JP5039896B2 - Urethane (meth) acrylate, radiation curable composition, and cured film thereof - Google Patents

Description

  The present invention relates to a radiation curable composition, 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.] and has high hardness and high refractive index on the surface of the base material, as well as scratch resistance, base material and low refractive index. The present invention relates to a radiation curable composition capable of forming a coating film (film) excellent in adhesion to a layer, and a cured film obtained by curing the composition.

In recent years, it has excellent coating properties as a protective coating material to prevent scratches (scratches) and contamination on various substrate surfaces; adhesives and sealing materials for various substrates; and a binder material for printing inks, and Radiation curing that can form a cured film with excellent hardness, scratch resistance, abrasion resistance, low curl, adhesion, transparency, chemical resistance, and coating surface appearance on the surface of various substrates. There is a need for sex compositions.
In addition, in addition to the above requirements, a radiation curable composition capable of forming a cured film having a high refractive index is required for use in an antireflection film such as a film type liquid crystal element, a touch panel, and a plastic optical component.

  In order to satisfy such a demand, various compositions have been proposed. The composition has excellent coating properties as a radiation curable composition, and has a high hardness and a high refractive index when used as a cured film. In addition, it has excellent scratch resistance and adhesion to the substrate and the low refractive index layer used in the laminate described later, and has a low reflectance when it is a laminate in which a low refractive index film is laminated on the cured film by coating. At present, a product having the characteristics of having excellent hardness and pencil hardness is not yet obtained.

  For example, Patent Document 1 describes a conductive coating agent composed of ultrafine powder of a conductive filler and an ultraviolet curable resin as a binder, and this coating agent forms a coating cured film without increasing the temperature. It is possible to easily form a conductive coating cured film on a transparent substrate having no heat resistance. As the conductive filler, it is described that titanium oxide doped with antimony is particularly preferable in terms of dispersibility and low haze. And it is described using an acrylic resin, a urethane resin, or a silicone resin as an ultraviolet curable resin. However, there is no description suggesting that it is preferable to use a urethane resin to improve the adhesion to the substrate. Further, the conductive coating agent described in Patent Document 1 does not contain a solvent.

  Patent Document 2 includes a (meth) acrylic acid ester mixture (A), a photopolymerization initiator (B), an ethylenically unsaturated group-containing urethane oligomer (C), a colloidal silica sol (D), and a diluent (E). A photosensitive resin composition for a hard coat agent and a hard coat film comprising the same are described, and it is described that the obtained film has good pencil hardness, curl, and adhesion to a substrate. However, the inorganic particles ((D) above) used in the examples are only silica particles, and the silica particles are not subjected to surface modification of the particles. Moreover, since the silica particle is used, electroconductivity is not provided.

JP, 7-196956, A Claims 1, 4, 5, paragraph number 0022, Table 1 JP, 2002-233501, A Claim, paragraph number 0037

  The present invention has been made in view of the above-mentioned problems, has excellent coating properties, has high hardness and high refractive index on the surface of various substrates, and has scratch resistance, transparency and basicity. Provided are a radiation curable composition capable of forming a coating film (coating) excellent in adhesion to a material and a low refractive index layer, a cured film thereof, and a laminate having a low reflectance and an excellent antistatic property. For the purpose.

In order to achieve the above object, the inventors of the present invention have made extensive studies and use a curable resin composition containing a compound having a urethane bond in the molecule and containing two or more polymerizable unsaturated groups. Thus, it was found that a cured film having excellent adhesion to the base material (lower layer) and the upper layer was obtained, and the present invention was completed.
According to the present invention, the following radiation-curable composition, cured product thereof, and laminate can be provided.

[1] A compound represented by the following formula (1).
[2] (B) a compound represented by the following formula (2),
[In Formula (2), each R ¹ is independently a monovalent organic group having a (meth) acryloyl group, and each R ² is independently a divalent organic group having a (meth) acryloyl group. And m and n are each independently an integer of 0 to 3. ]
(C) a photopolymerization initiator, and (E) a radiation curable composition containing a solvent.
[3] The radiation curable composition according to the above [2], wherein the component (B) is a compound represented by the formula (1) according to the above [1].
[4] The radiation curable composition according to the above [2] or [3], which contains a compound having a polymerizable unsaturated group other than the components (D) and (B).
[5] (A) The main component is an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, and has a polymerizable unsaturated group. The radiation curable composition according to any one of the above [2] to [4], which contains particles.
[6] The radiation curable composition according to [5], wherein the organic compound containing a polymerizable unsaturated group in the component (A) has a group represented by the following formula (3) in addition to the polymerizable unsaturated group. object.
-UC (= V) -NH- (3)
[In Formula (3), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]
[7] A cured film obtained by curing the radiation curable composition according to any one of [2] to [6].
[8] A laminate including the cured film according to [7].

