JP4706373B2 - Curable composition containing conductive particles, cured product and laminate - Google Patents

Description

  The present invention relates to a curable composition containing conductive particles, a cured product thereof, and a laminate. More specifically, it has excellent coating properties and various base materials [for example, plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin. , Norbornene-based resins, etc.), metal, wood, paper, glass, slate, etc.] can form a coating film (film) having excellent scratch resistance and adhesion to the substrate and the substrate or adjacent layers. The present invention relates to a conductive particle-containing curable composition and a cured film (hard coat) for a printer belt or a printer drum.

  In recent years, it has excellent coating properties as a protective coating material for preventing scratches (scratching) on various substrate surfaces and preventing contamination; adhesives and sealing materials for various substrates; and a binder material for printing inks. There is a demand for a curable composition capable of forming a cured film having excellent hardness, flexibility, scratch resistance, abrasion resistance, and adhesion on the surface of various substrates.

  The printer belt is a transfer belt or a conveyance belt used as a component of an image forming apparatus of a laser printer or an ink jet printer, and is formed using a polycarbonate resin or a fluororesin material containing an antistatic agent. Since the printer belt repeatedly comes into frictional contact with other parts and paper, there has been a demand for improving the scratch resistance and extending the life. The printer drum is a photosensitive drum or a transfer drum used as a component of an image forming apparatus of a laser printer. The photosensitive drum has a structure in which a photoconductive coating layer having a thickness of about several tens of μm is provided on the outer peripheral surface of a cylinder made of aluminum or the like. The transfer drum is made of the same resin material as the transfer belt. The printer drum has also been requested to improve the scratch resistance and extend the life because it repeatedly comes into frictional contact with other parts and paper.

  As a printing method for laser printers, an intermediate transfer belt method for forming an electrostatic latent image on a photosensitive drum or a photosensitive belt and transferring the toner image obtained by developing the electrostatic latent image with toner onto a transfer belt, on a photosensitive drum There are known a transfer drum system in which an electrostatic latent image is formed and a toner image is transferred to a transfer drum, and a tandem system in which a photosensitive drum is provided for each basic color of a color printer. The above-described problems exist with respect to the printer belt and the printer drum used in any of these methods.

  On the other hand, Patent Document 1 discloses a haze (cloudiness) in which a zinc antimonate sol is dispersed in an ultraviolet curable (meth) acrylate having at least one (meth) acryloyl group in the molecule using a dispersant. Discloses an antistatic hard coat resin composition having a transparency of 1.5 or less. It is described that by curing this composition, anti-static ability with good abrasion resistance and excellent transparency can be imparted to the substrate.

  Patent Document 2 discloses a cured product of a composition containing a compound having an isocyanurate ring structure, but no particles are used. Hardness is expressed by increasing the film thickness. Further, no conductive particle component is blended.

JP-A-10-231444 JP 2004-141732 A

Although the antistatic hard coat resin composition disclosed in Patent Document 1 can improve scratch resistance, for example, when used as a hard coat material for printer belts or printer drums that repeatedly undergo frictional contact In addition, the scratch resistance was insufficient.
In addition, even if it has scratch resistance, the surface of the hard coat layer tends to be smooth like a mirror surface, resulting in insufficient slidability and close contact with other members, and the printer belt does not move smoothly. In other cases, noise may be generated by rubbing against other members, which may adversely affect the quietness of the printer.

  The present invention has been made in view of the above problems, has excellent coating properties, imparts antistatic properties to the surfaces of various substrates, and has excellent scratch resistance and sliding properties. It is an object of the present invention to provide a curable composition capable of forming a coating film (coating) having, a cured product thereof, particularly a hard coat for a printer belt or a printer drum, and a laminate including the same.

  In order to achieve the above object, the present inventors have conducted intensive research, using a resin component mainly composed of an isocyanurate-based (meth) acrylate compound, and further using zinc antimonate particles as conductive particles. It has been found that antistatic properties can be imparted with an addition amount smaller than that of antimony-doped tin oxide (ATO) particles widely used as a property imparting material, and that excellent scratch resistance and slidability can be obtained. Was completed.

