternizing agent. Can be obtained.

  Examples of (meth) acrylates having an amino group include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) Examples thereof include acrylate, dipropylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, and dihydroxyethylaminoethyl (meth) acrylate.

  Examples of (meth) acrylamides having an amino group include dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminobutyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diethylaminopropyl (meth) Examples include acrylamide, dipropylaminoethyl (meth) acrylamide, dibutylaminoethyl (meth) acrylamide, and dihydroxyethylaminoethyl (meth) acrylamide.

  In addition, in the compound (b-1) represented by the general formula (1), the obtained copolymer (B) can be realized with high hydrolysis resistance, and bleedout of the quaternary ammonium salt can be further suppressed. For these reasons, a compound in which Y is NH is more preferable.

  Therefore, a compound obtained by quaternizing (meth) acrylamides having an amino group is preferable.

  Quaternizing agents include alkyl sulfates such as dimethyl sulfate, diethyl sulfate and dipropyl sulfate, sulfonate esters such as methyl p-toluenesulfonate and methyl benzenesulfonate, alkyl phosphates such as trimethyl phosphite, and alkyl benzyl. Various halides such as chloride, benzyl chloride, alkyl chloride, and alkyl bromide are used, and alkyl sulfates and sulfonate esters are particularly preferred from the viewpoint of thermal decomposition resistance.

That is, the anion (X ⁻ ) derived from the quaternizing agent in the general formula (1) has the general formula R ⁷ SO ₃ ⁻ or R ⁷ OSO ₃ ⁻ (wherein R ⁷ is a hydrogen atom or a carbon number of 1 to 20). An alkyl group, an aryl group or an aralkyl group which may contain a substituent is preferred.

  In addition, although m in General formula (1) is an integer greater than or equal to 1 or less, it can implement | achieve the high hydrolysis resistance of the copolymer (B) obtained, and can suppress the bleedout of a quaternary ammonium salt more. For reasons such as these, 2 or more and 6 or less are preferable.

  As the compound (b-2) having one unsaturated double bond copolymerizable with the compound (b-1) described above, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; methyl acrylate and ethyl acrylate Acrylic acid esters such as; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; acid anhydrides such as maleic anhydride and itaconic anhydride; maleimides such as N-phenylmaleimide; 2-hydroxyethyl acrylate and 2-hydroxy Hydroxy group-containing monomers such as propyl methacrylate; Nitrogen-containing monomers such as acrylamide and acrylonitrile; Epoxy group-containing monomers such as allyl glycidyl ether and glycidyl methacrylate; Terminal methacrylate polymethyl methacrylate, Terminal styryl polymethyl methacrylate , Terminal methacrylate polystyrene, terminal methacrylate polyethylene glycol, can be exemplified macromonomers such as terminal methacrylate acrylonitrile styrene copolymers, may be used as a mixture of two or more of these.

As the compound (b-2) having one unsaturated double bond capable of copolymerization, the following general formula (2) is used from the viewpoint of the balance of the properties of the resulting film.

Wherein R ⁵ is a hydrogen atom or a methyl group, R ⁶ is a hydrogen atom or an alkyl group, aryl group or aralkyl group which may contain a substituent having 1 to 18 carbon atoms, and A is a substituent having 2 to 4 carbon atoms. It is preferable to use the compound represented by the alkylene group which may contain, n represents the integer of 0-500.

  In particular, when a compound represented by n = 2 to 500 in the general formula (2) is used, the compatibility between the copolymer (B), the polymerizable compound (a-1) and the compound (a-2) becomes good. The photocurable resin composition is preferable because it can be uniformly cured.

  In the general formula (2), compounds represented by n = 2 to 500 include polyethylene glycol (4) mono (meth) acrylate, polyethylene glycol (23) mono (meth) acrylate, polyethylene glycol (300) mono (meta) ) Acrylate, polypropylene glycol (23) mono (meth) acrylate, polybutylene glycol (23) mono (meth) acrylate, polyethylene glycol (23) mono (meth) acrylate monomethyl ether, polyethylene glycol (23) mono (meth) Acrylate monobutyl ether, polyethylene glycol (23) mono (meth) acrylate monostearyl ether, polyethylene glycol (23) mono (meth) acrylate monophenyl ether, polyethylene glycol (23) mono (meth) acrylate monobenzyl ether, can be exemplified polyethylene glycol (23) mono (meth) acrylate mono oleyl ether and the like. The number in parentheses represents the number of polyalkylene glycol units.

