JP5976349B2 - Active energy ray-curable resin composition, method for producing the same, coating agent, and laminate - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition, a production method thereof, a coating agent, and a laminate, and more specifically, an activity for forming a coating film excellent in low refractive index, scratch resistance, and transparency. The present invention relates to an energy ray curable resin composition and a production method thereof, and a coating agent and a laminate using the energy ray curable resin composition.

  Conventionally, in order to make display display easy to see, an antireflection film is laminated on the display surface. In order to maximize the effect of this anti-reflection film, it is usually often used as a structure in which a high refractive index layer and a low refractive index layer are sequentially laminated on a transparent resin substrate. ing.

  Here, since the low refractive index layer is a layer located on the outermost surface of the antireflection film, it is important to impart scratch resistance. On the other hand, the low refractive index layer has a thickness less than the visible light wavelength, preferably about 1/4 of the visible light wavelength in order to exhibit the effect. Yes.

  For this reason, in order to impart scratch resistance, a hard coat layer is applied and formed as a low refractive index layer, but active as a low refractive index layer forming material in order to increase productivity. An energy ray curable resin, particularly an ultraviolet curable resin is often used. The ultraviolet curable resin uses a photopolymerization initiator that generates radicals and / or cations when irradiated with ultraviolet rays, whereby the ultraviolet curable resin is radically or / and cationically polymerized.

  However, as described above, it is preferable that the low refractive index layer has a thickness of less than a visible light wavelength, specifically, a thickness of less than 1 μm. When using a curable resin to form a radical (photoradical polymerization initiator) that generates radicals as the photopolymerization initiator, radicals generated by light irradiation are exposed at the film interface in the atmosphere. There was a problem that it quickly deactivated by reacting with oxygen, and as a result, it was difficult to give scratch resistance. For this reason, for example, a method for solving the above problem by substituting the ultraviolet irradiation portion with nitrogen is known, but a new problem arises that new equipment investment is required.

For this reason, several methods have been proposed to use a so-called photocationic polymerization initiator that generates cations by light irradiation as a photopolymerization initiator and to ensure scratch resistance by using silica. Yes. For example, a reactive silica having a particle size of 1 to 200 nm having a radical polymerizable group or a cationic polymerizable group, a fluorine-containing vinyl monomer polymer unit, and a polymer unit having a radical polymerizable group or a cationic polymerizable group in the side chain An antireflective film having a low refractive index layer made of a cured film using a copolymerizable composition containing the above has been proposed (see Patent Document 1). In addition, inorganic oxide fine particles mainly composed of colloidal silica, and —O—Si—R ¹ —S— bond (R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms) to the inorganic oxide fine particles. Organic-inorganic hybrid resin composition comprising an organic-inorganic composite having an organic polymer having a side chain having a ring-opening polymerizable group capable of photocationic polymerization, and a cationically polymerizable photoinitiator. It has been proposed to cure a product to form a film with high hardness (see Patent Document 2).

JP 2004-93947 A JP 2005-336255 A

  However, in the technique disclosed in Patent Document 1, it is supposed to have a radically polymerizable group or a cationically polymerizable group as silica that is a reactive fine particle, but when silica having a radically polymerizable group is used, it is less than 1 μm. This film thickness is not preferable because oxygen inhibition during the curing reaction is remarkable, and a large amount of radical photopolymerization initiator is used or a large amount of ultraviolet irradiation is required. In addition, when using a silica having a cationic polymerizable group, the photo cationic polymerization initiator needs to be close to the silica surface, but strongly binds and aggregates with the originally acidic silica surface, so that it is a pot as a coating agent. There is a problem that life is significantly shortened.

  On the other hand, in the technique disclosed in Patent Document 2, since the surface of the inorganic oxide fine particles is covered with an organic polymer, the photocationic polymerization initiator is not close enough to the surface of the inorganic oxide fine particles to cause aggregation. However, since the resulting organic / inorganic composite is bonded to inorganic oxide fine particles only at the end of the organic polymer, the coating of inorganic oxide fine particles contributes to lowering the refractive index and scratch resistance. However, the organic polymer effective only in the portion close to the inorganic oxide fine particles is poor in efficiency and it is difficult to exert the effect of imparting scratch resistance, and the scratch resistance is not sufficiently satisfactory.

  The present invention has been made in view of such circumstances, and can form a film thickness that is less than the visible light wavelength, and can form a cured film that is excellent in transparency, low refractive index, and scratch resistance. It is an object of the present invention to provide an active energy ray-curable resin composition that can be used, a method for producing the same, a coating agent, and a laminate.

As a result of intensive studies to achieve the above object, the present inventor, as an active energy ray-curable resin composition containing a photocationic polymerization initiator, contains a hydroxyl group and contains a fluorine atom-containing structural site. And an inorganic oxide fine particle (B) mainly composed of colloidal silica surface-modified with an epoxy group-containing silane coupling agent (b1) , an alkoxy group in one molecule. When an inorganic oxide-acrylic resin composite (α) formed by bonding via a bonding site represented by the following general formula (1 ) derived from the silicon compound (E) having both of an isocyanate group and By using inorganic oxide fine particles (B) mainly composed of colloidal silica surface-modified with the epoxy group-containing silane coupling agent (b1), In order to prevent the aggregation of the inorganic oxide fine particles (B) by the photocationic polymerization initiator while placing the polymerizable reactive sites close to the inorganic oxide fine particles (B) advantageous for exhibiting scratch resistance, It has been found that the hydroxyl group can be contained in the resin (A), the affinity with the inorganic oxide fine particles (B) can be improved, and the pot life can be improved. Furthermore, it has been found that the above-described problems can be solved by performing a reduction in refractive index by providing the acrylic resin (A) with a fluorine atom-containing structure. Moreover, in the active energy ray-curable resin composition, inorganic inorganic fine particles (B) and acrylic resin (A) are bonded via a bonding site represented by the general formula (1) described later, It was found that the oxide fine particles (B) were appropriately coated and the inorganic oxide fine particles (B) were less likely to fall off even when rubbed with the cured coating, and the scratch resistance was improved, and the present invention was achieved. .

<< Summary of the Invention >>
The present invention mainly comprises an acrylic resin (A) containing a hydroxyl group and containing a fluorine atom-containing structure , and colloidal silica surface-modified with an epoxy group-containing silane coupling agent (b1). Inorganic oxide fine particles (B) to be bonded through a bonding site represented by the following general formula (1) derived from a silicon compound (E) having both an alkoxy group and an isocyanate group in one molecule An active energy ray-curable resin composition containing an oxide-acrylic resin composite (α) and a cationic photopolymerization initiator (β) is a first gist.
[Chemical formula 1]
—O—Si—R ¹ —NHCOO— (1)
In [the formula (1), R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms. ]

And this invention is a manufacturing method of the active energy ray curable resin composition which is the said 1st summary,
[I] fluorine atom-containing by copolymerizing copolymer component [I] containing fluorine atom-containing (meth) acrylic acid ester monomer (a1) and hydroxyl group-containing (meth) acrylic acid ester monomer (a2) Producing an acrylic resin (A) containing a structural site;
[Ii] A reaction product (AE) is produced by reacting the hydroxyl group in the acrylic resin (A) with an isocyanate group of a silicon compound (E) having both an alkoxy group and an isocyanate group in one molecule. And a process of
[Iii] Surface modification with an epoxy group-containing silane coupling agent (b1) by reacting an epoxy group-containing silane coupling agent (b1) with inorganic oxide fine particles (B) containing colloidal silica as a main component A step of producing inorganic oxide fine particles (B) mainly composed of colloidal silica,
[Iv] An inorganic oxide mainly composed of an alkoxy group in a reaction product (AE) obtained by reacting the acrylic resin (A) with a silicon compound (E) and the surface-modified colloidal silica. Inorganic oxide fine particles mainly composed of colloidal silica surface-modified with the acrylic resin (A) and the epoxy group-containing silane coupling agent (b1) by reacting with hydroxyl groups in the fine particles (B). (B) and the process of producing the inorganic oxide-acrylic-resin composite ((alpha)) couple | bonded through the coupling | bonding site shown by following General formula (1),
[Chemical formula 2]
—O—Si—R ¹ —NHCOO— (1)
In [the formula (1), R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms. ]
[V] A second summary of a method for producing an active energy ray-curable resin composition comprising a step of mixing a photocationic polymerization initiator (β) together with the inorganic oxide-acrylic resin composite (α). It is what.

Furthermore, this invention makes the coating agent formed by containing the active energy ray-curable resin composition which is the said 1st summary into a 3rd summary, and on a transparent base material surface, it is 3rd summary. A laminate in which an antireflection film is formed using a certain coating agent is a fourth gist.

Thus, the active energy ray-curable resin composition of the present invention includes an acrylic resin (A) containing a hydroxyl group and containing a fluorine atom-containing structural moiety, and an epoxy group-containing silane coupling agent (b1). And the inorganic oxide fine particles (B) whose main component is colloidal silica whose surface is modified in the above formula (1) derived from the silicon compound (E) having both an alkoxy group and an isocyanate group in one molecule And an inorganic oxide-acrylic resin complex (α) formed through a bonding site represented by the formula (1) and a photocationic polymerization initiator (β). For this reason, the reactive energy capable of photocationic polymerization is present at a position close to the inorganic oxide fine particles (B) advantageous for exhibiting scratch resistance, and in such a design, active energy ray curability has been a problem in the past. It becomes possible to make the pot life of the resin composition better. Furthermore, by combining with the acrylic resin (A), which is a polymer capable of lowering the refractive index, to form the inorganic oxide-acrylic resin composite (α), a low refractive index and scratch resistance can be obtained by light irradiation. Can be obtained. Therefore, by using the active energy ray-curable resin composition of the present invention, it is possible to obtain a laminate in which an antireflection film excellent in scratch resistance as well as a low refractive index is formed.