［式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、一価の有機基であって、Ｒ^１〜Ｒ^３のうち少なくとも２つが、−Ｒ^４ＯＣＯＣＲ^５＝ＣＨ_２であり、Ｒ^４は、炭素数２〜８の２価の有機基であり、Ｒ^５は、水素原子又はメチル基である。］で示される化合物 １０〜５０質量％、
（Ｃ）前記（Ａ）及び（Ｂ）成分以外の多官能（メタ）アクリレート化合物 １０〜７０質量％、及び
（Ｄ）動的光散乱法で測定した数平均粒径が０．１〜３μｍである有機微粒子若しくは無機微粒子 ０．２〜９質量％
を含有することを特徴とする硬化性組成物。
［２］前記（Ｂ）成分が、トリス（（メタ）アクリロキシエチル）イソシアヌレートであることを特徴とする上記［１］に記載の硬化性組成物。
［３］前記（Ｄ）成分の微粒子が、炭化水素系単量体、（メタ）アクリル酸エステル誘導体、又はアクリルアミド系誘導体を含む２種以上の単量体の共重合体からなる粒子である、請求項１又は２に記載の硬化性組成物。
［４］前記（Ｂ）成分を、組成物中の（Ａ）成分以外の全（メタ）アクリレート成分１００質量％に対して２０質量％以上含有することを特徴とする上記［１］〜［３］のいずれかに記載の硬化性組成物。
［５］上記［１］〜［４］のいずれかに記載の硬化性組成物を硬化させてなることを特徴とする硬化膜。
［６］プリンタベルト用ハードコート膜であることを特徴とする上記［５］に記載の硬化膜。
［７］プリンタドラム用ハードコート膜であることを特徴とする上記［５］に記載の硬化膜。
［８］上記［５］に記載の硬化膜を含むことを特徴とする積層体。 According to the present invention, the following curable composition, cured product thereof, and laminate can be provided.
[1] The following component (A) zinc antimonate particles 5 to 50% by mass with respect to the total amount of the composition excluding the solvent,
(B) The following formula (1)

[In Formula (1), R ¹ , R ² and R ³ are each independently a monovalent organic group, and at least two of R ^{1 to} R ³ are —R ⁴ OCOCR ⁵ ═CH ₂ . Yes, R ⁴ is a divalent organic group having 2 to 8 carbon atoms, and R ⁵ is a hydrogen atom or a methyl group. 10 to 50% by mass of a compound represented by
(C) The polyfunctional (meth) acrylate compound other than the components (A) and (B) is 10 to 70% by mass, and (D) the number average particle diameter measured by the dynamic light scattering method is 0.1 to 3 μm. Some organic fine particles or inorganic fine particles 0.2-9 mass%
A curable composition comprising:
[2] The curable composition according to the above [1], wherein the component (B) is tris ((meth) acryloxyethyl) isocyanurate.
[3] The fine particles of the component (D) are particles made of a copolymer of two or more monomers including a hydrocarbon monomer, a (meth) acrylate derivative, or an acrylamide derivative. The curable composition according to claim 1 or 2.
[4] The above-mentioned [1] to [3], wherein the component (B) is contained in an amount of 20% by mass or more with respect to 100% by mass of all (meth) acrylate components other than the component (A) in the composition. ] The curable composition in any one of.
[5] A cured film obtained by curing the curable composition according to any one of [1] to [4].
[6] The cured film as described in [5] above, which is a hard coat film for a printer belt.
[7] The cured film as described in [5] above, which is a hard coat film for a printer drum.
[8] A laminate comprising the cured film according to [5].

According to the present invention, the curability has excellent coating properties, and can form a coating film (film) having excellent anti-scratch property and slidability on the surface of various substrates. A cured film comprising the composition and a cured product thereof can be provided.
According to the present invention, since a hard coat layer having excellent antistatic properties and scratch resistance can be formed on the surface of a printer belt or printer drum that repeatedly receives frictional contact, the life of the printer belt or printer drum can be extended. . In addition, it is possible to suppress the noise generated from the printer belt and the printer drum, and to improve the quietness during the printer operation.

Hereinafter, embodiments of the curable composition, the cured product and the laminate of the present invention will be specifically described.
I. Curable composition The curable composition of the present invention comprises (A) zinc antimonate particles, (B) a compound represented by the above formula (1), (C) (A) and a polyfunctional component other than the components (B) ( It contains a (meth) acrylate compound and (D) organic fine particles or inorganic fine particles having a number average particle diameter measured by a dynamic light scattering method of 0.1 to 3 μm.

Hereinafter, each structural component of the curable composition of this invention is demonstrated concretely.
1. Zinc antimonate particles (A)
The component (A) used in the present invention is zinc antimonate particles (A).