  The content of the compound (b-1) is 20% by mass or more and 99% by mass or less, preferably 90% by mass or less with respect to the copolymer (B) in order to realize good antistatic properties. On the other hand, the content of the compound (b-2) having one unsaturated double bond is 1% by mass or more and 80% by mass from the viewpoint of the uniformity of the photocurable resin composition and the adhesion to the base synthetic resin. % Or less, preferably 10% by mass or more.

  The copolymer (B) is obtained from the compounds (b-1) and (b-2) mixed at the above mass ratio in a solvent such as methanol using a polymerization initiator such as peroxide or azobis. It can be produced by solution polymerization method or the like.

  In the present invention, antistatic properties are imparted to the coating film by the action of the copolymer (B). The added amount of such a copolymer (B) is 0.5 parts by mass or more with respect to 100 parts by mass of the mixture (A) in order to realize sufficient antistatic properties, and has good scratch resistance. In order to realize, it is 30 parts by mass or less. Furthermore, it is preferable that it is 5 to 20 mass parts.

  The photopolymerization initiator (C) used in the present invention is not particularly limited. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, Benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, Carbonyl compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethyl Diphenylphosphine oxide, can be exemplified benzo dichloride ethoxy phosphine oxide and the like.

  The addition amount of the photopolymerization initiator (C) is 0.1 parts by mass or more with respect to 100 parts by mass of the mixture (A) in order to realize sufficient curability of the photocurable resin composition, and after curing. In order to suppress coloring of the film, the amount is 10 parts by mass or less. In the present invention, not only the initiator but also a plurality of initiators may be used in combination.

  The photocurable resin composition of the present invention contains a predetermined amount of a hindered amine compound (D) and dimethylaminoethyl (meth) acrylate. Therefore, the antistatic property, scratch resistance, transparency and the like of the resulting coating can be realized, and at the same time, bleedout of the quaternary ammonium salt can be suppressed even in a high temperature and high humidity environment. The mechanism is not clear, but the presence of the hindered amine compound (D) suppresses hydrolysis of the copolymer (B) obtained by copolymerizing the compounds (b-1) and (b-2). In addition, it is presumed that the presence of dimethylaminoethyl (meth) acrylate improves the affinity with the quaternary ammonium salt.

  The hindered amine compound (D) used in the present invention is not particularly limited as long as it can suppress bleed-out of the quaternary ammonium salt, but has a large suppression effect and is itself chemically stable. Therefore, a hindered amine compound having a piperidine skeleton in which all hydrogen on carbons at the 2 and 6 positions are substituted with methyl groups is preferable.

  Examples of the hindered amine compound (D) include bis (2,2,6,6-tetramethyl-4-piperidyl) succinate and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6 -Tetramethylpiperidine, 8-benzoyl 7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, tetrakis (2, Can be exemplified 6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, 4 Metokurirokishi-2,2,6,6-tetramethylpiperidine and the like.

  The addition amount of the hindered amine compound (D) is set to 0.01 parts by mass or more with respect to 100 parts by mass of the mixture (A) in order to sufficiently suppress bleed out under high temperature and high humidity conditions, and 0.05 mass. Part or more is preferred. Moreover, in order to maintain favorable sclerosis | hardenability of a photocurable resin composition and implement | achieve sufficient abrasion resistance, it is 3 mass parts or less, and 2.5 mass parts or less are preferable.

  The addition amount of dimethylaminoethyl (meth) acrylate used in the present invention is 0.3 parts by mass or more with respect to 100 parts by mass of the mixture (A) in order to sufficiently suppress bleed out under high temperature and high humidity conditions. 0.5 parts by mass or more is preferable. Moreover, in order to maintain favorable sclerosis | hardenability of a photocurable resin composition and implement | achieve sufficient abrasion resistance, it is 20 mass parts or less, and 15 mass parts or less are preferable.