The description of the constituent requirements described below is an example (representative example) of the embodiment of the present invention, and is not limited to these contents.
In the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acryl means acryl or methacryl, and (meth) acrylate means acrylate or methacrylate.
Hereinafter, the present invention will be described in detail.

The active energy ray-curable resin composition of the present invention comprises inorganic oxide fine particles mainly comprising colloidal silica surface-modified with a specific acrylic resin (A) and an epoxy group-containing silane coupling agent (b1). (B) contains an inorganic oxide-acrylic resin complex (α) formed by bonding via a bonding site represented by the following general formula (1), and a photocationic polymerization initiator (β). It will be.
[Chemical formula 4]
—O—Si—R ¹ —NHCOO— (1)
In [the formula (1), R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms. ]

<< Specific acrylic resin (A) >>
The specific acrylic resin (A) used in the present invention is an acrylic resin containing a fluorine atom-containing structural site (hereinafter sometimes referred to as “fluorine-containing group”) in its molecular chain. The fluorine-containing group is preferably present in the side chain of the polymer chain from the viewpoint that the polymer can be easily produced.

Examples of the fluorine atom-containing structure moiety include fluoroalkyl structures such as — (CF ₂ ) _n CF ₃ , — (CF ₂ ) _n CHF ₂ , — (CF ₂ ) _n CHCF ₂ (all n are integers of 0 or more). ).

  The higher the proportion of the fluorine atom-containing structural site in the acrylic resin (A) in the acrylic resin (A), the lower the refractive index of the low refractive index layer made of the coating film can be reduced. The antireflection effect when used as a body can be enhanced.

  If the fluorine atom-containing compound is not copolymerized in addition to the fluorine atom-containing (meth) acrylic acid ester monomer (a1) described below, the ratio of the fluorine atom-containing structural sites is quantitative analysis of the elements contained in the acrylic resin (A). And the weight ratio of fluorine atoms in the acrylic resin (A) can be estimated. Further, even if quantitative analysis of the contained elements is not performed, if the remaining unreacted monomer is reduced to less than about 1% by weight of the charged monomer amount at the time of the polymerization reaction for obtaining the acrylic resin (A), it is charged. Assuming that almost all monomers constitute the acrylic resin (A), it can be estimated from the weight ratio of the charged monomers. Further, it is preferable to perform polymerization so that the remaining unreacted monomer is reduced from the viewpoint of efficiently using the charged monomer and from the viewpoint that it is not necessary to separate and remove the unreacted monomer after the completion of the polymerization reaction.

The residual amount of the unreacted monomer is measured and quantified as follows, for example. That is, the solution of the acrylic resin (A) is analyzed by GC / MS, and the mass of the residual monomer in the acrylic resin (A-1) is determined from a calibration curve determined in advance, and the weight is based on the charged monomer mass. Calculate as a ratio. The GC / MS conditions are as follows.
AS part condition: 7683 Series manufactured by Agilent Technologies. Inject amount 1.0μL
GC section condition: 6890N Network GC System manufactured by Agilent Technologies. Column DB-17MS (Crosslinked Methyl Siloxane) 29.3 m (l) × 0.25 mm (id) × 0.25 μm (d), flow rate 1.0 mL / min. Column temperature 40 ° C. × 5 minutes → 220 ° C. × 10 minutes, heating rate 10 ° C./min. Inlet 220 ° C. Carrier gas He. Split ratio 30: 1.
MS part condition: 5973inert MassSelective Detector manufactured by Agilent Technologies. Mass range 10-600. Ion source temperature 230 ° C. Quadrupole temperature 150 ° C. The number of scans is 2.52 / second.

  The ratio of the fluorine atom-containing structural portion in the acrylic resin (A) is preferably 13 to 40% by weight, more preferably 17 to 35% by weight, as the weight ratio of fluorine atoms in the acrylic resin (A).

  The acrylic resin (A) of the present invention is preferably obtained by copolymerizing a copolymer component containing a fluorine atom-containing (meth) acrylic acid ester monomer (a1). In order to provide the structural site represented by the formula (1), it is particularly preferable to further include a hydroxyl group-containing (meth) acrylic acid ester monomer (a2) as a copolymerization component [I] for copolymerization.

<Fluorine atom-containing (meth) acrylic acid ester monomer (a1)>
As the fluorine atom-containing (meth) acrylic acid ester monomer (a1), a (meth) acrylic acid ester monomer containing a fluorine atom in the molecule may be used, and in particular, a (meth) having a fluoroalkyl group. It is preferable to use an acrylic ester.

Any (meth) acrylic acid ester having the fluoroalkyl group as an ester group may be used. Examples of the fluoroalkyl group include —COOCH ₂ (CF ₂ ) _n CF ₃ , —COOCH ₂ CH ₂ (CF ₂ ) _n CF ₃ , —COOCH ₂ (CF ₂ ) _n CHF ₂ , —COOCH ₂ CH ₂ ( CF ₂ ) _n CHCF _{2 and the} like (all n are integers of 0 or more), and these can be used alone or in combination of two or more. Preferably, the fluoroalkyl group has 0 to 12 (preferably 0 to 10) carbon atoms (n in the above) from the viewpoint of easy availability and easy effect. Specifically, CF ₃ CH ₂ - trade name of Kyoeisha Chemical Co., Ltd. having a group "M-3F", CF ₃ CF ₂ CH ₂ - trade name manufactured by Daikin Industries, Ltd. having a group "M-1210" , A product name “M-1420” manufactured by Daikin Industries, Ltd. having a F (CF ₂ ) ₄ CH ₂ CH ₂ — group, and a product manufactured by Daikin Industries, Ltd. having an F (CF ₂ ) ₆ CH ₂ CH ₂ — group. Name “M-1620” and the like.

  The amount of the fluorine atom-containing (meth) acrylic acid ester monomer (a1) used is preferably 40 to 90 parts by weight, particularly preferably 50 to 80 parts by weight with respect to 100 parts by weight of the copolymer component [I]. is there. If the amount of the fluorine atom-containing (meth) acrylic acid ester monomer (a1) is too large, the cost is increased, and the effect of improving the scratch resistance on the film obtained by photocuring the active energy ray-curable resin composition There is a tendency that it is difficult to demonstrate. Moreover, when there is too little usage-amount, the tendency for achievement of the desired low refractive index reduction in the film | membrane obtained by photocuring an active energy ray-curable resin composition will become difficult.

<Hydroxyl group-containing (meth) acrylic acid ester monomer (a2)>
In the present invention, a hydroxyl group can be contained in the acrylic resin by copolymerizing the hydroxyl group-containing (meth) acrylic acid ester monomer (a2), and the hydroxyl group reacts with an isocyanate group to react with the general formula (1). ) Will form a urethane bond in the binding site.
Examples of the hydroxyl group-containing (meth) acrylic acid ester monomer (a2) include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like. These may be used alone or in combination of two or more. Among these, it is particularly preferable to use 2-hydroxyethyl (meth) acrylate because it is easily available and has good affinity with silica.

  The amount of the hydroxyl group-containing (meth) acrylic acid ester monomer (a2) used is preferably 10 to 60 parts by weight, particularly preferably 20 to 50 parts by weight, based on 100 parts by weight of the copolymer component [I]. . When the amount of the hydroxyl group-containing (meth) acrylic acid ester monomer (a2) used is too large, unreacted hydroxyl groups increase in the resin composition, so that the active energy ray-curable resin composition is photocured. There is a tendency that it is difficult to achieve a desired low refractive index in the resulting film, and if the amount used is too small, it tends to be difficult to ensure a good pot life of the active energy ray-curable resin composition. is there.

<Other monomer components>
Furthermore, other monomer components other than the fluorine atom-containing (meth) acrylic acid ester monomer (a1) and the hydroxyl group-containing (meth) acrylic acid ester monomer (a2) can be used. For example, the alkyl (meth) acrylic acid ester monomer (a3) may be copolymerized from the viewpoint of improving copolymerization and adhesion. In addition, as said alkyl (meth) acrylic acid ester monomer (a3), the monomer component which does not have a fluorine atom containing structural unit, a hydroxyl group, and an epoxy group is used.

  Examples of the alkyl (meth) acrylate monomer (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, and tert-butyl ( (Meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl acrylate, isodecyl (meth) acrylate, lauryl (meth) ) Acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, iso-stearyl (meth) acrylate and other (meth) acrylic acid alkyl esters; cyclohexyl (meth) acrylate, isobornyl (meth) a Alicyclic such Relate (meth) acrylic acid ester. In the case of the above (meth) acrylic acid alkyl ester, the alkyl group preferably has 1 to 20 carbon atoms, particularly preferably 1 to 12, more preferably 1 to 8, and particularly preferably 4 to 8. These can be used alone or in combination of two or more. Among these, methyl (meth) acrylate is preferably used because it is easily available and has good copolymerizability.

  The amount of the alkyl (meth) acrylic acid ester monomer (a3) used is preferably 10 to 30 parts by weight, particularly preferably 15 to 25 parts by weight with respect to 100 parts by weight of the copolymer component [I].

<Method for Producing Specific Acrylic Resin (A)>
The specific acrylic resin (A) includes the fluorine atom-containing (meth) acrylic acid ester monomer (a1), the hydroxyl group-containing (meth) acrylic acid ester monomer (a2), and, if necessary, the alkyl ( It can be produced by copolymerizing the (meth) acrylate monomer (a3). Examples of the copolymerization method include solution radical polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Among them, a copolymerization method by solution radical polymerization is preferable from the viewpoint of easy control of the reaction. This solution radical polymerization method is carried out, for example, by mixing or dropping each of the monomer components such as a1 and a2 and a3, which is appropriately used as necessary, and a polymerization initiator in a solvent, followed by heating and stirring. Although the said heating conditions are suitably set by the solvent to be used, the kind of monomer component, and the kind of polymerization initiator, Usually, 50-150 degreeC and reaction time are 2 to 20 hours.