  According to the present invention, it has excellent coating properties, and has high hardness and high refractive index on the surface of various base materials, as well as scratch resistance, transparency, base material, low refractive index layer, and other hard coats. It is possible to provide a radiation curable composition capable of forming a coating film (coating) excellent in adhesion to a layer and the like, a cured film thereof, and a laminate having low reflectivity and excellent scratch resistance.

Hereinafter, embodiments of the radiation curable composition, the cured product, and the laminate of the present invention will be specifically described.
I. Radiation curable composition The radiation curable composition of the present invention comprises (A) an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. , A particle having a polymerizable unsaturated group, (B) a compound represented by formula (2),
[In Formula (2), each R ¹ is independently a monovalent organic group having a (meth) acryloyl group, and each R ² is independently a divalent organic group having a (meth) acryloyl group. And m and n are each independently an integer of 0 to 3. ]
It comprises (C) a photopolymerization initiator, (D) a compound having a polymerizable unsaturated group other than components (B), and (E) a solvent. Among these components, the components (B), (C), and (E) are essential components, and the other components are non-essential components.

Hereinafter, each component of the radiation curable composition of the present invention will be specifically described.
1. Metal oxide particles having a polymerizable unsaturated group (A)
The metal oxide particle (A) having a polymerizable unsaturated group used in the present invention is at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Particles mainly composed of oxides (hereinafter sometimes referred to as “oxide particles (Aa)”) and organic compounds containing polymerizable unsaturated groups (hereinafter referred to as “organic compounds (Ab)”) )) (Hereinafter also referred to as “reactive particles”).

(1) Oxidic particles (Aa)
Oxide particles (Aa) used as needed in the present invention are silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, from the viewpoint of colorlessness of the cured film of the resulting radiation-curable composition. Particles mainly composed of an oxide of at least one element selected from the group consisting of antimony and cerium. Among these, since zirconium, titanium, and the like have a large refractive index of 1.50 or more, by using oxide particles of these elements, the refractive index of the cured film can be increased and the scratch resistance can be improved. . Further, by using particles such as aluminum-doped zinc oxide, tin-doped indium oxide, and antimony-doped tin oxide as oxide particles of zinc, indium, and antimony, respectively, conductivity can be imparted to the cured film.

  As these oxide particles (Aa), for example, silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, tin-doped indium oxide (ITO), antimony oxide, cerium oxide and the like are mainly used. The particle | grains used as a component can be mentioned. Among these, silica, alumina, zirconia and antimony oxide particles are preferable from the viewpoint of high hardness. These can be used singly or in combination of two or more. Furthermore, the oxide particles (Aa) are preferably in the form of powder or solvent dispersion sol. In the case of a solvent dispersion sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent 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.

The number average particle diameter of the oxide particles (Aa) is preferably 0.001 μm to 2 μm, more preferably 0.001 μm to 0.2 μm, and particularly preferably 0.001 μm to 0.1 μm. If the number average particle diameter exceeds 2 μm, the transparency when cured is reduced, or the surface state when coated is likely to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.
The number average particle diameter of the oxide particles (Aa) can be measured by, for example, a dynamic light scattering particle size distribution measuring apparatus manufactured by Horiba, Ltd.

  As a product marketed as silicon oxide particles (for example, silica particles), for example, colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned. As the powder silica, product names manufactured by Nippon Aerosil Co., Ltd .: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, manufactured by Asahi Glass Co., Ltd. Product names: Sildex H31, H32, H51, H52, H121 H122, manufactured by Nippon Silica Kogyo Co., Ltd., trade names: E220A, E220, manufactured by Fuji Silysia Co., Ltd., trade name: SYLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd., trade names: SG flakes and the like.

  Moreover, as an aqueous dispersion product of alumina, product names manufactured by Nissan Chemical Industries, Ltd .: Alumina sol-100, -200, -520; As an isopropanol dispersion product of alumina, product names manufactured by Sumitomo Osaka Cement Co., Ltd .: AS- As a toluene dispersion of alumina 150I, manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: AS-150T; As a zirconia toluene dispersion, manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: HXU-110JC; zinc antimonate powder Product name: Celnax; Alumina, titanium oxide, tin oxide, indium oxide, zinc oxide and other powder and solvent dispersion products are manufactured by C-Chemicals Co., Ltd. Name: Nanotech; Antimony-doped tin oxide aqueous dispersion sol manufactured by Ishihara Sangyo Co., Ltd. Product name: SN-100 ; The ITO powder, Mitsubishi Materials Co., Ltd. product; a cerium oxide aqueous dispersion, Taki Chemical Co., trade name: Nidoraru like.