(1) Zinc antimonate particles (A)
The zinc antimonate particles (A) used in the present invention are added as a component imparting electrical conductivity, but also contribute to improving the scratch resistance of the resulting cured film.
The size of the zinc antimonate particles is preferably in the range of 10 to 100 nm, more preferably in the range of 10 to 30 nm, as measured by the dynamic scattering method. When the size of the zinc antimonate particles is in the range of 10 to 100 nm, the scratch resistance of the cured product is good.

  The zinc antimonate particles (A) are preferably in the form of powder or dispersion. In the case of a dispersion, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide and dimethylacetamide And amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

In addition, as the zinc antimonate particles used in the present invention, commercially available products may be used. Specific examples thereof include “CELNAX CX-Z210IP” (zinc oxide (ZnO) and antimony pentoxide (Sb) manufactured by Nissan Chemical Industries, Ltd. ₂ O ₅ ) and a double oxide (ZnO.Sb ₂ O ₅ ) sol, oxide concentration: 20.9 mass%, dispersion medium: isopropanol, number average particle size: 158 nm), CX-Z300H, CX-Z300H-F, CX-Z401M, CX-Z401M-F, CX-Z403M, CX-Z403M-F, CX-Z410M, CX-Z410M-F, CX-Z210IP-F, and the like can be given.

The shape of the zinc antimonate particles (A) is not particularly limited, but is spherical, hollow, porous, rod-like, plate-like, fibrous, or indeterminate, and preferably spherical. The specific surface area of the zinc antimonate particles (A) (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m ² / g, and more preferably 100 to 500 m ² / g. These zinc antimonate particles (A) can be used in a state of being dispersed in a dry powder, water or an organic solvent. For example, a finely divided dispersion of zinc antimonate particles known in the art as the dispersion can be used directly. In particular, it is preferable to use a dispersion of zinc antimonate particles in applications that require excellent transparency in the cured product.

  The amount (inclusive) of the zinc antimonate particles (A) in the curable composition is 5 to 50% by mass, preferably 5 to 20% by mass, with the total amount of the composition excluding the organic solvent being 100% by mass. If it is 5-50 mass%, scratch resistance is favorable.

  Moreover, as (A) component of this invention, it can replace with said zinc antimonate particle | grains, or can also use ATO particle | grains together with a zinc antimonate particle | grain.

2. Compound (B) represented by Formula (1)
The component (B) used in the present invention has a function of reducing curl and imparting flexibility while maintaining the hardness of the cured product. Moreover, it has the function to improve steel wool resistance in a laminated body with a specific low refractive index layer.

［式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、一価の有機基であって、Ｒ^１〜Ｒ^３のうち少なくとも２つが、−Ｒ^４ＯＣＯＣＲ^５＝ＣＨ_２であり、Ｒ^４は、炭素数２〜８の２価の有機基であり、Ｒ^５は、水素原子又はメチル基である。］ The compound (B) represented by the following formula (1) which is the component (B) used in the present invention is an isocyanuric acid derivative having a polymerizable unsaturated group.

[In Formula (1), R ¹ , R ² and R ³ are each independently a monovalent organic group, and at least two of R ^{1 to} R ³ are —R ⁴ OCOCR ⁵ ═CH ₂ . Yes, R ⁴ is a divalent organic group having 2 to 8 carbon atoms, and R ⁵ is a hydrogen atom or a methyl group. ]

  The component (B) preferably has two or more polymerizable unsaturated groups in the molecule, and the polymerizable unsaturated group is not particularly limited, but is preferably a (meth) acrylate group. By having two or more polymerizable unsaturated groups, the crosslinking density in the cured film is increased, and the decrease in hardness can be reduced.

  Specific examples of the component (B) that can be used in the present invention include tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2 -Hydroxyethyl) isocyanurate mono (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate mono (meth) acrylate, and their starting alcohols Examples thereof include (meth) acrylates of ethylene oxide (EO), propylene oxide, or caprolactam adduct. Of these, isocyanuric acid EO (ethylene oxide) modified tri (meth) acrylate is particularly preferable.

  Examples of commercially available products that can be suitably used as the compound (B) include Aronix M-313, M-315, M-325, M-326, M-327 (above, manufactured by Toa Gosei Chemical Co., Ltd.), SR-368. (Manufactured by Sartomer). Said compound can be used individually by 1 type or in combination of 2 or more types.

