JP5976357B2 - Active energy ray-curable resin composition, coating agent using the same, and laminate - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition, a coating agent using the same, and a laminate, and more specifically, a coating material having a good pot life and excellent in low refractive index, scratch resistance and transparency. The present invention relates to an active energy ray-curable resin composition for forming a film, a coating agent using the same, and a laminate.

  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 photopolymerization initiator that generates radicals or cations by photoirradiation as a photopolymerization initiator and to ensure scratch resistance by using silica. ing. For example, as a film that can be used on the outermost surface of the display, it contains reactive silica having a particle size of 1 to 200 nm having a radical polymerizable group or a cationic polymerizable group, and includes a fluorine-containing vinyl monomer polymerization unit and radical polymerization in the side chain. An antireflection film having a low refractive index layer composed of a cured film using a copolymerizable composition containing a polymerizable unit or a polymerizable unit having a cationic polymerizable group has been proposed (see Patent Document 1).

JP 2004-93947 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 silica having a cationic polymerizable group is used, it is necessary for the photocationic polymerization initiator to come close to the silica surface, but this photocationic polymerization initiator is strongly bonded to and aggregated with the originally acidic silica surface. Therefore, there is a problem that the pot life of the coating agent is remarkably shortened.

  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, has a good pot life, and 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 capable of forming a cured film, a coating agent using the same, and a laminate.

  That is, as a result of intensive research to achieve the above object, the present inventor has obtained a fluorine atom-containing structural site, an epoxy group and a hydroxyl group in an active energy ray-curable resin composition containing a photocationic polymerization initiator. By using the acrylic resin (A) contained, it was found that the hydroxyl group exerts a compatibility improving effect on the epoxy group-containing silicate oligomer (B), thereby improving the pot life. Furthermore, in the same manner as the acrylic resin (A) having photocationic polymerizability, by using the epoxy group-containing silicate oligomer (B) having photocationic polymerizability, in addition to the good pot life, Scratch resistance is imparted to the coating film, and an active energy ray-curable resin composition with a low refractive index is obtained by introducing a fluorine atom-containing structure site into the acrylic resin (A). The present invention has been reached.

  The present invention provides an activity comprising an acrylic resin (A) containing a fluorine atom-containing structural moiety, an epoxy group and a hydroxyl group, an epoxy group-containing silicate oligomer (B), and a photocationic polymerization initiator (C). The energy ray curable resin composition is the first gist.

  And this invention makes the 2nd summary the coating agent formed by containing the active energy ray-curable resin composition which is the said 1st summary. Furthermore, this invention makes the 3rd summary the laminated body by which an anti-reflective film is formed in the transparent base material surface using the coating agent which is the said 2nd summary.

  Thus, the active energy ray-curable resin composition of the present invention includes an acrylic resin (A) containing a fluorine atom-containing structural site, an epoxy group and a hydroxyl group, an epoxy group-containing silicate oligomer (B), A cationic photopolymerization initiator (C). For this reason, since photocationic polymerization can be performed, a coating film excellent in scratch resistance can be formed even with a film thickness required for a low refractive index of less than 1 μm. Moreover, since the acrylic resin (A) has a hydroxyl group while having a low refractive index, it has an affinity for the epoxy group-containing silicate oligomer (B). Since both the acrylic resin (A) and the epoxy group-containing silicate oligomer (B) have an epoxy group which is a functional group capable of photocationic polymerization, the epoxy group-containing silicate oligomer (B) is converted into the acrylic resin by light irradiation. Since it is fixed to (A), for example, when used for film formation on the outermost surface of the laminate, the silica particles are prevented from falling off even when rubbed, and a coating film excellent in maintaining scratch resistance is obtained. Can be obtained. Therefore, by using the active energy ray-curable resin composition of the present invention, an antireflection laminate having a low refractive index and excellent scratch resistance can be obtained.

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 a specific acrylic resin (A), an epoxy group-containing silicate oligomer (B), and a photocationic polymerization initiator (C).

<< Specific acrylic resin (A) >>
The specific acrylic resin (A) used in the present invention contains, in its molecular chain, a fluorine atom-containing structural site (hereinafter sometimes referred to as “fluorine-containing group”), an epoxy group, and a hydroxyl group. It is preferable that the fluorine-containing group, the epoxy group, and the hydroxyl group are present in the side chain of the polymer chain from the viewpoint that the polymer can be easily prepared, and the fluorine-containing group, the epoxy group, and the hydroxyl group are It is preferable that each exists as a separate group.

Examples of the fluorine atom-containing structure site 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 can be enhanced when it is made into a body, but on the other hand, when the ratio is too high, for example, the ratio of epoxy groups and hydroxyl groups in the acrylic resin (A) is reduced. By reducing the ratio of groups, the density of crosslinking points formed upon irradiation with active energy rays will be reduced, and by reducing the ratio of hydroxyl groups, compatibility with the silicate oligomer (B) described later will be reduced. Is not preferable. That is, there are preferred ranges for the ratio of the fluorine atom-containing structural sites, the ratio of epoxy groups, and the ratio of hydroxyl groups in the acrylic resin (A).

  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, the mass of the residual monomer in the acrylic resin (A) is obtained from a calibration curve obtained in advance, and is used as the weight ratio with respect to the charged monomer mass. Ask. 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 epoxy group in the acrylic resin (A) can be estimated as a molar ratio by obtaining the epoxy equivalent of the acrylic resin (A) according to JIS K7236. Similarly to the determination of the weight ratio of fluorine atoms, if polymerization is performed so that the remaining unreacted monomer is reduced, it can be estimated from the weight ratio of charged monomers.