  As the solvent, an acrylic resin (A) can be dissolved and mixed with inorganic oxide fine particles (B) mainly composed of colloidal silica, which will be described later, and can react with isocyanate groups such as alcohol and amine. It is preferable to use one having no group. That is, when a solvent having a functional group that reacts with an isocyanate group such as alcohol or amine is used as a solvent, an acrylic resin (A) and inorganic oxide fine particles (B) containing colloidal silica as main components are used in a subsequent step. When bonding is attempted through the bonding site represented by the general formula (1), not only the acrylic resin (A) and the inorganic oxide fine particles (B) mainly composed of colloidal silica are bonded but also a solvent. And inorganic oxide fine particles (B) mainly composed of colloidal silica are bonded, and a large number of particles not bonded to the acrylic resin (A) are not preferable. For this reason, for example, esters such as 1-methoxy-2-procelacetate, 1,2-diacetoxypropane, ethyl acetate, butyl acetate, ethers such as tetrahydrofuran, 1,4-dioxane, etc. are used. . These may be used alone or in combination of two or more.

  As the polymerization initiator, a normal radical polymerization initiator can be used. For example, azo polymerization initiators such as azobisisobutyronitrile and azobisdimethylvaleronitrile, benzoyl peroxide, lauryl peroxide, Peroxide-based polymerization initiators such as -t-butyl peroxide and cumene hydroxy peroxide can be used.

  In the polymerization, a chain transfer agent can be used. Examples of the chain transfer agent include mercaptans such as octyl mercaptan and lauryl mercaptan. Moreover, when using the said chain transfer agent, the usage-amount is preferably 1 to 10 weight% with respect to the whole acrylic resin (A), Most preferably, it is 1 to 5 weight%.

  The specific acrylic resin (A) thus obtained preferably has a weight average molecular weight of 10,000 to 100,000, more preferably 20,000 to 50,000. The weight average molecular weight can be controlled by the amount of polymerization initiator used and the polymerization temperature conditions, and can be further finely adjusted by blending a chain transfer agent if necessary. When the weight average molecular weight is too large, the viscosity of the active energy ray-curable resin composition tends to be high and it tends to be difficult to apply to a film thickness of less than 1 μm. When the weight average molecular weight is too small, When formed on the antireflection film, it tends to be difficult to maintain the shape of the coating film.

In addition, the said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, gel permeation chromatography, specifically, a weight average molecular weight is by standard polystyrene molecular weight conversion, and is a high performance liquid chromatography (Japan “Waters 2695 (main body)” and “Waters 2414 (detector)”, columns: Shodex GPC KF-806L (exclusion molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theory) It is measured by using three series of stages: 10,000 stages / line, filler material: styrene-divinylbenzene copolymer, filler particle diameter: 10 μm.

<< Inorganic oxide fine particles (B) mainly composed of surface-modified colloidal silica >>
The inorganic oxide fine particles (B) whose main component is the surface-modified colloidal silica are the inorganic oxide fine particles (B) whose main component is the colloidal silica whose surface is modified with the epoxy group-containing silane coupling agent (b1). ).

  The inorganic oxide fine particles (B) containing colloidal silica as a main component for surface modification (hereinafter sometimes abbreviated as “inorganic fine particles (B)”) are neutralized with acid using water glass as a raw material. Or can be obtained by a known method such as a method of hydrolyzing an alkyl silicate with an alkali, for example, a commercially available product can be easily obtained.

  The inorganic fine particles (B) are not particularly defined as long as they have colloidal silica as a main component. “Colloidal silica as a main component” means that colloidal silica usually occupies 50% by weight or more, and includes that it is composed only of colloidal silica.

  Examples of the shape of the inorganic fine particles (B) include a spherical shape, a hollow shape, a porous shape, a rod shape, a fiber shape, a plate shape, and an indefinite shape, and a spherical shape is more preferable. The term “spherical” as used in the present invention is intended to include not only exact spheres but also substantially spherical ones.

  In the present invention, in the form of an organosilica sol dispersed in an organic solvent, it is easy to mix with the specific acrylic resin (A), and it is easy to obtain a uniform active energy ray-curable resin composition. It is preferable to use colloidal silica. Examples of the organic solvent include 2-propanol, 1-methoxy-2-propanol, 2-propanone, and the like. Further, as the inorganic oxide fine particles (B), those having a hollow structure are preferable because the refractive index can be further lowered.

And from a viewpoint of providing transparency of the antireflection film having a low refractive index layer finally obtained, the average particle diameter of the inorganic oxide fine particles (B) is preferably 10 to 100 nm, particularly preferably 10. ~ 50 nm. If the average particle size is too large, secondary aggregation tends to occur and the transparency tends to decrease, and if it is too small, mechanical properties tend to decrease.
The average particle size is calculated from the average specific surface area of the particles determined by the BET method in accordance with JIS R 1626 and the true specific gravity of the particles.

  Specifically, as the inorganic oxide fine particles (B) mainly composed of colloidal silica, a product name “IPA-ST” (2-propanol dispersion, average particle diameter of 10 to 15 nm) manufactured by Nissan Chemical Industries, Ltd. The name “PGM-ST” (1-methoxy-2-propanol dispersion, average particle size 10 to 15 nm), the trade name “MEK-ST” (2-propanone dispersion, average particle size 10 to 15 nm), and the like. Moreover, as an example of a commercial product in which silica has a hollow structure, a trade name “Thruria” manufactured by JGC Catalysts & Chemicals Co., Ltd. can be cited.

  In the present invention, the surface of the inorganic oxide fine particles (B) mainly composed of colloidal silica is modified using the epoxy group-containing silane coupling agent (b1), so that the surface-modified colloidal silica is obtained. Inorganic oxide fine particles (B) as a main component are obtained.

  As a reaction method for the surface modification of the inorganic oxide fine particles (B) mainly composed of colloidal silica surface-modified with the epoxy group-containing silane coupling agent (b1), an epoxy group-containing silane coupling agent (b1) The silicon compound (E) having both the acrylic resin (A), an alkoxyl group that can be hydrolyzed in one molecule to be described later, and an isocyanate group that can react with a hydroxyl group is obtained by modifying the colloidal silica surface in advance. However, from the viewpoint of simplifying the production process, the epoxy group-containing silane coupling agent (b1) and the reaction between the acrylic resin (A) and the silicon compound (E) A method in which the product (AE) is reacted with the inorganic oxide fine particles (B) mainly containing colloidal silica is preferable. At this time, as the silane coupling agent, in addition to the epoxy group-containing silane coupling agent (b1), a silane coupling agent (b2) having no epoxy group may be used in combination.

  The epoxy group-containing silane coupling agent (b1) may be a compound having an epoxy group and an alkoxysilyl group in one molecule. For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. These may be used alone or in combination of two or more. As such an epoxy group-containing silane coupling agent (b1), specifically, trade name “KBM-403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd. Trade name “KBE-402” (3-glycidoxypropylmethyldiethoxysilane), trade name “KBM-303” manufactured by Shin-Etsu Chemical Co., Ltd. [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane] Etc. Among them, the reaction when photocuring the active energy ray-curable resin composition is fast, and the bulky cyclohexyl group prevents the cationic photopolymerization initiator from approaching the silica surface, so that the pot life is less likely to occur. From the viewpoint of increasing the length, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferably used.

The amount of the epoxy group-containing silane coupling agent (b1) used is the solid content silica of the inorganic oxide fine particles (B) mainly composed of colloidal silica from the viewpoint of achieving both cationic curability and dispersion stability. On the other hand, it is preferably 1 × 10 ⁻² to 2 × 10 ⁻¹ mmol / silica g, and particularly preferably 1 × 10 ⁻² to 1 × 10 ⁻¹ mmol / silica g.

  As said silane coupling agent (b2) which does not have an epoxy group, what has an alkyl group or a phenyl group is preferable from a viewpoint of ensuring a dispersion stability improvement and pot life. Examples of such silane coupling agent (b2) include methyltrimethoxysilane, dimethyldiethoxysilane, and phenyltriethoxysilane. These may be used alone or in combination of two or more. Specifically, trade name “KBM-13” (methyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-22” (dimethyldiethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd. Trade name “KBE-103” (phenyltriethoxysilane) and the like.

The amount of the silane coupling agent (b2) having no epoxy group is preferably 5 × 10 ⁻ to the silica in the solid content of the inorganic oxide fine particles (B) mainly composed of the colloidal silica. ^{1 to 10} mmol / g of silica, particularly preferably ^{1 to} 4 mmol / g of silica.

  Further, the average particle size of the inorganic oxide fine particles (B) mainly composed of colloidal silica surface-modified with the epoxy group-containing silane coupling agent (b1) thus obtained is the inorganic value described above. It is preferably 10 to 100 nm, particularly preferably 10 to 50 nm, almost the same as the average particle diameter of the oxide fine particles (B). Also, the calculation method of the average particle diameter is calculated from the average specific surface area of the particles determined by the BET method in accordance with JIS R 1626 and the true specific gravity of the particles, as described above.