The oxide particles (Aa) have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indeterminate shape, and preferably a spherical shape. The specific surface area of the oxide particles (Aa) (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 oxide particles (Aa) can be used in a dry state, or dispersed in water or an organic solvent. For example, a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above oxide can be used directly. In particular, use of a solvent-dispersed sol of an oxide is preferable in applications that require excellent transparency in a cured product.

(2) Organic compound (Ab)
The organic compound (Ab) used in the present invention is a compound containing a polymerizable unsaturated group in the molecule, and is preferably a specific organic compound containing a group represented by the following formula (3).
-UC (= V) -NH- (3)
[In Formula (3), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]
More preferably, it includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH— group. It preferably contains at least one of the groups. Moreover, it is preferable that this organic compound (Ab) is a compound which has a silanol group in a molecule | numerator, or a compound which produces | generates a silanol group by hydrolysis.

(I) Polymerizable unsaturated group The polymerizable unsaturated group contained in the organic compound (Ab) is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, and ethynyl. Preferred examples include a group, a cinnamoyl group, a maleate group and an acrylamide group.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) The group represented by the formula (3) The group [—UC (═V) —NH—] represented by the formula (3) contained in the specific organic compound is specifically [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—]. , [—NH—C (═S) —NH—], and [—S—C (═S) —NH—]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH-] groups.
The group [—UC— (V) —NH—] represented by the formula (3) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion to the material and heat resistance.

(Iii) A silanol group or a group that generates a silanol group by hydrolysis The organic compound (Ab) is a compound having a silanol group in the molecule (hereinafter sometimes referred to as “silanol group-containing compound”) or a silanol group by hydrolysis. It is preferable that it is a compound (hereinafter, sometimes referred to as “silanol group-generating compound”). Examples of such a silanol group-forming compound include compounds in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom. An alkoxy group or an aryloxy group is bonded to a silicon atom. Bonded compounds, that is, alkoxysilyl group-containing compounds or aryloxysilyl group-containing compounds are preferred.
The silanol group-generating site of the silanol group or the silanol group-generating compound is a structural unit that binds to the oxide particles (Aa) by a condensation reaction or a condensation reaction that occurs following hydrolysis.

(Iv) Preferred Embodiment As a preferred specific example of the organic compound (Ab), for example, a compound represented by the following formula (4) can be mentioned.

In the formula, R ³ and R ⁴ , which may be the same or different, are a hydrogen atom or an alkyl group or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, phenyl, A xylyl group etc. can be mentioned. Here, p is an integer of 1 to 3.
Examples of the group represented by [(R ³ O) _p R ⁴ _3-p Si—] include trimethoxysilyl group, triethoxysilyl group, triphenoxysilyl group, methyldimethoxysilyl group, dimethylmethoxysilyl group and the like. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
R ⁵ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms and may contain a chain, branched or cyclic structure.
R ⁶ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500.
R ⁷ is a (q + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. Moreover, q is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

  Specific examples of the compound represented by formula (4) include compounds represented by the following formula (5) or formula (6).

[In the formulas (5) and (6), “Acryl” represents an acryloyl group. ]

  For the synthesis of the organic compound (Ab) used in the present invention, for example, a method described in JP-A-9-100111 can be used. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate and reacted at 60 to 70 ° C. for several hours, then pentaerythritol triacrylate is added, and further at 60 to 70 ° C. for several hours. Produced by reacting to some extent. Typically, a mixture of the compound represented by the above formula (5) and the compound represented by the above formula (6) is obtained.

  The amount of the organic compound (Ab) bonded to the oxide particles (Aa) is preferably 0, based on 100% by mass of the reactive particles (A) (the total of the oxide particles (Aa) and the organic compound (Ab)). 0.01 mass% or more, more preferably 0.1 mass% or more, and particularly preferably 1 mass% or more. When the binding amount of the organic compound (Ab) bound to the oxide particles (Aa) is less than 0.01% by mass, the dispersibility of the reactive particles (A) in the composition is not sufficient, and the cured product obtained Transparency and scratch resistance may not be sufficient. Moreover, the compounding ratio of the oxide particles (Aa) in the raw material during the production of the reactive particles (A) is preferably 5 to 99% by mass, and more preferably 10 to 98% by mass.