  Various additives conventionally used may be added to the photocurable resin composition in the present invention. Examples of the additive include a surfactant, a leveling agent, a dye, a pigment, an antioxidant, an ultraviolet absorber, a stabilizer, a flame retardant, and a plasticizer.

  As a method for obtaining a laminate having the anti-bleeding property and the scratch resistance by using the photo-curable resin composition of the present invention, bleed-out is suppressed, a roller coating method, a bar coating method, a spraying method is applied to the base resin surface. A method of applying the photocurable resin composition of the present invention by a coating method, an air knife coating method, a dipping method or the like and curing it with light; a photocurable resin of the present invention between glass and a base resin There is a method in which the composition is sandwiched and photocured to transfer the film onto the surface of the base resin. Also, a method in which the photocurable resin composition is applied to the mold surface by the above method and cured by light, and then a mold is produced with the obtained coating as the inside, a resin raw material is injected, polymerized, cured, and peeled off from the mold Is mentioned. The material of the mold used for this method is not particularly limited. For example, stainless steel, a glass plate, etc. are preferable. This cast polymerization can also be carried out continuously. For example, the raw material is continuously injected into a mold formed by opposing surfaces of a pair of stainless steel endless belts that run facing each other at a predetermined interval and two gaskets that run following the running of the endless belt. It is possible to use a so-called continuous casting method in which the polymer is cured and cured, and the polymer is peeled off from the endless belt. In this case, the photocurable resin composition may be applied to the surface of the endless belt and cured. This method is excellent in productivity.

  The base resin used in the present invention is not particularly limited, but preferred examples include acrylic resin, polycarbonate resin, vinyl chloride resin, ABS resin, styrene resin and the like.

  In the present invention, the thickness of the film made of the photocurable resin composition is preferably 0.5 μm or more and more preferably 1 μm or more in order to achieve sufficient antistatic properties and scratch resistance. Moreover, in order to suppress problems, such as a crack generate | occur | produced in a film or a film missing when a laminated body is cut | disconnected, 100 micrometers or less are preferable and 50 micrometers or less are more preferable.

  In the laminate of the present invention, an antireflection film can be further provided on the coating made of the photocurable resin composition as necessary. Moreover, the film which consists of a photocurable resin composition of this invention can be provided in the single side | surface of a laminated body, and other functional thin films, such as an antireflection film and an adhesive film, can also be provided in the other side.

The surface of the laminate of the present invention is excellent in transparency, scratch resistance and antistatic properties, and bleed out is suppressed. The antistatic property can be evaluated by a surface resistance value and a charge half-life, and the surface resistance value is preferably 1 × 10 ¹³ Ω / □ or less, more preferably 5 × 10 ¹² Ω / □ or less; Is preferably 30 seconds or shorter, and more preferably 10 seconds or shorter. The scratch resistance can be evaluated by scratch haze, and the scratch haze is preferably 10% or less, more preferably 5% or less. Further, according to the present invention, it is possible to prevent bleeding out after the moisture resistance test.

  According to the laminate having a cured film obtained by photocuring the photocurable resin composition of the present invention on at least a part of the surface of the base resin, it has antistatic properties, so that it is difficult for dust to adhere to it. Since it has scratch resistance, it is difficult to be scratched by handling, etc., there is no coloring, etc., transparency is good, and bleeding out of the quaternary ammonium salt is suppressed, so that a good appearance can be maintained.

  Therefore, the laminate of the present invention can be used for component covers, glazing materials, vehicle members, display materials, lighting materials, nameplates, etc., in particular, front plates for various displays such as CRTs, liquid crystal televisions, projection televisions, It can be suitably used as a face plate for a mobile phone.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not restrict | limited by these Examples.

  Unless otherwise specified, commercially available special grade products were used for all reagents. “Part” means “part by mass”.

(Evaluation methods)
(A) Total light transmittance:
In order to evaluate the transparency of the laminate, the total light transmittance was measured by HAZE METER NDH2000 manufactured by Nippon Denshoku Co., Ltd. according to the measurement method shown in JIS-K7361.