  The content of the inorganic oxide fine particles (B) mainly composed of the surface-modified colloidal silica is preferably 25 to 100 parts by weight, particularly preferably 100 parts by weight of the specific acrylic resin (A). Is 40 to 70 parts by weight. If the content is too high, it tends to be difficult to maintain the shape of the coating film when formed on the antireflection film. If the content is too low, the scratch resistance of the resulting antireflection film is reduced. There is a tendency to

<< Inorganic oxide-acrylic resin composite (α) >>
In the present invention, an acrylic resin (A) containing the hydroxyl group and containing a fluorine atom-containing structural site (hereinafter sometimes referred to as “specific acrylic resin (A)”), The inorganic oxide fine particles (B) mainly composed of the surface-modified colloidal silica are represented by the following general formula (1) derived from a silicon compound (E) having both an alkoxy group and an isocyanate group in one molecule. By using an inorganic oxide-acrylic resin composite (α) that is bonded through a bonding site, a coating agent having excellent pot life can be obtained, and a coating formed using this coating agent can be obtained. By anti-curing the film, an antireflection film having good scratch resistance and having a low refractive index layer can be obtained.
[Chemical formula 5]
—O—Si—R ¹ —NHCOO— (1)
In [the formula (1), R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms. ]

In the above formula (1), R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, and the alkylene group preferably has 1 to 4 carbon atoms, specifically a methyl group or an ethyl group. N-propyl group, iso-propyl group, n-butyl group and tert-butyl group are preferable.

  A method for producing a binding site represented by the above general formula (1), wherein the specific acrylic resin (A) is bonded to inorganic oxide fine particles (B) mainly composed of surface-modified colloidal silica. As, a silicon compound (E) having both a hydrolyzable alkoxy group and a hydroxyl group-reactive isocyanate group in one molecule (hereinafter sometimes referred to as “silicon compound (E)”) is used. There are methods. Examples of the silicon compound (E) include 3-isocyanatopropyltriethoxysilane. Specifically, trade name “KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd., and the like can be mentioned. This silicon compound (E) is produced by allowing the fine particles (B) to coexist when the isocyanate groups react with the hydroxyl groups of the specific acrylic resin (A) and the alkoxysilyl groups are hydrolyzed. It is also combined with (B).

<Method for producing inorganic oxide-acrylic resin composite (α)>
As a manufacturing method of the said inorganic oxide-acrylic-type resin composite ((alpha)), when the mixing order of a mixing | blending component was considered, [1] making specific acrylic resin (A) and a silicon compound (E) react. Then, a method of adding inorganic oxide fine particles (B) mainly composed of surface-modified colloidal silica, [2] inorganic oxide fine particles (B) mainly composed of surface-modified colloidal silica and a silicon compound ( A method of adding a specific acrylic resin (A) after reacting E) is mentioned.

  In the said manufacturing method, when what reacts with the isocyanate group of silicon compound (E), such as alcohol and an amine, is contained in the solvent used by specific acrylic resin (A), specific acrylic resin ( This is not preferable because the initial purpose of combining A) with the inorganic oxide fine particles (B) mainly composed of surface-modified colloidal silica cannot be achieved.

  However, in the case of the production method [2] in which the inorganic oxide fine particles (B) mainly composed of surface-modified colloidal silica and the silicon compound (E) are reacted first, the surface-modified colloidal silica is the main component. Since it is considered that the isocyanate group of the silicon compound (E) may be affected during the hydrolysis reaction of the inorganic oxide fine particles (B), the specific acrylic resin (A) and the silicon compound (E) may The above production method [1], in which the inorganic oxide fine particles (B) whose main component is colloidal silica whose surface is modified, is added to this after the reaction.

  In addition, when only the solvent of the inorganic oxide fine particles (B) whose main component is surface-modified colloidal silica contains an alcohol, an amine, or the like that reacts with the isocyanate group of the silicon compound (E), First, a specific acrylic resin (A) and a silicon compound (E) are reacted, and then reacted with inorganic oxide fine particles (B) mainly composed of surface-modified colloidal silica. Further, as described above, the inorganic oxide fine particles (B) mainly composed of colloidal silica whose surface has been modified in advance using an epoxy group-containing silane coupling agent (b1) are used as a specific acrylic resin (A). It may be added to the reaction product of silicon compound (E), but from the viewpoint of simplification of the process, the reaction product of specific acrylic resin (A) and silicon compound (E), and epoxy group It is preferable that the silane coupling agent (b1) containing the silane coupling agent (b2) having no epoxy group is reacted with the inorganic oxide fine particles mainly containing colloidal silica at the same time.

<[1] Method for producing inorganic oxide-acrylic resin composite (α)>
First, [1] a specific acrylic resin (A) and a silicon compound (E) are reacted, and then inorganic oxide fine particles (B) mainly composed of surface-modified colloidal silica are added to make inorganic oxidation. A method for producing the product-acrylic resin composite (α) will be described.

  The manufacturing method [1] of the inorganic oxide-acrylic resin composite (α) is performed as follows. First, a fluorine atom-containing structure is obtained by copolymerizing a copolymer component [I] containing a fluorine atom-containing (meth) acrylic acid ester monomer (a1) and a hydroxyl group-containing (meth) acrylic acid ester monomer (a2). A specific acrylic resin (A) containing a site and a hydroxyl group is prepared. Next, the specific acrylic resin (A) is blended with a silicon compound (E) having both a hydrolyzable alkoxy group and a hydroxyl group-reactive isocyanate group in one molecule, and further if necessary. The catalyst is blended, and both are reacted under reaction conditions of room temperature (about 25 ± 10 ° C.) to about 80 ° C. until the isocyanate group derived from the component (E) is no longer detected.

  The amount of the silicon compound (E) used is appropriately set depending on how much the hydroxyl group in the specific acrylic resin (A) is to be reacted. For example, the specific acrylic resin (A) Although the hydroxyl group derived from the hydroxyl group-containing (meth) acrylic acid ester monomer (a2) exists, it is set to such an extent that it reacts with one to several hydroxyl groups per molecular chain of the specific acrylic resin (A). The

  And the usage-amount of the said silicon compound (E) can be calculated | required from the following methods. That is, the specific acrylic resin is calculated from the molecular weight of the specific acrylic resin (A) and the amount of the hydroxyl group-containing (meth) acrylic acid ester monomer (a2) used during the synthesis of the specific acrylic resin (A). The number of hydroxyl groups per molecular chain in (A) can be estimated. Moreover, it can also estimate from what calculated | required the molecular weight of specific acrylic resin (A), and the hydroxyl value of specific acrylic resin (A) by the method based on JISK0070. The silicon compound (E) is preferably used to such an extent that it can be reacted with one to several of the number of hydroxyl groups per molecular chain of the specific acrylic resin (A) thus determined. For example, the amount of the hydroxyl group-containing (meth) acrylic acid ester monomer (a2) used at the time of creating a specific acrylic resin (A) is the same, and the molecular weight is 20,000 and 40,000. If the number of hydroxyl groups introduced per chain is the same, the number of hydroxyl groups per molecular chain is twice as many as those with a molecular weight of 40,000, so the amount of silicon compound (E) used is half. Expected to finish.

  The reaction time at this time is appropriately set depending on whether or not the catalyst is used and the reaction temperature, but is usually 0.5 to 24 hours. Moreover, a well-known urethanization catalyst can be used as said catalyst, For example, a dialkyl dialkoxy tin etc. are mention | raise | lifted. And the usage-amount of the said catalyst is the range of 50-1,000 ppm with respect to the whole reaction system normally in conversion of the metal salt of a catalyst.

  Next, after the reaction between the specific acrylic resin (A) and the silicon compound (E) is completed, the reaction product is cooled to about room temperature, and then the epoxy group-containing silane coupling agent (b1) is added to the reaction product. Correspondingly, hydrolyzing the silane coupling agent (b2) having no epoxy group, inorganic oxide fine particles mainly composed of colloidal silica (for example, in an organosilica gel state), and alkoxy groups in the silicon compound (E). Silicon in the reaction product is blended by blending as much water as possible, further blending a catalyst as necessary, and stirring and mixing under reaction conditions of room temperature (about 25 ± 10 ° C.) to about 80 ° C. Inorganic oxidation surface-modified with compound (E), epoxy group-containing silane coupling agent (b1), and silane coupling agent (b2) having no epoxy group as necessary The reaction between the fine particles (B) is performed, and the specific acrylic resin (A) and the surface-modified inorganic oxide fine particles (B) are bonded through the bonding site represented by the general formula (1). An inorganic oxide-acrylic resin composite (α) is prepared.

  The reaction time in the reaction between the silicon compound (E) and the inorganic oxide fine particles (B) is appropriately set depending on whether or not a catalyst is used and the reaction temperature, but is usually 0.5 to 24 hours. Moreover, as said catalyst, a well-known thing can be used, For example, an acid, a base, or a metal complex is mention | raise | lifted. Specific examples include acidic catalysts such as acetic acid and propionic acid, basic catalysts such as sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide and triethylamine, and metal complexes such as aluminum acetylacetonate. Can do. The amount of the catalyst used is usually set to 100 to 1000 ppm by weight with respect to the total mass of the resin solids.

<[2] Manufacturing method of inorganic oxide-acrylic resin composite (α)>
Next, [2] inorganic oxide fine particles (B) containing colloidal silica whose surface is modified as a main component and silicon compound (E) are reacted, and then a specific acrylic resin (A) is added to make inorganic oxidation. A method for producing the product-acrylic resin composite (α) will be described.