1-90 mass% is preferable with respect to the composition whole quantity except a solvent, and, as for the compounding (content) amount in the radiation-curable composition of a reactive particle (A), 15-85 mass% is more preferable. When the content is less than 1% by mass, a material having a high refractive index may not be obtained. When the content exceeds 90% by mass, film formability may be insufficient.
In this case, the content of the oxide particles (Aa) constituting the reactive particles (A) in the composition is preferably 65 to 90% by mass.
The amount of the reactive particles (A) means a solid content, and when the reactive particles (A) are used in the form of a solvent-dispersed sol, the amount of the solvent does not include the amount of the solvent.

2. Compound (B) represented by the following formula (2)
(B) a compound represented by the following formula (2),
[In Formula (2), each R ¹ is independently a monovalent organic group having a (meth) acryloyl group, and each R ² is independently a divalent organic group having a (meth) acryloyl group. And m and n are each independently an integer of 0 to 3. ]

Since the component (B) of the present invention has a high refractive index and has a plurality of (meth) acryloyl groups in the molecule, the refractive index of the cured film of the radiation curable composition of the present invention is increased. It is used to improve the scratch resistance of the cured film by increasing the crosslinking density. Thus, R ¹ in the formula (2) is preferably a monovalent organic group having 3 or more (meth) acryloyl groups.

Specific examples of the component (B) of the present invention are not limited as long as they are compounds represented by the above formula (2). For example, compounds represented by the following formula (1) are preferable.

The component (B) of the present invention usually reacts with a compound having (b1) an acrylic acid adduct of bisphenol A diglycidyl ether, (b2) toluene diisocyanate, (b3) hydroxyl group and two or more (meth) acryloyl groups. Can be obtained.
The urethane (meth) acrylate which is the compound (B) having a urethane bond is not particularly limited, but is basically obtained by reacting (a) a polyisocyanate compound and (b) a hydroxy group-containing (meth) acrylate monomer. It is done. Urethane (meth) acrylate may have other oligomer as a main chain and urethane bond thereto.
Urethane (meth) acrylate must contain at least two (meth) acryloyl groups bonded to the main chain of the oligomer, preferably four or more, and more preferably six or more. .
The proportion of (a) polyisocyanate compound and (b) hydroxy group-containing (meth) acrylate monomer used for the synthesis of urethane (meth) acrylate is hydroxy with respect to 1 equivalent of isocyanate group contained in (a) polyisocyanate compound. It is preferable that the hydroxyl group of the group-containing (meth) acrylate monomer is 1.0 to 2 equivalents.
As a specific method for producing such urethane (meth) acrylate (B), for example, (c) a polyol compound, (a) a polyisocyanate compound, and (b) a hydroxy group-containing (meth) acrylate monomer are charged together. (C) a polyol compound and (a) a polyisocyanate compound are reacted, and then (b) a hydroxy group-containing (meth) acrylate monomer is reacted; (a) a polyisocyanate compound and (b) A method of reacting a hydroxy group-containing (meth) acrylate monomer and then (c) a polyol compound; (a) reacting a polyisocyanate compound and (b) a hydroxy group-containing (meth) acrylate monomer, and then (c) a polyol The compound is reacted and finally (b) a hydroxy A method in which reacting group-containing (meth) acrylate monomers.

(B1) Examples of commercially available acrylic acid adducts of bisphenol A diglycidyl ether include VR-77 (Showa Polymer Co., Ltd.).

(B2) As the toluene diisocyanate, 2,4-toluene diisocyanate is preferable.

(B3) Specific examples of the compound having a hydroxyl group and two or more (meth) acryloyl groups include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, tri Examples include methylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, and tetramethylolmethane triacrylate. Among these, tetramethylol methane triacrylate is preferable, and examples of the commercially available product include NK ester A-TMM-3LM-N (Shin Nakamura Chemical Co., Ltd.).

  In the synthesis of component (B), copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1 It is preferable to use 0.01 to 1% by mass of a urethanization catalyst such as 1,4-diazabicyclo [2.2.2] octane based on the total amount of the reactants. Moreover, reaction temperature is 5-90 degreeC normally, Especially 10-80 degreeC is preferable.

  It is preferable to mix | blend 1-99 mass% with respect to the composition whole quantity except a solvent, and, as for the compounding (content) amount of (B) component used for this invention, 10-98 mass% is further more preferable. If it is less than 1% by mass or more than 99% by mass, a cured product may not be obtained with a high hardness, and the adhesion of the coating film may be lowered.