The content of the compound (B) used in the present invention is 10 to 50% by mass, preferably 20 to 50% by mass, more preferably 35 to 50% by mass, with the total amount of the composition excluding the organic solvent being 100% by mass. %. When the amount is less than 10% by mass, the curling property of the cured film may be increased. When the amount exceeds 50% by mass, the hardness of the cured film may be insufficient.
Further, the content of the compound (B) is preferably 20% by mass or more, and 40% by mass or more with respect to 100% by mass of all (meth) acrylate components other than the (A) component in the composition of the present invention. If it is more preferable, it is especially preferable if it is 60 mass% or more. By being 20 mass% or more, the curvature of a cured film can be reduced effectively. Here, the total (meth) acrylate component other than the (A) component refers to a (meth) acrylate component contained in the total soluble component excluding the (A) component which is an insoluble particle. Specifically, it means the total amount of the component (B) and the component (C) described later.

3. Polyfunctional (meth) acrylate compounds (C) other than components (A) and (B)
The compound (C) is particularly preferably used for increasing the flexibility of the cured film.

  The polyfunctional (meth) acrylate compound as the component (C) is a (meth) acrylate monomer containing two or more polymerizable unsaturated groups in the molecule. The polyfunctional (meth) acrylate compound is suitably used for increasing the curability and hardness of the cured film. Here, polyfunctional means having two or more (meth) acryloyl groups in one molecule, and a trifunctional or higher (meth) acrylate compound is preferable from the viewpoint of film-forming properties and hardness, and five or more functional groups. The (meth) acrylate compound is more preferable.

Preferable specific examples of the polyfunctional (meth) acrylate compound include pentaerythritol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like.
Commercially available products of polyfunctional (meth) acrylate compounds include KAYARAD DPHA, PET-30 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-305, M-400, M-402, M-404 (Toagosei Co., Ltd.) And NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  The content of the component (C) used in the present invention is 10 to 70% by mass, more preferably 20 to 60% by mass, based on 100% by mass of the total composition excluding the organic solvent. If it is 70% by mass or more, the flexibility and curling properties of the cured film may be inferior, and if it is less than 10%, the hardness of the cured film may be inferior.

4). Organic fine particles or inorganic fine particles (D) having a number average particle diameter measured by a dynamic light scattering method of 0.1 to 3 μm
The component (D) used in the present invention imparts slidability to a cured film obtained by curing the composition. By blending the component (D), noise generated from the printer belt and the printer drum is reduced, so that the quietness of the printer is improved.
Here, the slidability means the slipperiness of the cured film. If the unevenness on the surface of the cured film is too large, the frictional resistance will increase and the slidability will be reduced. The mobility is reduced. (D) component of this invention improves the slidability of a cured film by providing moderate unevenness | corrugation to the cured film surface.

  The component (D) is not particularly limited as long as it has the above-mentioned number average particle diameter, and organic fine particles or inorganic fine particles can be used. The organic fine particles (D) are not particularly limited as long as they are particles made of an organic polymer. However, the organic fine particles obtained by copolymerizing a crosslinkable monomer are preferable because they are excellent in hardness and can further improve the slidability of the cured film. Examples of other monomers copolymerized with the crosslinkable monomer include aromatic vinyl compounds and diene monomers.

  Specific examples of preferred crosslinkable monomers include hydrocarbon monomers such as divinylbenzene, divinyltoluene, divinylxylene, divinylethylbenzene, divinylnaphthalene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene. Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolpropane tri (meth) acrylate , (Meth) acrylic acid ester derivatives such as tetramethylol methanetri (meth) acrylate, acrylamide derivatives such as methylenebis (meth) acrylamide, and other monomers having two or more polymerizable double bonds per molecule The body is raised. These monomers may be used alone or in combination of two or more. Of these, divinylbenzene is preferred.

  Specific examples of preferred aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene and the like. Examples of the olefin include ethylene and propylene. These monomers may be used alone or in combination of two or more. Of these, styrene is preferred.

  Specific examples of preferable diene monomers include 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,3-hexadiene, 2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3- Butadiene, 1,2-heptadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,3-heptadiene, 2,5-heptadiene, 3,4-heptadiene, In addition to 3,5-heptadiene, cyclopentadiene, dicyclopentadiene, ethylidene norbornene, etc., branched aliphatic compounds having 4 to 7 carbon atoms There can be mentioned alicyclic dienes. These can be used alone or in combination of two or more. Of these, 1,3-butadiene and isoprene are particularly preferred.

  Preferable specific examples of the organic fine particles obtained by copolymerizing such a crosslinkable monomer include particles made of a copolymer of two or more monomers including divinylbenzene, and in particular, a copolymer of divinylbenzene and styrene. Polymer particles and the like are preferred.