  The manufacturing method [2] of the inorganic oxide-acrylic resin composite (α) is performed as follows. First, inorganic oxide fine particles (B) mainly composed of colloidal silica (for example, in an organosilica gel state), an epoxy group-containing silane coupling agent (b1), and, if necessary, a silane coupling having no epoxy group Agent (b2), and a silicon compound (E) having both a hydrolyzable alkoxy group and a hydroxyl group-reactive isocyanate group in one molecule, and an alkoxy group in the silicon compound (E) can be hydrolyzed. A silicon compound (E) and an epoxy group are mixed by mixing an amount of water and, if necessary, a catalyst and stirring and mixing under reaction conditions of room temperature (about 25 ± 10 ° C.) to about 80 ° C. A reaction product (BE) is produced by reacting the inorganic oxide fine particles (B) whose surface is modified with the containing silane coupling agent (b1).

  The amount of the silicon compound (E) used is appropriately set depending on how much the hydroxyl group in the specific acrylic resin (A) is to be reacted, as in the above production method [1]. The specific acrylic resin (A) has a hydroxyl group derived from a hydroxyl group-containing (meth) acrylic acid ester monomer (a2), but one hydroxyl group per molecule chain of the specific acrylic resin (A). It is set to the extent that it reacts with individuals.

  And although the said reaction time is suitably set by the presence or absence of use of a catalyst, and reaction temperature, it is 0.5 to 24 hours normally. Moreover, as said catalyst, a well-known thing can be used, For example, an acid, a base, or a metal complex is mention | raise | lifted. Specific examples include acidic catalysts such as acetic acid and propionic acid, basic catalysts such as sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide and triethylamine, and metal complexes such as aluminum acetylacetonate. Can do. The amount of the catalyst used is usually set to 100 to 1000 ppm by weight with respect to the total mass of the resin solids.

  On the other hand, by copolymerizing the copolymer component [I] containing the fluorine atom-containing (meth) acrylic acid ester monomer (a1) and the hydroxyl group-containing (meth) acrylic acid ester monomer (a2), the fluorine atom content A specific acrylic resin (A) containing a structural site and a hydroxyl group is prepared.

  Next, after cooling the reaction product (BE) to near room temperature, the reaction product is mixed with the specific acrylic resin (A) solution, and a catalyst is blended as necessary. The mixture between the silicon compound (E) and the specific acrylic resin (A) in the reaction product (BE) is obtained by stirring and mixing under reaction conditions of room temperature (about 25 ± 10 ° C.) to about 80 ° C. The inorganic oxide formed by bonding the specific acrylic resin (A) and the surface-modified inorganic oxide fine particles (B) via the bonding site represented by the general formula (1). -An acrylic resin composite (α) is prepared.

  The reaction time in the reaction between the silicon compound (E) and the specific acrylic resin (A) in the reaction product (B-E) is appropriately set depending on whether or not a catalyst is used and the reaction temperature. .5-24 hours. Moreover, a well-known urethanization catalyst can be used as said catalyst, For example, a dialkyl dialkoxy tin etc. are mention | raise | lifted. And the usage-amount of the said catalyst is the range of 50-1,000 ppm with respect to the whole reaction system normally in conversion of the metal salt of a catalyst.

  In the above production method, the blending ratio of the specific acrylic resin (A) and the inorganic oxide fine particles (B) mainly composed of the surface-modified colloidal silica is 100 wt% of the solid content of the specific acrylic resin (A). The solid content of the inorganic oxide fine particles (B) containing colloidal silica as a main component is preferably 25 to 100 parts by weight, particularly preferably 40 to 70 parts by weight with respect to parts. When the blending ratio of the inorganic oxide fine particles (B) is too large, it tends to be difficult to maintain the shape of the coating film when formed on the antireflection film. Moreover, when there are too few compounding ratios of inorganic oxide microparticles | fine-particles (B), the tendency for the abrasion resistance of the antireflection film formed to fall will be seen.

  Surface modification with a specific acrylic resin (A) bonded through the bonding site represented by the general formula (1) of the inorganic oxide-acrylic resin composite (α) obtained by the above production method The degree of bonding of the inorganic oxide fine particles (B) mainly composed of colloidal silica can be appropriately adjusted depending on the amount of the silicon compound (E) used. The minimum amount of the bond is such that, on average, it reacts with one of the hydroxyl groups present in one molecular chain of the specific acrylic resin (A), and the maximum amount of the bond is the above molecule. It reacts with all hydroxyl groups present in the chain. If the degree of bonding is too small, there is a concern that there are many specific acrylic resins (A) to which the silicon compound (E) is not bonded, and there is a tendency for the pot life and scratch resistance to be adversely affected. On the other hand, if the degree of bonding is too large, the silicon compound (E) becomes excessive, which is not preferable in terms of cost.

  The degree of bonding between the specific acrylic resin (A) and the inorganic oxide fine particles (B) is preferably averaged out of the hydroxyl groups present in one molecular chain of the specific acrylic resin (A). And several hydroxyl groups react with the silicon compound (E). For example, the average degree of polymerization of the specific acrylic resin (A) is 100, and the amount of the hydroxyl group-containing (meth) acrylic acid ester monomer (a2) used is all for producing the specific acrylic resin (A). When it is 25 mol% in the monomer, it is estimated that about 25 hydroxyl groups exist on average in one molecular chain of the specific acrylic resin (A). Accordingly, the amount of the silicon compound (E) used is 1 mol% relative to the hydroxyl group-containing (meth) acrylate monomer (a2) in the minimum amount, and the hydroxyl group-containing (meth) acrylate monomer (max) in the maximum amount. Although it is estimated to be 25 mol% with respect to a2), it is preferably 1 to 5 mol% with respect to the hydroxyl group-containing (meth) acrylic acid ester monomer (a2). At this time, since it is presumed that hydroxyl groups are present on average in the molecular chain in the specific acrylic resin (A), the silicon compound (E) is also averaged in the molecular chain of the specific acrylic resin (A). It is assumed that it reacts. That is, the silicon compound (E) may react with a hydroxyl group that may be present at the end of the molecular chain of the specific acrylic resin (A), but the center of the molecular chain of the specific acrylic resin (A). When the active energy ray-curable resin composition is presumed to have a high ratio of reacting with more hydroxyl groups, the specific acrylic resin (A) is mainly composed of surface-modified colloidal silica. The inorganic oxide fine particles (B) are effectively covered. Therefore, when the hydroxyl group present more in the center of the molecular chain of the specific acrylic resin (A) reacts with the silicon compound (E), the specific acrylic resin (A) extending on both sides of the reaction point The molecular chain also covers the surface-modified inorganic oxide fine particles (B), and the specific acrylic type is more than the case where the hydroxyl group present in the molecular chain of the specific acrylic resin (A) exists only at the terminal portion. It can be said that the molecular chain of the resin (A) can be used effectively.

  In addition, when many hydroxyl groups existing in the molecular chain in the specific acrylic resin (A) are reacted with the silicon compound (E), the silicon compound (B) can be bonded at many reaction points. The purpose of covering the surface-modified inorganic oxide fine particles (B) is, on average, from one hydroxyl group in which the silicon compound (E) is present in one molecular chain of the specific acrylic resin (A). Since it is achieved to the extent that it reacts with 10 or preferably several hydroxyl groups, even if the silicon compound (E) is used excessively more than necessary, it is only economical and is not economical.

Thus, the main component is an acrylic resin (A) containing a hydroxyl group and containing a fluorine atom-containing structure , and colloidal silica surface-modified with an epoxy group-containing silane coupling agent (b1). The inorganic oxide fine particles (B) are bonded via a bonding site represented by the general formula (1) derived from the silicon compound (E) having both an alkoxy group and an isocyanate group in one molecule. An inorganic oxide-acrylic resin composite (α) can be produced.

<< Photocationic polymerization initiator (β) >>
The photocationic polymerization initiator (β) has a catalytic action for initiating a cationic polymerization reaction upon irradiation with light, and generates a cationic polymerization catalyst such as a Lewis acid by irradiating ultraviolet rays or the like. Can be used. For example, diazonium salt, sulfonium salt, iodonium salt and the like can be mentioned. Specifically, diazonium salts such as benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroborate, 4,4'-bis [bis (2-hydroxyethoxyphenyl) sulfonio] phenyl sulfide bishexafluorophosphate, sulfonium salts such as diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexa Fluorophosphate, bis (4-tert-butylphenyl) Iodonium hexafluorophosphate, bis (4-t- butylphenyl) iodonium salts such as iodonium hexafluoroantimonate and the like. Of these, iodonium salts are most often used. These may be used alone or in combination of two or more.

  Specific examples of the photocationic polymerization initiator (β) include a product name “Adekaoptomer SP-150” (triallylsulfonium hexafluorophosphate) manufactured by ADEKA, and a product name “Adekaoptomer SP-170”. (Triallylsulfonium hexafluoroantimonate) and the like.

  The amount of the cationic photopolymerization initiator (β) used is preferably 0.1 to 10 parts by weight, particularly preferably 1 to 5 parts by weight with respect to 100 parts by weight of the inorganic oxide-acrylic resin composite (α). Part. If the amount of the cationic photopolymerization initiator (β) used is too large, it is not economical, and the inorganic oxide fine particles in which the cationic photopolymerization initiator (β) is surface-modified in the active energy ray-curable resin composition ( B) The surface tends to approach and the pot life tends to decrease. Moreover, when there is too little usage-amount, the tendency for the abrasion resistance of the antireflection film formed to fall will be seen.

<< Hydrolyzed product of epoxy group-containing alkoxysilane (C) >>
To the active energy ray-curable resin composition of the present invention, an epoxy group-containing alkoxysilane hydrolyzate (C) may be added for the purpose of improving the stability of the resin composition and improving the scratch resistance. The epoxy group-containing alkoxysilane hydrolyzate (C) is obtained by hydrolytic condensation of an epoxy group-containing alkoxysilane with an acid or a base. The epoxy group-containing alkoxysilane used as a raw material may be a compound having an epoxy group and an alkoxysilyl group, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane or the like is preferably used. These may be used alone or in combination of two or more. Specifically, trade name “KBM-403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-402” (3-glycidoxypropyl) manufactured by Shin-Etsu Chemical Co., Ltd. Methyl diethoxysilane), trade name “KBM-303” [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane] manufactured by Shin-Etsu Chemical Co., Ltd. and the like can be mentioned.