3. Photopolymerization initiator (C)
In the composition of the present invention, the photopolymerization initiator (C) together with the compound (B) having a urethane bond and a solvent (E) described later, and the reactive particles (A) to be blended as necessary. Is blended.

  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.Among these, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, and the like are preferable.

  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, CG 24- 61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Ubekrill P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B Etc.

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.

  The compounding amount of the photopolymerization initiator (C) used in the present invention is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the composition excluding the solvent. preferable. When it is less than 0.01% by mass, the film formability may be insufficient, and when it exceeds 20% by mass, a cured product with high hardness may not be obtained.

4). Compound (D)
In the composition of the present invention, the compound (D) used as necessary is a compound having a polymerizable unsaturated group other than the component (B) (hereinafter referred to as “compound (D)” or “(D) component”). There are things). This compound (D) is suitably used for enhancing the film formability of the composition. The compound (D) is not particularly limited as long as it contains two or more polymerizable unsaturated groups in the molecule, and examples thereof include melamine acrylates, (meth) acrylic esters, and vinyl compounds. . Of these, (meth) acrylic esters are preferred.

Hereinafter, specific examples of the preferred compound (D) used in the present invention include the following formula (7).
Or the following formula (8)
(In the formulas (7) and (8), R ⁸ represents a hydrogen atom or a halogen atom excluding fluorine, and R ⁹ represents a hydrogen atom, a halogen atom excluding fluorine, Ph—C (CH ₃ ) ₂ —, Ph— Or an alkyl group having 1 to 20 carbon atoms, and R ¹⁰ represents a (meth) acrylate having a structure represented by —CH ₂ —, —S— or —C (CH ₃ ) ₂ —. be able to. The (meth) acrylate compound having such a structure is preferable in terms of increasing the refractive index of the cured film.

  Among the (D) components, examples of the (meth) acrylate having the structure represented by the formula (7) include phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, and phenoxyethoxyethyl (meth) acrylate. , 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 3- (2-phenylphenyl) -2-hydroxypropyl (meth) Acrylate, (meth) acrylate of p-cumylphenol reacted with ethylene oxide, 2-bromophenoxyethyl (meth) acrylate, 4-bromophenoxyethyl (meth) acrylate, 2,4-dibromophenoxyethyl (meth) acrylate DOO, 2,6-dibromo phenoxyethyl (meth) acrylate, 2,4,6-bromophenyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate. Among them, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, (meth) acrylate of p-cumylphenol reacted with ethylene oxide, 2,4,6-tribromophenoxyethyl (meth) acrylate, etc. preferable.

  Moreover, as (meth) acrylate which has a structure represented by Formula (8) among (D) component, ethylene oxide addition bisphenol A (meth) acrylic acid ester, ethylene oxide addition tetrabromobisphenol A (meth) acrylic acid ester, Propylene oxide-added bisphenol A (meth) acrylic acid ester, propylene oxide-added tetrabromobisphenol A (meth) acrylic acid ester, bisphenol A epoxy obtained by epoxy ring-opening reaction of bisphenol A diglycidyl ether and (meth) acrylic acid ( Tetrabromobisphenol A epoxy (meth) acrylate, bisphenol obtained by epoxy ring-opening reaction of (meth) acrylate, tetrabromobisphenol A diglycidyl ether and (meth) acrylic acid Bisphenol F epoxy (meth) acrylate obtained by epoxy ring-opening reaction between F diglycidyl ether and (meth) acrylic acid, Tetra obtained by epoxy ring-opening reaction between tetrabromobisphenol F diglycidyl ether and (meth) acrylic acid Bromobisphenol F epoxy (meth) acrylate and the like. Among them, ethylene oxide-added bisphenol A (meth) acrylic acid ester, ethylene oxide-added tetrabromobisphenol A (meth) acrylic acid ester, bisphenol A epoxy obtained by epoxy ring-opening reaction of bisphenol A diglycidyl ether and (meth) acrylic acid ( Particularly preferred are (meth) acrylate and tetrabromobisphenol A epoxy (meth) acrylate.

  Commercially available products of (meth) acrylate having a structure represented by formula (7) include Aronix M113, M110, M101, M102, M5700, TO-1317 (above, manufactured by Toagosei Co., Ltd.), Biscote # 192, # 193, # 220, 3BM (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK ester AMP-10G, AMP-20G (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), light acrylate PO-A, P- 200A, epoxy ester M-600A, light ester PO (above, manufactured by Kyoeisha Chemical Co., Ltd.), New Frontier PHE, CEA, PHE-2, BR-30, BR-31, BR-31M, BR-32 (above, Daiichi Kogyo Seiyaku Co., Ltd.).