  As commercially available products of such organic fine particles, W-450A manufactured by Mitsubishi Rayon Co., Ltd., organic filler manufactured by Nippon Kasei Co., Ltd., organic filler JT, J-4PY manufactured by Negami Kogyo Co., Ltd., MX150 manufactured by Soken Chemical Co., Ltd. MX180, SX130H, Nisshin Chemical Co., Ltd. R-170S, Sekisui Chemical Co., Ltd. XX-49L, etc. are mentioned.

  As specific examples of the inorganic fine particles (D), inorganic particles that are insoluble in organic solvents such as calcium carbonate, magnesium carbonate, ceria, silica, zirconia, alumina, and titanium oxide and do not have conductivity are preferable.

  Examples of commercially available inorganic fine particles include Caltex 5 manufactured by Maruo Chemical Co., Ltd., high purity fine particle cerium oxide, cerium oxide HS manufactured by Daiichi Rare Element Co., Ltd., and the like.

  The number average particle size of the organic fine particles of component (D) is required to be 0.1 to 3 μm, and preferably 0.3 to 2 μm. When the number average particle diameter is in this range, the slidability of the cured film can be effectively improved.

  Content of (D) component used for this invention is 0.2-9 mass% by making the composition whole quantity except an organic solvent into 100 mass%, Preferably, it is 1-5 mass%. If it exceeds 9% by mass, the scratch resistance of the cured film is deteriorated, and excessive fine particles may be deposited on the coating film to deteriorate the appearance. If it is less than 0.2% by mass, sufficient slidability is obtained. There are things you can't get.

5. Radical polymerization initiator (E)
In the composition of this invention, (E) radical polymerization initiator can be mix | blended as needed.
Examples of such radical polymerization initiator (E) include a compound that thermally generates active radical species (thermal polymerization initiator) and a compound that generates active radical species by radiation (light) irradiation (radiation). (Light) polymerization initiator).

  The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy Roxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- ( 1-methylvinyl) phenyl) propanone) and the like.

  As a commercial item of a radiation (photo) polymerization initiator, for example, Ciba Specialty Chemicals Co., Ltd. trade name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG24-61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Ubekril P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B and the like.

  The blending amount of the radical polymerization initiator (E) used as necessary in the present invention is preferably 0.01 to 10% by weight, with the total amount of the composition excluding the organic solvent being 100% by weight, -5 mass% is further more preferable. If it is less than 0.01% by mass, the hardness when it is a cured product may be insufficient. If it exceeds 10% by mass, it may not be cured to the inside (lower layer) when it is a cured product.

When hardening the composition of this invention, a photoinitiator and a thermal-polymerization initiator can be used together as needed.
Preferable thermal polymerization initiators include, for example, peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. it can.

6). Organic solvent (F)
The composition of the present invention can be used after being diluted with (F) an organic solvent in order to adjust the thickness of the coating film. For example, the viscosity when used as an antireflection film or a coating material is usually 0.1 to 50,000 mPa · sec / 25 ° C., and preferably 0.5 to 10,000 mPa · sec / 25 ° C.

  (F) Although it does not specifically limit as an organic solvent, Since the compound of (B) component has high crystallinity, since the composition of this invention can be apply | coated uniformly, it is preferable to use a high boiling point solvent. (E) Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate and ethyl lactate , Γ-butyrolactone, esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylform Examples include amides such as amide, dimethylacetamide, and N-methylpyrrolidone. Among these, high-boiling solvents such as methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, toluene and xylene are preferable.

  The compounding quantity of the (F) solvent in the composition of this invention is 30-80 mass% normally in all the compositions, and 40-80 mass% is preferable. If it exists in the range of 30-80 mass%, coating property is favorable.

7). Other ingredients (G)
In the curable composition of the present invention, as long as the effects of the present invention are not impaired, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, a surfactant, Plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, inorganic fillers, pigments, dyes, lubricants, and the like can be appropriately blended.

8). Method for Producing Composition The composition of the present invention is produced as follows.
Zinc antimonate particle dispersion (component (A)), radiation (photo) polymerization initiator (component (E)), compound represented by formula (1) (component (B)), polyfunctional (meth) acrylate (( Component C), organic or inorganic fine particles (component (D)) are placed in a reaction vessel equipped with a stirrer and stirred at 35 ° C. to 45 ° C. for 2 hours to obtain the composition of the present invention.
When the solvent is replaced with a solvent (β) of a different type from the solvent (α) used in the first zinc antimonate particle dispersion, 1.3% of the mass of the solvent (α) in the zinc antimonate particle dispersion is used. Double the solvent (β) is also added and stirred under the same conditions. Next, this composition solution is concentrated under reduced pressure to the mass before adding the solvent (β) using a rotary evaporator to obtain the composition of the present invention.