  The amount of the epoxy group-containing alkoxysilane hydrolyzate (C) is preferably 50 to 250 parts by weight, particularly preferably 80 to 200 parts by weight, based on 100 parts by weight of the specific acrylic resin (A). is there. If the amount is too large, it tends to be difficult to maintain the shape of the coating film when formed on the antireflection film. If the amount is too small, the antireflection film to be formed has scratch resistance. There is a tendency to decrease.

<< Sensitizer (F) >>
Furthermore, in the active energy ray-curable resin composition of the present invention, a sensitizer (F) that promotes cationic polymerization can be used in combination with the photocationic polymerization initiator (β) as necessary. Examples include anthracene, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-di (methoxyethoxy) anthracene. These may be used alone or in combination of two or more. Among these, 2-ethyl-9,10-di (methoxyethoxy) anthracene is preferably used from the viewpoint of the compatibility of the resin composition.

  The amount of the sensitizer (F) used is preferably 1 to 100 parts by weight, particularly preferably 5 to 50 parts by weight, with respect to 100 parts by weight of the cationic photopolymerization initiator (β).

《Other additives》
In the active energy ray-curable resin composition of the present invention, a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer and the like can be appropriately blended as necessary in addition to the above-described blending components.

  Examples of the leveling agent include fluorine compounds and silicone compounds, and examples of the ultraviolet absorber include benzotriazole compounds, benzophenone compounds, and triazine compounds. Examples of the light stabilizer include hindered compounds.

  Furthermore, an antioxidant, a flame retardant, an antistatic agent, a stabilizer, a reinforcing agent, a matting agent, organic fine particles, and the like can be added to the active energy ray-curable resin composition of the present invention.

  The active energy ray-curable resin composition of the present invention can be used by blending an organic solvent and adjusting the viscosity as necessary. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, toluene, xylene And the like, glycol ethers such as propylene glycol monomethyl ether, acetates such as methyl acetate, ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more.

  When two or more organic solvents are used, a combination of glycol ethers such as propylene glycol monomethyl ether and ketones such as methyl ethyl ketone and alcohols such as methanol, or a combination of ketones such as methyl ethyl ketone and alcohols such as methanol From the viewpoint of the coating film appearance, it is preferable to use two or more alcohols such as methanol in combination.

  The active energy ray-curable resin composition of the present invention can be diluted to 3 to 60% by weight, preferably 5 to 40% by weight, using the organic solvent, and applied to a substrate.

  In the production of the active energy ray-curable resin composition of the present invention, the surface-modified inorganic oxide-acrylic resin composite (α), the photocationic polymerization initiator (β), which are essential components, and The above components (C), (F), and other additives, which are optional components, can be obtained by appropriately mixing them in any order, but photocation polymerization is initiated in terms of preventing aggregation. It is preferable to add the agent (β) last. Further, the mixing method is not particularly limited, and the mixing can be performed by various methods.

"Coating agent"
The active energy ray-curable resin composition of the present invention is effectively used as a curable resin composition for coating film formation, such as a coating agent on various substrates, and is particularly antireflective formed on the display surface. It is preferably used as a film forming material. Among these, the antireflective film composed of a high refractive index layer and a low refractive index layer is useful as a material for forming a low refractive index layer that is the outermost layer. For example, the active energy ray-curable resin composition of the present invention is applied to a substrate (after further drying if a composition diluted with an organic solvent is applied), then the active energy ray Is cured by irradiation.

  As the substrate, a transparent film such as polyester, polyolefin, polyacrylate, polycarbonate, acetylated cellulose, polyether sulfone and the like can be used. Furthermore, you may use what provided the easily bonding layer on the base-material surface, and what surface-treated, such as corona treatment.

  Moreover, when the low refractive index layer formed by hardening the active energy ray-curable resin composition of the present invention is used on the substrate having a high refractive index layer provided thereon as described above. The antireflection effect can be further improved, which is preferable. When used in the above applications, it is more preferable that the high refractive index layer also has scratch resistance. Examples of a method for forming a layer having a high refractive index and scratch resistance (high refractive index layer) on the substrate include titanium oxide, zirconium oxide, zinc oxide, tin oxide, indium tin oxide, and antimony-doped oxide. A base material, which is a transparent film, comprising a resin composition having a high refractive index such as tin and fine particles having an average particle diameter of 1 to 200 nm dispersed in the active energy ray-curable resin composition of the present invention. The method of apply | coating and hardening to the surface is mention | raise | lifted.

  Examples of the method for coating the base material with the coating agent containing the active energy ray-curable resin composition of the present invention include bar coater coating, air knife coating, gravure coating, dip coating, and spin coat coating. A known coating method such as can be used.

  The thickness of the coating film formed by applying the coating agent is such that the film thickness after drying is less than the visible light wavelength, and if possible, the thickness is ¼ of the visible light wavelength. It is preferable to apply, specifically, the thickness is more preferably 100 to 300 nm, particularly preferably 100 to 200 nm. In other words, the coating film thickness is set so that the wavelength indicating the minimum value of the reflectance in the low refractive index layer to be an antireflection film formed using the coating agent is 500 to 700 nm, more preferably 520 to 650 nm. It is preferable to do.

  The conditions for applying the coating agent are preferably set to low humidity because the cationic polymerization by irradiation with active energy rays proceeds smoothly. Specifically, the relative humidity is less than 40%. It is preferable to set the conditions.

  And the said coating agent is apply | coated to a base material, a coating-film layer is formed, an active energy ray is irradiated to this, and a coating-film layer is hardened, and an antireflection film is formed in the base-material surface.

  When the said coating agent contains a solvent, it is preferable to harden | cure by performing active energy ray irradiation after removing a solvent by making it dry. The drying condition is not particularly limited as long as the solvent can be removed in a temperature range that does not damage the substrate, and examples include drying conditions at 60 to 100 ° C. for several minutes.

  Thus, the thickness of the cured layer obtained by curing the coating layer may be less than the visible light wavelength, and if possible, it may be a thickness of 1/4 of the visible light wavelength. Specifically, the thickness is preferably 100 to 300 nm, particularly preferably 100 to 200 nm.

  As the active energy rays, for example, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous because of the availability of the irradiation device and the price.

As a method of curing by ultraviolet irradiation, a high pressure mercury lamp emitting ultra-high pressure mercury lamp, ultra high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, LED, etc. There is a method of curing by irradiating with ultraviolet rays. Further, the irradiation amount is appropriately set depending on the irradiation device or the like, but it is sufficient that it can be cured to such an extent that the scratch resistance can be exhibited. In the case of ultraviolet irradiation, usually 100 to 2000 mJ / cm ^2. It is. In addition, after the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

  Specifically, the active energy ray-curable resin composition of the present invention is used as a material for forming an antireflection film (low refractive index layer) formed on a display (transparent resin substrate). Excellent pot life. Furthermore, the antireflection film formed by cationic photopolymerization is formed into a coating film having excellent scratch resistance even when the film thickness is less than 1 μm and is necessary for lowering the refractive index. The active energy ray-curable resin composition of the present invention is useful as various film forming materials such as various protective coating agents including the coating agent that becomes the antireflection film forming material.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the examples, “parts” and “%” mean weight standards.

[Example 1]
<Preparation of base film>
5.0 parts of urethane (meth) acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “UV-7600”), 1-hydroxycyclohexyl phenyl ketone (made by Ciba Japan Co., Ltd., trade name “Irgacure” as photo radical polymerization initiator) 184 ") and 5.0 parts of 1-methoxy-2-propanol as a solvent were prepared, and these were mixed to prepare an active energy ray-curable resin composition for a high refractive index layer. Next, after applying the active energy ray-curable resin composition for a high refractive index layer on the surface of a polyethylene terephthalate (PET) film (manufactured by Toray Industries Inc., Lumirror: film thickness 100 μm) with a # 8 bar coater (film) After drying for 2 minutes at 80 ° C. (thickness: 5.6 μm), the substrate film was produced by irradiating with ultraviolet rays (irradiation amount: 500 mJ / cm ² ) and curing.

<Preparation of acrylic resin (A)>
A 500 mL flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, and a thermometer was purged with nitrogen, and then, the fluorine atom-containing (meth) acrylic acid ester monomer (a1) was added to this flask as 1H, 1H-tri 22.5 parts of fluoroethyl methacrylate (trade name “M-3F”, manufactured by Kyoeisha Chemical Co., Ltd.), 7.5 parts of 2-hydroxyethyl methacrylate as a hydroxyl group-containing (meth) acrylic acid ester monomer (a2), a chain transfer agent As a polymerization initiator, 1.5 parts of lauryl mercaptan and 90 parts of 1-methoxy-2-propyl acetate as a solvent were added, and 2,2′-azobisdimethylvaleronitrile (trade name “ADVN” manufactured by Otsuka Chemical Co., Ltd.) 0.125 parts was added and the reaction was started at 65 ° C. After 3 hours, 0.125 part of the polymerization initiator was added and reacted for another 3 hours, then the temperature was raised to 100 ° C. and kept for 0.5 hours, and then cooled to room temperature (25 ° C.), An acrylic resin (A-1) (solid content 25%; weight average molecular weight 30,000) solution containing a fluorine atom-containing structural moiety and a hydroxyl group was obtained.

  The weight average molecular weight of the obtained acrylic resin (A-1) was measured according to the method shown below.