  Commercially available products of (meth) acrylate having a structure represented by the formula (8) include Biscote # 700, # 540 (above, manufactured by Osaka Organic Chemical Co., Ltd.), Aronix M-208, M-210 (above , Manufactured by Toagosei Co., Ltd.), NK ester BPE-100, BPE-200, BPE-500, A-BPE-4 (above, Shin-Nakamura Chemical Co., Ltd.), light ester BP-4EA, BP-4PA, Epoxy ester 3002M, 3002A, 3000M, 3000A (manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD R-551, R-712 (manufactured by Nippon Kayaku Co., Ltd.), BPE-4, BPE-10, BR- 42M (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Lipoxy VR-77, VR-60, VR-90, SP-1506, SP-1506, SP-1507, SP- 509, SP-1563 (manufactured by Showa High Polymer Co., Ltd.), NEOPOL V779, NEOPOL V779MA (manufactured by Japan U-PICA Co., Ltd.), and the like.

In addition to the above, as the component (D), for example, the following compounds can be used.
(Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and starting alcohols thereof Poly (meth) acrylates of adducts with ethylene oxide or propylene oxide, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoethers (meth) acrylates, oligourethanes (meth) Examples include acrylates and oligoepoxy (meth) acrylates. Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and a compound represented by the following formula (9) are preferable. .
[In the formula (9), “Acryl” represents an acryloyl group. ]

  Examples of vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

  As a commercial item of such a compound (D), for example, Sanwa Chemical Co., Ltd. product name: Nikarac MX-302, Toagosei Co., Ltd. product name: Aronix M-400, M-408, M- 450, M-305, M-309, M-310, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO- 924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, manufactured by Nippon Kayaku Co., Ltd. Trade name: KAYARAD D 310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR- 9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO- 303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-62 R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA KS-TPGDA, KS-TMPTA, manufactured by Kyoeisha Chemical Co., Ltd. Trade name: Light acrylate PE-4A, DPE-6A, DTMP-4A, and the like.

  It is preferable to mix | blend 0-80 mass% with respect to the composition whole quantity except a solvent, and, as for the compounding (content) amount of the compound (D) arbitrarily used for this invention, 0-50 mass% is more preferable.

5. (E) Solvent The solvent that can be used in the present invention is not particularly limited as long as the solubility and dispersibility of components other than the solvent are not impaired. For example, methanol, ethanol, isopropanol, butanol, octanol and the like Alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethylene glycol Ethers such as monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, N-methyl Amides such as Rupiroridon like. Moreover, the usage-amount of this solvent is although it does not restrict | limit in particular, It is 5-100,000 mass parts normally with respect to 100 mass parts of composition whole quantity except a solvent, Preferably it is 10-10,000 mass parts.
The thickness of the coating film can be adjusted by diluting with a solvent. 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.

6). Other components In the radiation 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, Surfactants, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, inorganic fillers, pigments, dyes and the like can be appropriately blended.

7). Method of Applying Composition (Coating) The composition of the present invention is suitable for use as an antireflection film or a coating material. Examples of the base material to be antireflection or coated include plastics (polycarbonate, polymethacrylate, polystyrene). Polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate and the like. 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 0.01 to 400 μm, preferably 0.1 to 200 μm after drying and curing.

8). Method of Curing the Composition The composition of the present invention can be cured by radiation. 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, a laser, or the like is visible. Sun rays, lamps, fluorescent lamps, lasers, etc. as ray sources, mercury lamps, halide lamps, lasers, etc. as ultraviolet ray sources, and electron beam sources, generated from commercially available tungsten filaments Examples include a method using hot electrons, a cold cathode method in which a metal is generated through a high voltage pulse, and a secondary electron method in which secondary electrons generated by collision of ionized gaseous molecules with a metal electrode are used. Moreover, as a source of alpha rays, beta rays, and gamma rays, for example, a fission material such as Co ⁶⁰ can be cited. For the gamma rays, a vacuum tube or the like that causes accelerated electrons to collide with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.

II. Cured film The cured film of the present invention can be obtained by coating and curing the radiation 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. Further, the material of the base material is not particularly limited, and examples thereof include triacetyl cellulose (TAC), polyethylene terephthalate (PET), and norbornene resin (Arton manufactured by JSR Corporation).