  (A) The surface resistance value was measured as an index of antistatic properties. As a measurement method, a super insulation resistance meter (manufactured by TOA, ULTRA MEGOHMMETER MODEL SM-10E) is used, and the measurement temperature is 23 ° C. and the measurement humidity is 50% relative humidity (hereinafter referred to as “% relative humidity”). The surface resistance value (Ω / □) after 1 minute was measured at an applied voltage of 500 V under the conditions of. In addition, as a sample for a measurement, what was previously conditioned at 23 ° C. and 50 RH% for 1 day was used.

  (C) The charge half-life was measured as another index of antistatic properties. As a measuring method, a static Honest meter (manufactured by Ashito Shokai) is used, and measurement is performed under the conditions of an applied voltage of 10000 V, a sample rotation speed of 1550 rpm, an application time of 30 seconds, a measurement temperature of 23 ° C., and a measurement humidity of 50 RH%. The time required for the sample voltage to halve after the applied voltage was cut off was defined as the charge half-life time (seconds). In addition, as a sample for a measurement, what was previously conditioned at 23 ° C. and 50 RH% for 1 day was used.

(D) The scratch resistance was evaluated by the change in haze (scratch haze) before and after the scratch test. That is, a circular pad with a diameter of 25.4 mm with # 000 steel wool was placed on the surface of the sample coating side, and under a load of 9.8 N, a 20 mm distance was scratched 100 times, and before and after scratching. The difference in haze value was calculated from the following formula (1);
[Abrasion haze (%)]
= [Haze after abrasion (%)]-[haze before abrasion (%)] (1)
In addition, haze was measured based on the measuring method shown by JIS-K7136 by Nippon Denshoku HAZE METER NDH2000.

(E) Bleed-out was evaluated by a moisture resistance test. That is, after leaving the sample for 10 days and 30 days under the conditions of 40 ° C. and 95 RH%, the appearance of the coating was visually observed and evaluated in the following two stages;
○: No change ×: Appearance decreased due to bleeding

  (Synthesis of Copolymer B) 188 parts of dimethylaminopropylmethacrylamide and 228 parts of methanol were put into a glass flask equipped with stirring blades, and a mixture of 136 parts of dimethylsulfuric acid and 41.3 parts of methanol was stirred at an internal temperature. Was dropped to 15 ° C. or lower and stirring was continued for 30 minutes after completion of the dropping to obtain a compound solution having a quaternary ammonium base.

  In this solution, 2.4 parts of 2,2-azobis (2,4-dimethylvaleronitrile), 2.4 parts of n-octyl mercaptan, 384 parts of methanol, polyethylene glycol (23) monomethacrylate monomethyl ether (the parentheses are polyethylene glycol) 485 parts of the number of units) was added, polymerized in a nitrogen atmosphere at 60 ° C. for 6 hours, and vacuum-dried at 50 ° C. for 3 days to obtain a copolymer B imparting antistatic properties.

[Example 1]
As compound (a-1), trimethylolpropane triacrylate (Aronix M-309 manufactured by Toagosei Co., Ltd., hereinafter also referred to as “M309”) 47.5 parts, polyethylene glycol diacrylate having a weight average molecular weight of about 200 (Shin Nakamura) NK Ester A200 manufactured by Chemical Industry Co., Ltd., 13.75 parts, hereinafter referred to as “A200”), 1,6-hexanediol diacrylate (Biscoat # 230, manufactured by Osaka Organic Chemical Co., Ltd., hereinafter also referred to as “C6DA”) 13.75 Part, pentaerythritol triacrylate (Aronix M-305 manufactured by Toagosei Co., Ltd., hereinafter also referred to as “M305”), a succinic acid / trimethylolethane / acrylic acid molar ratio 1: 2: 4 condensation reaction mixture (Osaka) Copolymerized with 20 parts of Organic Chemical Industries, Ltd. (hereinafter also referred to as “TAS”) 11 parts of the body (B), and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173 manufactured by Ciba Specialty Chemicals Co., Ltd.) as the photopolymerization initiator (C). 1.5 parts, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine (Sanyo LS744, hereinafter also referred to as “LS744”) as hindered amine compound (D) 0. 3 parts and 1.0 part of dimethylaminoethyl methacrylate (Acrylic ester DM manufactured by Mitsubishi Rayon Co., Ltd., hereinafter also referred to as “DM”) were mixed to prepare a photocurable resin composition.