9. Method of applying composition (coating) The curable composition of the present invention is suitable for use in hard coats and coating materials, and is particularly useful as a hard coat for laser printer belts and printer drums. Examples of the base material to be coated include plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass And slate. A thermoplastic resin material is preferably used as a material for the printer belt or transfer drum (a base material to be coated). For example, polyvinylidene fluoride, polyethylene, polypropylene, polymethylpentene-1, polystyrene, polyamide, polysulfone, polyarylate, polyethylene terephthalate, polyphenylene sulfide, polyethersulfone, polyethernitrile, thermoplastic polyimide-based material, polyetheretherketone, Examples thereof include thermoplastic resin materials such as thermotropic liquid crystal polymer, polyamic acid, polycarbonate and polymethyl methacrylate, mixed resins thereof, and thermoplastic elastomers formed from the mixed resins. On the other hand, cadmium sulfide, a selenium compound, polysilane, or the like is preferably used as the surface material of the photosensitive drum (base material to be coated).
The shape of these substrates may be a plate, film or three-dimensional molded body, and the coating method is a normal coating method such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating, etc. Can be mentioned. The thickness of the coating film in these coatings is usually 0.1 to 400 μm, preferably 1 to 200 μm after drying and curing.

10. Method of curing composition The curable composition of the present invention can be cured by heat and / or radiation (light). When using heat, as the heat source, for example, an electric heater, an infrared lamp, hot air, or the like can be used. In the case of radiation (light), the radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, Commercially available lasers, etc., as visible ray sources, sunlight, lamps, fluorescent lamps, lasers, etc., ultraviolet ray sources, mercury lamps, halide lamps, lasers, etc., and electron beam sources Using thermionic electrons generated from the tungsten filament, cold cathode method for generating metal through a high voltage pulse, and secondary electron method using secondary electrons generated by collision of ionized gaseous molecules with metal electrodes Can be mentioned. Moreover, as a source of alpha rays, beta rays, and gamma rays, for example, a fission material such as Co ⁶⁰ can be cited, and for the gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.
The curing reaction of the composition of the present invention can be performed under an anaerobic condition such as nitrogen in an air atmosphere, and even when cured under an anaerobic condition, the cured product has excellent scratch resistance. Have

II. Cured film The cured film of the present invention can be obtained by coating and curing the curable composition on various substrates, for example, plastic substrates. Specifically, after coating the composition and preferably drying the volatile component at 0 to 200 ° C., it can be obtained as a coated molded body by performing the above-described curing treatment with heat and / or radiation. . The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a range of 10 seconds to 24 hours. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, as for the irradiation conditions of a preferable electron beam, a pressurization voltage is 10-300 KV, an electron density is 0.02-0.30 mA / cm < ² >, and an electron beam irradiation amount is 1-10 Mrad.

  The cured film of the present invention has characteristics that can form a coating film (film) having antistatic properties and excellent scratch resistance and adhesion to a substrate and an adjacent layer. It is particularly preferably used for applications that require antistatic properties such as hard coats for printer drums.

III. Laminated body The cured film of the present invention is usually used by being laminated on a substrate as a hard coat layer, and is used for applications requiring antistatic properties and scratch resistance, particularly for printer belts or printer drums. It is suitably used as a hard coat. Here, the printer belt is the transfer (resin) belt 1 as shown in FIG. 1, the suction conveyance (resin) belt 21 as shown in FIG. The printer drum is the photosensitive drum 7 shown in FIGS. 1 to 3 or the transfer drum shown in FIG.

The laminate of the present invention in which the curable composition of the present invention is applied onto a substrate and UV cured is excellent in scratch resistance. The reason why the laminate or cured film of the present invention is excellent in scratch resistance is that the component (B) (isocyanuric acid derivative having a polymerizable unsaturated group) has a ring structure and is crystalline, so that the hardness decreases. Presumed to not.
Furthermore, it is estimated that by blending the component (B) (isocyanuric acid derivative having a polymerizable unsaturated group), the adhesion to the substrate is improved and the scratch resistance is improved.
In addition, the laminated body of this invention may contain layers other than the cured film of this invention as needed.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to the description of these examples. In the examples, unless otherwise specified, the amount of each component means “parts” by mass and “%” means mass%.