  The cured film of the present invention has the characteristics that it has a high hardness and a high refractive index, and can form a coating film (film) excellent in scratch resistance and adhesion to the substrate and the low refractive index layer. Therefore, it is particularly suitably used as a hard coat or antireflection film for film type liquid crystal elements, touch panels, plastic optical components and the like.

  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. Moreover, unless otherwise indicated, the compounding quantity of each component in an Example means the mass part and the mass%.

Production Example 1 Production of Compound Represented by Formula (1) Into a reaction vessel, 1 part of dibutyltin laurate, 1 part of 2,6-di-t-butyl-p-cresol and 2,4-toluene diisocyanate are added. 5 parts were charged and the temperature was 20 ° C. The reaction solution was sealed while introducing dry air into the reaction vessel. Here, 54.3 parts of tetramethylol methane triacrylate was dropped with a dropping funnel, and the reaction was carried out for 1 hour while maintaining the reaction temperature at 20 ° C to 30 ° C. Thereafter, 27.2 parts of an acrylic acid adduct of bisphenol A diglycidyl ether (VR-77; Showa High Polymer Co., Ltd.) was dissolved in 27.2 parts of methyl ethyl ketone, and added dropwise with a dropping funnel. It was kept at ˜50 ° C. and allowed to react for 1 hour. It was confirmed that the isocyanate content was 0.1 part or less, and the target compound represented by the formula (1) was obtained. After the synthesis, 2 g of the sample was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 78%.

The production of the target product was confirmed with a time-of-flight mass spectrometer (MALDI-TOFMAS; Voyager Elite, manufactured by Applied Biosystems). The analysis results are shown in FIG. As a Na ⁺ ion adduct, a molecular weight of 1462.4 was confirmed.

Production Example 2: Production of Organic Compound (Ab) Containing Polymerizable Unsaturation Group In dry air, 222 parts of isophorone diisocyanate was stirred with respect to a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate. However, after dropwise addition at 50 ° C. over 1 hour, the mixture was stirred with heating at 70 ° C. for 3 hours. This is composed of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. 549 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Ab) containing a polymerizable unsaturated group. When the amount of residual isocyanate in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. In the infrared absorption spectrum of the product, the absorption peak of 2550 Kaiser characteristic of mercapto group in the raw material and the absorption peak of 2260 Kaiser characteristic of raw material isocyanate compound disappeared, and new urethane A 1660 Kaiser peak characteristic of the bond and the S (C = O) NH- group and a 1720 Kaiser peak characteristic of the acryloxy group are observed, with an acryloxy group as the polymerizable unsaturated group It was shown that -S (C = O) NH- and an acryloxy group-modified alkoxysilane having both urethane bonds were formed. As a result, a total of 773 parts of the mixture of the compound represented by the formula (5) and the compound represented by the previous formula (6) (Ab) and 220 parts of pentaerythritol tetraacrylate not involved in the reaction were obtained. .

Production Example 3: Production of reactive zirconia particles (component (A)) 2.23 parts of an organic compound (Ab) containing a polymerizable unsaturated group produced in Production Example 2, zirconia particle dispersion (Aa) (zirconia particles 33) .3 mass% methyl ethyl ketone dispersion) 97.37 parts, 0.03 part of ion-exchanged water, and 0.02 part of p-hydroxyphenyl monomethyl ether were stirred at 60 ° C. for 4 hours, and then methyl orthoformate. Reactive particles (dispersion liquid (A-1)) were obtained by adding 0.34 parts and further stirring with heating at the same temperature for 1 hour. When 2 g of this dispersion (A-1) was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour and weighed to determine the solid content, it was 34.9%. Further, 2 g of the dispersion (A-1) was weighed in a magnetic crucible, preliminarily dried on a hot plate at 80 ° C. for 30 minutes, and baked in a muffle furnace at 750 ° C. for 1 hour. The inorganic content was determined to be 85.8%.

Production Example 4: Production of polyfunctional acrylate represented by the above formula (9) For a solution comprising 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a vessel equipped with a stirrer, NK manufactured by Shin-Nakamura Chemical Co., Ltd. Ester A-TMM-3LM-N (participating in the reaction is only pentaerythritol triacrylate having a hydroxyl group) 93 parts dropwise at 10 ° C. for 1 hour, then at 60 ° C. for 6 hours. The reaction solution was stirred under conditions.
The product in this reaction solution, that is, the amount of residual isocyanate was measured by FT-IR in the same manner as in Production Example 2 and found to be 0.1% by mass or less, confirming that the reaction was carried out almost quantitatively. did. Moreover, it confirmed that a molecule | numerator contained a urethane bond and an acryloyl group (polymerizable unsaturated group) in a molecule | numerator.
As a result, 75 parts of the compound represented by the formula (9) and 37 parts of pentaerythritol tetraacrylate which was not involved in the reaction were obtained.