The obtained photocurable resin composition was dropped on a SUS plate, and a 20 μm thick polyethylene terephthalate (hereinafter also referred to as “PET”) biaxially stretched film (Diafoil) was placed thereon. The thickness of the photocurable resin composition layer was set to 20 μm by ironing with a rubber roll having a JIS hardness of 40 °. Then, under a fluorescent ultraviolet lamp with an output of 40 W (Toshiba, FL40BL), a 10 cm position was passed through the PET film surface at a speed of 2 m / min and precured, and then the PET film was peeled off. Next, a position of 20 cm under a high-pressure mercury lamp with an output of 30 W / cm ² was passed through the coating at a speed of 0.8 m / min and cured. The two SUS plates treated in this way were opposed so that the cured film was on the inside, and the periphery was sealed with a gasket made of soft vinyl chloride to produce a cell for casting polymerization. In this cell, 100 parts of syrup composed of 20% by mass of a methyl methacrylate polymer having a weight average molecular weight of 220,000 and 80% by mass of methyl methacrylate, 0.05 part of azobisdimethylvaleronitrile, and dioctylsulfosuccinate A resin raw material consisting of 0.005 part of sodium salt was injected, the distance between the opposing SUS plates was adjusted to 2.7 mm, and polymerized in an 80 ° C. water bath for 1 hour and then in a 130 ° C. air furnace for 1 hour. . After cooling, the resin plate was peeled from the SUS plate to obtain an acrylic resin laminate having a cured coating on the surface.

The obtained acrylic resin laminate was excellent in transparency, and had a surface resistivity value of 2.0 × 10 ¹¹ Ω / □, a charge half-life of 1 second, and an abrasion haze of 0.2%. Moreover, there was no change in the external appearance of the acrylic resin laminate even after the moisture resistance test. The evaluation results are shown in Table 1.

[Examples 2 to 11, Comparative Examples 1 to 11]
An acrylic resin laminate was produced in the same manner as in Example 1 except that the raw material compositions shown in Table 1 and Table 2 were adopted. The evaluation results are shown in Tables 1 and 2.

[Example 12]
The photocurable resin composition used in Example 1 was applied to a glass plate, and then a 1.5 mm thick acrylic resin plate (Acrylite L manufactured by Mitsubishi Rayon Co., Ltd.) and a glass plate were used to form the photocurable resin composition. Then, the thickness of the photocurable resin composition layer was set to 20 μm by rubbing with a rubber roller. In this superposed state, the glass surface was heated with a far-infrared heater to raise the glass surface temperature to 70 ° C. and held in that state for 1 minute. Next, a position 20 cm below the high-pressure mercury lamp with an output of 120 W / cm ² was passed at a speed of 2 m / min with the glass surface facing up, and the photocurable resin composition was cured. The acrylic resin laminate was obtained by peeling the acrylic resin plate from the glass after curing. Table 1 shows the evaluation results on the cured film side of the obtained acrylic resin laminate.

[Comparative Example 12]
An acrylic resin plate (Acrylite L, manufactured by Mitsubishi Rayon Co., Ltd.) that was not formed with a film was evaluated. The evaluation results are shown in Table 2.