[Production Example 1]
Synthesis of Silicone Compound (Component (G)) 80 parts of α- [3- (2′-hydroxymethoxy) propyl] polymethylsiloxane (FM0411 manufactured by Toray Dow) are introduced into a reaction vessel. Thereafter, 2,6-di-t-butylcresol and 1 part or less of phenothiazine and 10 parts of 2,4-diisocyanatotoluene are added as polymerization inhibitors, and the liquid temperature is kept at 15 to 25 ° C. Thereafter, 1 part or less of dibutyltin dilaurate is introduced as a catalyst, and the liquid temperature is raised to 35 ° C to 45 ° C. After the reaction for 1 hour, 10 parts of 2-hydroxyethyl acetate is introduced and the liquid temperature is kept at 50 ° C to 60 ° C. After 2 hours, the isocyanate content was measured, and it was confirmed that it was 0.1 parts or less to obtain the desired reactive silicone.

Example 1
In a reaction vessel equipped with a stirrer, zinc antimonate particle dispersion (CELNAX CX-Z210IP, zinc antimonate double oxide manufactured by Nissan Chemical Industries, Ltd., dispersion medium: isopropanol, solid content concentration: 21% by mass) 41 .5 parts (8.71 parts as zinc antimonate particles), 83.71 parts of methyl ethyl ketone and 139.64 parts of methyl isobutyl ketone were added and stirred, and tris (2-hydroxyethyl) isocyanuric acid acrylate (Toagosei Co., Ltd.) was added. Aronix M-315) 32.74 parts, dipentaerythritol hexaacrylate 49.28 parts, 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals photopolymerization initiator, Irgacure 184) 2.07 parts 2-methyl-1- [4- (methylthiophenyl) 2-morpholinopropan-1-one (Ciba Specialty Chemicals Co., Ltd. photopolymerization initiator, Irgacure 907) 2.07 parts, methoxyphenol (Wako Pure Chemical Industries, Ltd. polymerization inhibitor) 0.01 parts, production example 0.13 parts of the silicone compound produced in 1 and organic fine particles 1 (particles made of a copolymer of divinylbenzene and styrene (SX8743 (C) -03, number average particle size 0.3 μm, manufactured by JSR Corporation)) 5 0.000 part was further added, and it stirred at normal temperature for 60 minutes, and obtained the uniform composition. 2 g of this composition was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 28%.

Examples 2-8 and Comparative Examples 1-5
A curable composition was obtained in the same manner as in Example 1 except that the components shown in Table 1 were blended in the proportions shown in Table 1.

<Production of cured film>
A curable composition was applied to each of the examples shown in Table 1 using an applicator bar (# 20) on an easily adhesive PET substrate (A4300, Toyobo Co., Ltd.). The coating film thickness was adjusted to 5 μm after curing. This was left to stand at 80 ° C. for 3 minutes for drying, and then irradiated with UV using a high-pressure mercury lamp to obtain a cured film. The illuminance of UV was 1200 mJ / cm ² .

<Characteristics of cured film>
(1) Surface resistance (Ω / □)
The surface resistance (Ω / □) of the cured film was measured using a high resistance meter (Agilent Technology Co., Ltd. Agilent 4339B) and Resistivity Cell 16008B (Agilent Technology Co., Ltd.) with an applied voltage of 100V. Measured under conditions. The obtained results are shown in Table 1.

(2) Sliding property Two cured films were held by hand, and both cured film surfaces were rubbed together by hand to evaluate sliding properties. The slidability was judged by the good slidability when two cured films were rubbed together. When the two sheets were rubbed together, the case where the cured film surface did not stick was evaluated as good slidability, and the case where it stuck was evaluated as poor slidability and indicated as “x”.

(3) Scratch resistance Steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was attached to a Gakushin type abrasion resistance tester (AB-301, manufactured by Tester Sangyo Co., Ltd.) The surface was repeatedly rubbed 10 times under a load of 500 g, and the presence or absence of scratches on the surface of the cured film was visually confirmed. The case where almost no peeling or scratching of the cured film was observed was evaluated as “◯”, and the case where peeling occurred in a part of the cured film or the surface of the cured film had a streak was evaluated as “X”. .