<Method for measuring weight average molecular weight>
The weight average molecular weight is based on standard polystyrene molecular weight conversion, and high-performance liquid chromatography (manufactured by Japan Waters, “Waters 2695 (main body)” and “Waters 2414 (detector)”), column: Shodex GPC KF-806L ( Exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plate / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) It was measured by using this series.

Moreover, when the unreacted monomer residual amount in acrylic resin (A-1) was quantified according to the following method, it was 0.5%.
And the weight ratio which a fluorine atom occupies in acrylic resin (A-1) calculated | required from the preparation monomer weight ratio, since the unreacted monomer residual amount was less than 1 weight% of the preparation monomer amount, and 25 weight % Was estimated.

<Quantification method of remaining amount of unreacted monomer>
The solution of the acrylic resin (A-1) is analyzed by GC / MS, and the mass of the residual monomer in the acrylic resin (A-1) is determined from a calibration curve determined in advance, and the weight is calculated based on the charged monomer mass. As a ratio. The conditions of GC / MS are as follows.
AS part condition: 7683 Series manufactured by Agilent Technologies. Inject amount 1.0μL
GC section condition: 6890N Network GC System manufactured by Agilent Technologies. Column DB-17MS (Crosslinked Methyl Siloxane) 29.3 m (l) × 0.25 mm (id) × 0.25 μm (d), flow rate 1.0 mL / min. Column temperature 40 ° C. × 5 minutes → 220 ° C. × 10 minutes, heating rate 10 ° C./min. Inlet 220 ° C. Carrier gas He. Split ratio 30: 1.
MS part condition: 5973inert MassSelective Detector manufactured by Agilent Technologies. Mass range 10-600. Ion source temperature 230 ° C. Quadrupole temperature 150 ° C. The number of scans is 2.52 / second.

<Preparation of Inorganic Oxide-Acrylic Resin Composite (α) (Production Method [1])>
To the acrylic resin (A-1) solution (solid content 25%) 120 parts, 3-isocyanatopropyltriethoxysilane (E) (trade name “KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.29 parts [1.2 mmol, equivalent to 2 mol% of all hydroxyl groups in the acrylic resin (A-1)] was added to 1.5 parts of 1-methoxy-2-propylacetate, and dibutyltin dilaurate as a catalyst was added in an amount of 0. The reaction product of the said acrylic resin (A-1) and the said 3-isocyanatopropyltriethoxysilane (E-1) was obtained by adding 03 parts and making it react at 80 degreeC for 2 hours. When the liquid at the end of the reaction was titrated with an amine, no isocyanate group was observed.

Next, colloidal silica (Nissan Chemical Co., Ltd.) dispersed in 1-methoxy-2-propyl acetate in 120 parts of the reaction product of the acrylic resin (A-1) and 3-isocyanatopropyltriethoxysilane (E-1). Made by Kogyo Co., Ltd., trade name “PMA-ST”; average particle size 10-15 nm; solid content 30% by weight) 60 parts, epoxy group-containing silane coupling agent (b1), 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-303”) 0.72 part (2.9 mmol), methyltrimethoxysilane (Shin-Etsu) as a silane coupling agent (b2) having no epoxy group Chemical Industry Co., Ltd., trade name “KBM-13”) 7.2 parts (53 mmol), water 1.0 parts, acetic acid 2.7 parts as a catalyst was charged at 70 ° C. Colloidal silica surface-modified with the acrylic resin (A-1), the epoxy group-containing silane coupling agent (b1), and the silane coupling agent (b2) having no epoxy group by reacting for a period of time A silica-acrylic resin composite, wherein (B) is bonded to the binding site represented by the formula (1) [wherein R ¹ is —CH ₂ CH ₂ CH ₂ —] (Α-1) was obtained. Here, the amounts of the epoxy group-containing silane coupling agent (b1) and the silane coupling agent (b2) having no epoxy group with respect to silica are 1.6 × 10 ⁻¹ mmol / silica g, and 2. The amount of the colloidal silica (B) surface-modified with respect to 100 parts of the acrylic resin (A) was 60 parts.

<Preparation of hydrolyzate of epoxy group-containing alkoxysilane (C)>
In a 300 mL flask equipped with a stirrer, a cooler, and a thermometer, 48 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-303”), 2-butanone While adding 96 parts, while stirring, 5 parts of a 0.1 wt% aqueous potassium hydroxide solution was added, and a hydrolysis reaction was carried out at 70 ° C. for 4 hours. Next, after cooling to room temperature (25 degreeC), the acetic acid was added and neutralized, and the hydrolyzate (C-1) of the epoxy group containing alkoxysilane was obtained by removing a solvent with a rotary evaporator.

<Preparation of active energy ray-curable resin composition>
3.6 parts of the surface-modified silica-acrylic resin composite (α-1), 1.0 part of the hydrolyzate of the epoxy group-containing alkoxysilane (C-1), a cationic photopolymerization initiator (β- The active energy ray-curable resin composition was prepared by mixing 0.056 part of a trade name “Adekaoptomer SP-170” manufactured by ADEKA as 1) and 5.8 parts of 1-methoxy-2-propyl acetate as a solvent. Got.

The active energy ray-curable resin composition is applied onto the previously prepared base film using a # 2 bar coater, dried at 80 ° C. for 2 minutes, and then irradiated with ultraviolet rays at a dose of 500 mJ / cm ^2. Was applied to cure the coating film to obtain a laminate (an antireflection film which is a cured coating layer formed on the base film). The thickness of the coating film cured layer made of the active energy ray-curable resin composition after curing was 0.52 μm.

[Example 2]
<Preparation of active energy ray-curable resin composition>
3.6 parts of the surface-modified silica-acrylic resin composite (α-1) produced in Example 1 above, manufactured by ADEKA as a cationic photopolymerization initiator (β-1), trade name “Adekaoptomer SP” An active energy ray-curable resin composition was obtained by mixing 0.056 part of -170 "and 1.8 parts of 1-methoxy-2-propyl acetate as a solvent.

The active energy ray-curable resin composition is applied onto the previously prepared base film using a # 2 bar coater, dried at 80 ° C. for 2 minutes, and then irradiated with ultraviolet rays at a dose of 500 mJ / cm ^2. Was applied to cure the coating film to obtain a laminate (an antireflection film which is a cured coating layer formed on the base film). The thickness of the coating film hardening layer which consists of this active energy ray curable resin composition after hardening was 0.50 micrometer.

[Comparative Example 1]
<Preparation of Inorganic Oxide-Acrylic Resin Composite (α) (Production Method [1])>
In a solution of the acrylic resin (A-1) prepared in Example 1 above, 0.29 parts [1] 3-isocyanatopropyltriethoxysilane (E) (trade name “KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) .2 mmol, equivalent to 2 mol% of all hydroxyl groups in acrylic resin (A)] was added to 1.5 parts of 1-methoxy-2-propylacetate, and 0.03 part of dibutyltin dilaurate was added as a catalyst. And the reaction product of the said acrylic resin (A-1) and the said 3-isocyanatopropyltriethoxysilane (E) was obtained by making it react at 80 degreeC for 2 hours. When the liquid at the end of the reaction was titrated with an amine, no isocyanate group was observed.

  Next, the reaction product of the acrylic resin (A-1) and 3-isocyanatopropyltriethoxysilane (E) is used without using the epoxy group-containing silane coupling agent (b1) and 1-methoxy-2-propyl. Colloidal silica dispersed in acetate (manufactured by Nissan Chemical Industries, trade name “PMA-ST”; average particle size 10-15 nm; solid content 30% by weight) 60 parts, silane coupling agent having no epoxy group (b2 ), 7.2 parts (53 mmol) of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-13”), 1.0 part of water, and 2.7 parts of acetic acid as a catalyst were charged at 70 ° C. By reacting for 4 hours, a silica-acrylic resin composite (α-3) surface-modified with methyltrimethoxysilane was obtained. Here, the amount of the silane coupling agent (b2) having no epoxy group with respect to silica is 2.9 mmol / g of silica, and the surface-modified silica (B) is blended with 100 parts of the acrylic resin (A). The amount was 60 parts.

<Preparation of active energy ray-curable resin composition>
3.6 parts of the surface-modified silica-acrylic resin composite (α-3), 1.0 part of hydrolyzate of epoxy group-containing alkoxysilane prepared in Example 1 (C-1), photocation By mixing 0.056 part of a trade name “Adekaoptomer SP-170” manufactured by ADEKA as a polymerization initiator (β-1) and 5.8 parts of 1-methoxy-2-propyl acetate as a solvent, an active energy is obtained. A linear curable resin composition was obtained.

The active energy ray-curable resin composition is applied onto the previously prepared base film using a # 2 bar coater, dried at 80 ° C. for 2 minutes, and then irradiated with ultraviolet rays at a dose of 500 mJ / cm ^2. Was applied to cure the coating film to obtain a laminate (an antireflection film which is a cured coating layer formed on the base film). The thickness of the coating film cured layer made of the active energy ray-curable resin composition after curing was 0.52 μm.

[Comparative Example 2]
3.6 parts of acrylic resin (A-1) prepared in Example 1 above, colloidal silica dispersed in 1-methoxy-2-propyl acetate (manufactured by Nissan Chemical Industries, trade name “PMA-ST”; average 60 parts by particle size 10-15 nm; solid content 30% by weight) 1.0 parts hydrolyzate of epoxy group-containing alkoxysilane prepared in Example 1 (C-1), photocationic polymerization initiator (β-1 The active energy ray-curable resin composition is prepared by mixing 0.056 part of a trade name “ADEKA OPTMER SP-170” manufactured by ADEKA Corporation and 5.8 parts of 1-methoxy-2-propyl acetate as a solvent. Obtained.