The abbreviations in the table indicate the following compounds.
“M309”: trimethylolpropane triacrylate “DPHA”: dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)
“A200”: diacrylate “C6DA” of polyethylene glycol having a weight average molecular weight of about 200: 1,6-hexanediol diacrylate “M305”: pentaerythritol triacrylate “TAS”: mole of succinic acid / trimethylolethane / acrylic acid Ratio 1: 2: 4 condensation reaction mixture “HEA”: 2-hydroxyethyl acrylate “MAA”: methacrylic acid “701A”: 2-hydroxy-3-acryloyloxypropyl methacrylate (NK Nakamura Chemical Co., Ltd., NK ester 701A )
“A-SA”: 2-acryloyloxyethyl succinic acid (NK ester A-SA manufactured by Shin-Nakamura Chemical Co., Ltd.)
“R167”: 1,6-hexanediylbis [oxy (2-hydroxypropane-1,3-diyl)] diacrylate (KAYARAD R-167 manufactured by Nippon Kayaku Co., Ltd.)
“BIP”: Benzoin isopropyl ether (Seikol BIP manufactured by Seiko Chemical Co., Ltd.)
“D1173”: 2-hydroxy-2-methyl-1-phenyl-propan-1-one “DM”: dimethylaminoethyl methacrylate

  As shown in Table 1, in Examples 1 to 12, sufficient antistatic property, scratch resistance and transparency were realized in the laminate in which the film obtained from the photocurable resin composition of the present invention was formed. It was also found that quaternary ammonium salt bleedout was also suppressed.

  On the other hand, as shown in Table 2, in Comparative Examples 1, 4 to 10, fogging due to bleed out occurred. In Comparative Examples 2 and 11, the scratch resistance was insufficient. In Comparative Example 3, the antistatic property was insufficient. In Comparative Example 12, the antistatic property and the scratch resistance were insufficient.

  The laminate having a film obtained by photocuring the photocurable resin composition obtained by the present invention exhibits sufficient antistatic properties and is excellent in scratch resistance, transparency, and the like. It is suitable for various applications such as telephone face plates.

Claims (8)

80 to 100% by mass of a polymerizable compound (a-1) having at least two (meth) acryloyloxy groups in the molecule and a compound (a) having one α, β-ethylenically unsaturated bond in the molecule (a -2) 100 parts by mass of a mixture (A) composed of 0 to 20% by mass, and the following general formula (1)

(Wherein R ¹ is a hydrogen atom or a methyl group, R ^{2 to} R ⁴ are alkyl groups that may contain a substituent having 1 to 9 carbon atoms, m is an integer of 1 to 10, and X ⁻ is derived from a quaternizing agent. An anion of the above, Y represents an oxygen atom or NH), and 20 to 99% by mass of the compound (b-1) represented by the compound, and one unsaturated double bond copolymerizable with the compound (b-1). 0.5 to 30 parts by mass of a copolymer (B) obtained by polymerizing 1 to 80% by mass of the compound (b-2) having, 0.1 to 10 parts by mass of a photopolymerization initiator (C), A photocurable resin composition comprising 0.01 to 3 parts by mass of a hindered amine compound (D) and 0.3 to 20 parts by mass of dimethylaminoethyl (meth) acrylate. The photocurable resin composition according to claim 1, wherein the compound (b-2) is a compound represented by the following general formula (2).

Wherein R ⁵ is a hydrogen atom or a methyl group, R ⁶ is a hydrogen atom or an alkyl group, aryl group or aralkyl group which may contain a substituent having 1 to 18 carbon atoms, and A is a substituent having 2 to 4 carbon atoms. An alkylene group which may contain, n represents an integer of 0 to 500.) The anion (X ⁻ ) derived from the quaternizing agent in the general formula (1) is represented by the general formula R ⁷ SO ₃ ^— or R ⁷ OSO ₃ ^— (wherein R ⁷ is a hydrogen atom or a substituent having 1 to 20 carbon atoms). 3 represents an alkyl group, an aryl group, or an aralkyl group that may contain a photocurable resin composition.   The photocurable resin composition according to any one of claims 1 to 3, wherein Y in the general formula (1) is NH.   5. The photocuring according to any one of claims 1 to 4, wherein the hindered amine compound (D) is a compound having in its molecule a piperidine skeleton in which all hydrogen on carbons at the 2 and 6 positions are substituted with methyl groups. Resin composition.   The laminated body which has the cured film of the photocurable resin composition in any one of Claims 1 thru | or 5 in the surface of at least one part of base resin.   A display front plate comprising the laminate according to claim 6.   A cellular phone face plate comprising the laminate according to claim 6.