Zinc antimonate particles: Cellax CX-Z210IP, manufactured by Nissan Chemical Industries, Ltd. Zinc antimonate double oxide, dispersion medium: isopropanol, solid content concentration: 21% by mass
Tris (2-hydroxyethyl) isocyanuric acid acrylate: manufactured by Toagosei Co., Ltd., Aronix M-315
1-hydroxycyclohexyl phenyl ketone: Photopolymerization initiator, Irgacure 184, manufactured by Ciba Specialty Chemicals
2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one: Photopolymerization initiator, Irgacure 907, manufactured by Ciba Specialty Chemicals
Methoxyphenol: Polymerization inhibitor manufactured by Wako Pure Chemical Industries, Ltd. Organic fine particles 1: Particles made of a copolymer of divinylbenzene and styrene (SX8743 (C) -03, number average particle size 0.3 μm: manufactured by JSR Corporation)
Organic fine particles 2: Particles made of a copolymer of divinylbenzene and styrene (SX8705 (P) -01, number average particle diameter 1.8 μm: manufactured by JSR Corporation)
Organic fine particles 3: Particles made of acrylic copolymer (AC-3355, number average particle size 0.5 μm: manufactured by Ganz Kasei Co., Ltd.)
Organic fine particles 4: Particles made of acrylic copolymer (W-450A, number average particle size 0.5μ, manufactured by Mitsubishi Rayon Co., Ltd.) Inorganic fine particles 1: Particles made of calcium carbonate (Caltex 5, number average particle size 1 .0 μm: Maruo Calcium Co., Ltd.)

  From the results shown in Table 1, the cured films of the examples have a small amount of components that impart conductivity (zinc antimonate particles), but have a low surface resistance and excellent scratch resistance and slidability. I understand. In contrast, in Comparative Example 1 in which the organic fine particles of the component (D) were not added, it can be seen that the slidability is inferior. In addition, in Comparative Examples 2 and 3 in which 0.1% by mass of the component (D) particles were added, the organic fine particles added were too small, and it was found that the slidability was poor. Further, in Comparative Examples 4 and 5 in which 10% by mass of the organic fine particles of component (D) are added, the slidability is good, but the amount of organic fine particles added is too large, so that the cured film becomes brittle and scratch resistance is poor.

  The curable composition of the present invention and the cured product thereof are useful for applications requiring antistatic properties and scratch resistance, particularly as hard coats for laser printer belts or printer drums.

FIG. 1 is a diagram showing an outline of the structure of an intermediate transfer belt type laser printer. FIG. 2 is a diagram showing an outline of the structure of a transfer drum type laser printer. FIG. 3 is a diagram showing an outline of the structure of a tandem laser printer. FIG. 4 is a diagram showing an outline of the structure of the ink jet printer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transfer (resin) belt 2 Transfer paper 3 Toner 4 Developer 5 Optical writing device 6 Charging charger 7 Photosensitive drum 8 Fixing device 9 Driving roller 10 Drive roller 11 Transfer charger 21 Adsorption conveyance (resin) belt 22, 22a Recording paper 23 Feeding unit 24 Feeding roller 25 Conveying roller 26 Driven roller 27 Pressure roller 28 Pinch roller 29 Drive roller 30 Bratten 31 Charging brush 32 Recording head 33 Spur 34 Unloading roller 35 Discharge tray 36 Transfer drum 37 Laser exposure unit 38 Rotary development vessel

Claims (6)

With respect to the total amount of the composition excluding the solvent, 5 to 50% by mass of the following component (A) zinc antimonate particles,
(B) The following formula (1)

[In Formula (1), R ¹ , R ² and R ³ are each independently a monovalent organic group, and at least two of R ^{1 to} R ³ are —R ⁴ OCOCR ⁵ ═CH ₂ . Yes, R ⁴ is a divalent organic group having 2 to 8 carbon atoms, and R ⁵ is a hydrogen atom or a methyl group. 10 to 50% by mass of a compound represented by
(C) The polyfunctional (meth) acrylate compound other than the components (A) and (B) is 10 to 70% by mass, and (D) the number average particle diameter measured by the dynamic light scattering method is 0.1 to 3 μm. Some organic fine particles or inorganic fine particles that are not the component (A) 0.2 to 9% by mass
A curable composition for a printer belt, comprising:   The curable composition according to claim 1, wherein the component (B) is tris ((meth) acryloxyethyl) isocyanurate.   The fine particles of the component (D) are particles made of a copolymer of two or more monomers including a hydrocarbon monomer, a (meth) acrylic acid ester derivative, or an acrylamide derivative. Or the curable composition of 2.   The said (B) component is contained 20 mass% or more with respect to 100 mass% of all (meth) acrylate components other than the (A) component in a composition, The any one of Claims 1-3 characterized by the above-mentioned. The curable composition according to 1.   The hard coat film | membrane for printer belts which hardens the curable composition as described in any one of Claims 1-4. A laminate comprising the hard coat film for a printer belt according to claim 5 .

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