The active energy ray-curable resin composition is applied onto the previously prepared base film using a # 2 bar coater, dried at 80 ° C. for 2 minutes, and then irradiated with ultraviolet rays at a dose of 500 mJ / cm ^2. Was applied to cure the coating film to obtain a laminate (an antireflection film which is a cured coating layer formed on the base film). The thickness of the coating film cured layer made of the active energy ray-curable resin composition after curing was 0.52 μm.

  The pot life of each active energy ray-curable resin composition thus obtained, and the refractive index and transparency (haze value) of the cured film formed using each active energy ray-curable resin composition. The scratch resistance was measured and evaluated according to the following method. These results are also shown in Table 1 below.

[Pot life]
Each obtained active energy ray-curable resin composition was stored at room temperature (25 ° C.), and the period until gelation was confirmed by visual observation was measured.

[Refractive index]
The active energy ray-curable resin composition was concentrated to about 80% solid content using a rotary evaporator, and then applied onto a polytetrafluoroethylene sheet using an applicator so as to have a film thickness of 200 μm. This was put into a dryer (80 ° C.) to remove the solvent, and then the coating film was cured by irradiating with ² J / cm ² of ultraviolet rays.
Next, the cured film was peeled from the polytetrafluoroethylene sheet. Using this cured film, the refractive index of the cured film was measured using an Abbe refractometer (manufactured by Atago Co., Ltd., NAR-1T) according to JIS K7105.

[Transparency (haze value)]
Using the laminates produced in Examples 1 and 2 and Comparative Examples 1 and 2, the haze value was measured according to JIS K7105. In addition, the haze meter (Nippon Denshoku Industries make, NDH2000) was used for the measurement.

[Abrasion resistance]
Using the laminates produced in Examples 1 and 2 and Comparative Examples 1 and 2, the test was conducted according to ASTM D1044 (Standard Test Method for Resistance of Transparent Plastics to Surface Abrasion). As shown. A smaller value (Δhaze) indicates that the antireflection film, which is a coating film cured layer in the scratch resistance test, is less damaged, and it can be said that the scratch resistance is excellent.

  From the above results, the laminates of Examples 1 and 2 formed using the active energy ray-curable resin composition containing the inorganic oxide-acrylic resin composite (α) have a low refractive index. It can be seen that the laminate is excellent in transparency and scratch resistance. Furthermore, it turns out that the active energy ray curable resin composition which is Examples 1 and 2 is excellent also in pot life. In particular, the product of Example 1 using the active energy ray-curable resin composition containing the hydrolyzate (C-1) of an epoxy group-containing alkoxysilane has an even better scratch resistance in addition to a good pot life. It was equipped with sex.

On the other hand, a surface-modified silica-acrylic resin composite produced using a silane coupling agent (b2) having no epoxy group without using an epoxy group-containing silane coupling agent (b1) ( The laminate of Comparative Example 1 formed using the active energy ray-curable resin composition using α-3) has a long pot life and good results regarding transparency. Although it was obtained, it was found that the refractive index was high, the Δ haze value was very high, and the scratch resistance was poor.
In addition, the hydrolyzate of epoxy group-containing alkoxysilane (C-1) is blended, and colloidal silica is simply mixed with the acrylic resin without using the surface-modified silica-acrylic resin composite (α). The laminate of Comparative Example 2 formed using the active energy ray-curable resin composition produced by the above method has a refractive index higher than that of the laminate of the example and does not have a sufficiently low refractive index. I understand. Moreover, it can be seen that the Δ haze value is extremely high and the scratch resistance is poor.

  The active energy ray-curable resin composition of the present invention is excellent in pot life, and further has a film having an effect of excellent scratch resistance even with a thickness required for a low refractive index of less than 1 μm by photocationic polymerization. Can be formed. Therefore, the active energy ray-curable resin composition of the present invention is useful as various coating agents such as a coating agent that forms an antireflection film that is a low refractive index layer formed on the surface of a transparent resin substrate such as a display. It is.

Claims (17)

An inorganic oxide mainly composed of colloidal silica surface-modified with an acrylic resin (A) containing a hydroxyl group and containing a fluorine atom-containing structure and an epoxy group-containing silane coupling agent (b1) Inorganic oxide-acrylic product in which fine particles (B) are bonded through a bonding site represented by the following general formula (1) derived from a silicon compound (E) having both an alkoxy group and an isocyanate group in one molecule An active energy ray-curable resin composition comprising a resin composite (α) and a cationic photopolymerization initiator (β).
[Chemical formula 1]
—O—Si—R ¹ —NHCOO— (1)
In [the formula (1), R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms. ]   The acrylic resin (A) is copolymerized with the copolymer component [I] containing the fluorine atom-containing (meth) acrylic acid ester monomer (a1) and the hydroxyl group-containing (meth) acrylic acid ester monomer (a2). 2. The active energy ray-curable resin composition according to claim 1, which is an acrylic resin obtained.   The active energy according to claim 2, wherein the proportion of the fluorine atom-containing (meth) acrylic acid ester monomer (a1) is 40 to 90 parts by weight with respect to 100 parts by weight of the copolymer component [I]. A linear curable resin composition.   4. The activity according to claim 2, wherein the proportion of the hydroxyl group-containing (meth) acrylic acid ester monomer (a2) is 10 to 60 parts by weight with respect to 100 parts by weight of the copolymer component [I]. Energy ray curable resin composition.   In addition to the fluorine atom-containing (meth) acrylic acid ester monomer (a1) and the hydroxyl group-containing (meth) acrylic acid ester monomer (a2), the acrylic resin (A) further contains a fluorine atom-containing structural unit, hydroxyl group and epoxy. The acrylic resin obtained by copolymerizing a copolymerization component [I] containing a (meth) acrylic acid ester monomer (a3) having no group, according to any one of claims 1 to 4 The active energy ray-curable resin composition according to one item.   The proportion of the fluorine atom-containing structural unit, the hydroxyl group and the (meth) acrylic acid ester monomer (a3) having no epoxy group is 10 to 30 parts by weight with respect to 100 parts by weight of the copolymerization component [I]. The active energy ray-curable resin composition according to claim 5.   The active energy ray-curable resin composition according to any one of claims 1 to 6, wherein the acrylic resin (A) does not contain an epoxy group-containing structural moiety.   The weight average molecular weight of acrylic resin (A) is 10,000-100,000, The active energy ray-curable resin composition as described in any one of Claims 1-7 characterized by the above-mentioned.   The average particle diameter of inorganic oxide microparticles | fine-particles (B) is 10-100 nm, The active energy ray-curable resin composition as described in any one of Claims 1-8 characterized by the above-mentioned.   The active energy ray-curable resin composition according to any one of claims 1 to 9, wherein the inorganic oxide fine particles (B) are silica having a hollow structure.   Inorganic oxide mainly composed of colloidal silica whose inorganic oxide fine particles (B) are surface-modified with an epoxy group-containing silane coupling agent (b1) and a silane coupling agent (b2) having no epoxy group The active energy ray-curable resin composition according to claim 1, wherein the active energy ray-curable resin composition is a fine particle. The amount of the epoxy group-containing silane coupling agent (b1) used is 1 × 10 ⁻² to 2 × 10 ⁻¹ mmol / g of silica relative to silica in the solid content of the inorganic oxide fine particles mainly composed of colloidal silica. The active energy ray-curable resin composition according to any one of claims 1 to 11, wherein the composition is an active energy ray-curable resin composition.   The amount of the inorganic oxide fine particles (B) mainly composed of surface-modified colloidal silica is 25 to 100 parts by weight with respect to 100 parts by weight of the acrylic resin (A). The active energy ray-curable resin composition according to any one of -12.   The active energy ray-curable resin composition according to claim 1, comprising a hydrolyzate (C) of an epoxy group-containing alkoxysilane. A method for producing an active energy ray-curable resin composition according to any one of claims 1 to 14,
[I] fluorine atom-containing by copolymerizing copolymer component [I] containing fluorine atom-containing (meth) acrylic acid ester monomer (a1) and hydroxyl group-containing (meth) acrylic acid ester monomer (a2) Producing an acrylic resin (A) containing a structural site;
[Ii] A reaction product (AE) is prepared by reacting the hydroxyl group in the acrylic resin (A) with an isocyanate group of a silicon compound (E) having both an alkoxy group and an isocyanate group in one molecule. And a process of
[Iii] Surface modification with an epoxy group-containing silane coupling agent (b1) by reacting an epoxy group-containing silane coupling agent (b1) with inorganic oxide fine particles (B) containing colloidal silica as a main component A step of producing inorganic oxide fine particles (B) mainly composed of colloidal silica,
[Iv] An inorganic oxide mainly composed of an alkoxy group in a reaction product (AE) obtained by reacting the acrylic resin (A) with a silicon compound (E) and the surface-modified colloidal silica. Inorganic oxide fine particles mainly composed of colloidal silica surface-modified with the acrylic resin (A) and the epoxy group-containing silane coupling agent (b1) by reacting with hydroxyl groups in the fine particles (B). (B) and the process of producing the inorganic oxide-acrylic-resin composite ((alpha)) couple | bonded through the coupling | bonding site shown by following General formula (1),
[Chemical formula 2]
—O—Si—R ¹ —NHCOO— (1)
In [the formula (1), R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms. ]
[V] A method for producing an active energy ray-curable resin composition comprising a step of mixing a photocationic polymerization initiator (β) together with the inorganic oxide-acrylic resin composite (α). .   A coating agent comprising the active energy ray-curable resin composition according to any one of claims 1 to 14. A laminate comprising an antireflection film formed on the surface of a transparent substrate using the coating agent according to claim 16 .