[Preparation of radiation curable composition]
Example 1
Reactive zirconia particle dispersion 50.1 parts produced in Production Example 3 (15.3 parts as reactive zirconia particles (A) (15 parts of zirconia particles (Aa) and organic compound (Ab) 0.285 bonded to the particles) 104.9 parts of the methyl ethyl ketone solution of the compound represented by the formula (1) produced in Production Example 1 (including 81.83 parts of the compound represented by the formula (1)), p-methoxy 0.01 part of phenol, 0.4 part of polyfunctional acrylate produced in Production Example 4 represented by the formula (9), 0.26 part of pentaerythritol tetraacrylate, 2.2 parts of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone A uniform composition was obtained by stirring 210 parts for 1 hour at 25 ° C. Among these, pentaerythritol tetraacrylate was an organic compound. (Ab) and derived from pentaerythritol tetraacrylate mixed in a polyfunctional acrylate obtained in Preparation Example 4 represented by the formula (9). Was determined the solids content of the composition was 30%.

Examples 2-4 and Comparative Examples 1-2
Except having changed into the composition shown in Table 1, the compositions of Examples 2 to 4 and Comparative Examples 1 and 2 were obtained in the same manner as in Example 1.

<Characteristic evaluation of cured film>
1. Preparation of Measurement Samples Using the coaters equipped with wire bar coaters (# 30) according to film thickness, the compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were used. And dried in an oven at 80 ° C. for 3 minutes to form a coating film. Subsequently, the coating film was UV-cured under a light irradiation condition of 0.2 J / cm ² using a high-pressure mercury lamp under nitrogen to form a cured film having a thickness of 6 to 7 μm.
2. Transparency (haze)
Using a color haze meter manufactured by Suga Seisakusho Co., Ltd., the haze value (%) was measured according to ASTM D1003 and evaluated as a value including a base film.

3. Pencil hardness Based on JIS K5600-5-4, the film hardened | cured on the glass substrate with a 500-g load was evaluated.

4). Refractive index The refractive index at 589 nm was measured with an Abbe refractometer at 25 ° C.
5. Appearance Appearance of the coating film is visually checked for the presence or absence of whitening of the coating film and the presence or absence of vertical streaks using a bar coater in the coating direction. The thing with a vertical line was set as x.

Acrylic acid adduct of bisphenol A diglycidyl ether (VR-77; Showa Polymer Co., Ltd.)
1-hydroxycyclohexyl phenyl ketone (Irgacure 184; Ciba Specialty Chemicals Co., Ltd.)

  From the results of Table 1 above, in the examples using the compound (B) having a urethane bond, the pencil hardness is as good as H, whereas in the comparative example not using the compound (B) having a urethane bond, the pencil is used. It can be seen that the hardness is F and the surface hardness is inferior. In addition, the appearance of the coating film is ◯ in the example, whereas it is x in the comparative example. From the above, it can be seen that in the examples, a coating film having a high refractive index and a good appearance can be formed by using a polyfunctional acrylate having a urethane bond.

  The radiation curable composition of the present invention, the cured product and the laminate thereof are damaged, for example, in plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, artificial marble, etc. Protective coating materials for preventing (scratching) and preventing contamination; antireflection films for film-type liquid crystal elements, touch panels, plastic optical components, etc .; adhesives and sealing materials for various substrates; especially reflective as printing ink binder materials It can be suitably used as a prevention film.

It is a chart which shows the mass spectrometry result of the compound shown by Formula (1).

Claims (6)

A compound represented by the following formula (1).
(B) a compound represented by the formula (1) according to claim 1,
A radiation curable composition containing (C) a photopolymerization initiator and (E) a solvent. (D) The radiation curable composition of Claim 2 containing the compound shown by following formula (9).
[In the formula (9), “Acryl” represents an acryloyl group. ] (A) Radiation curable of Claim 2 or 3 containing the reactive zirconia particle formed by making the compound shown by following formula (5), and the compound shown by following formula (6) bind to a zirconia particle. Composition.
[In the formulas (5) and (6), “Acryl” represents an acryloyl group. ]   A cured film obtained by curing the radiation curable composition according to any one of claims 2 to 4. A laminate comprising the cured film according to claim 5.