  Ratio of fluorine atom-containing structural sites in acrylic resin (A) (hereinafter sometimes referred to as “fluorine-containing ratio”), epoxy group ratio (hereinafter sometimes referred to as “epoxy-containing ratio”), hydroxyl group ratio (Hereinafter sometimes referred to as “hydroxyl-containing ratio”) is to evaluate the ratio in general, the fluorine-containing ratio is the epoxy-containing ratio as the weight ratio of the elements in the acrylic resin (A). And the hydroxyl group ratio is determined as the weight ratio of the functional groups in the acrylic resin (A), and therefore, an appropriate index cannot be shown. Therefore, preferred ranges are “fluorine-containing ratio”, “epoxy-containing ratio”, “ Each of them can be shown as “hydroxyl ratio”.

  That is, the “fluorine-containing ratio” is preferably 10 to 45% by weight, more preferably 15 to 35% by weight, as the weight ratio of fluorine atoms in the acrylic resin (A).

  The “epoxy-containing ratio” is preferably a value estimated from the amount of JIS K7236 or the remaining unreacted monomer and the charged monomer weight ratio as the epoxy equivalent of the acrylic resin (A), and is preferably 450 to 1500, and preferably 500 to 1250. Is more preferable.

Similarly, the ratio of the hydroxyl group in the acrylic resin (A) can be estimated as a molar ratio by obtaining the hydroxyl value of the acrylic resin (A) according to JIS K1557. Similarly to the case of the fluorine group and the epoxy group, if polymerization is performed so that the remaining unreacted monomer is reduced, it can be estimated from the weight ratio of the charged monomers.
“Hydroxyl-containing ratio” is a value estimated from JIS K1557 or the amount of residual unreacted monomer and the weight ratio of charged monomers as the hydroxyl value of the acrylic resin (A), preferably 40 to 130 KOHmg / g, and preferably 40 to 105 KOHmg / g. g is more preferable.

  The acrylic resin (A) used in the present invention comprises a fluorine atom-containing (meth) acrylic acid ester monomer (a1), an epoxy group-containing (meth) acrylic acid ester monomer (a2), and a hydroxyl group-containing (meth) acrylic. It is preferable that it is obtained by copolymerizing the copolymerization component [I] containing the acid ester monomer (a3). Further, from the viewpoint of improvement of copolymerization and adhesion, alkyl (meth) acrylic is used. It is particularly preferable that the acid ester monomer (a4) is contained 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 content of the fluorine atom-containing (meth) acrylic acid ester monomer (a1) is preferably 40 to 80 parts by weight, particularly preferably 50 to 80 parts by weight, relative to 100 parts by weight of the copolymer component [I]. More preferably, it is 50-70 weight part. If the content of the fluorine atom-containing (meth) acrylic acid ester monomer (a1) is too large, the cost becomes high, 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 content, 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 be seen.

<Epoxy group-containing (meth) acrylic acid ester monomer (a2)>
The epoxy group-containing (meth) acrylic acid ester monomer (a2) may be a (meth) acrylic acid ester having an epoxy group as part of the ester group, and the epoxy group has an alicyclic epoxy structure. What it has is preferable because the reaction at the time of photocuring the active energy ray-curable resin composition is fast. Examples thereof include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and more specifically, trade name “Acryester G” (glycidyl methacrylate) manufactured by Mitsubishi Rayon Co., Ltd., Daicel Chemical Industries, Ltd. A trade name “Cyclomer M100” (3,4-epoxycyclohexylmethyl methacrylate) manufactured by K.K. These can be used alone or in combination.

  The content of the epoxy group-containing (meth) acrylic acid ester monomer (a2) is preferably 10 to 30 parts by weight, particularly preferably 10 to 25 parts by weight, relative to 100 parts by weight of the copolymer component [I]. More preferably, it is 15-25 weight part. If the content of the epoxy group-containing (meth) acrylic acid ester monomer (a2) is too large, it is difficult to achieve a desired low refractive index in a film obtained by photocuring the active energy ray-curable resin composition. If the content is too small, it tends to be difficult to exert the effect of improving the scratch resistance on the film obtained by photocuring the active energy ray-curable resin composition.

<Hydroxyl group-containing (meth) acrylic acid ester monomer (a3)>
Examples of the hydroxyl group-containing (meth) acrylic acid ester monomer (a3) 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 content of the hydroxyl group-containing (meth) acrylic acid ester monomer (a3) is preferably 10 to 30 parts by weight, particularly preferably 10 to 25 parts by weight with respect to 100 parts by weight of the copolymer component [I]. . If the content of the hydroxyl group-containing (meth) acrylic acid ester monomer (a3) is too large, it is difficult to achieve a desired low refractive index in a film obtained by photocuring the active energy ray-curable resin composition. If the content is too small, the stability of the resulting active energy ray-curable resin composition tends to be lowered, phase separation tends to occur, and it tends to be difficult to ensure a good pot life.

<Other monomer components>
Furthermore, other than the fluorine atom-containing (meth) acrylic acid ester monomer (a1), epoxy group-containing (meth) acrylic acid ester monomer (a2), and hydroxyl group-containing (meth) acrylic acid ester monomer (a3) Other monomer components can be used. For example, the alkyl (meth) acrylic acid ester monomer (a4) may be copolymerized from the viewpoint of improving copolymerization and adhesion.

  Examples of the alkyl (meth) acrylate monomer (a4) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, 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 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. 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 content of the alkyl (meth) acrylic acid ester monomer (a4) 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 epoxy group-containing (meth) acrylic acid ester monomer (a2), and the hydroxyl group-containing (meth) acrylic acid ester. It can be produced by copolymerizing the monomer (a3) and, if necessary, the alkyl (meth) acrylate monomer (a4). 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 performed, for example, by mixing or dropping each monomer component such as a1 to a4 and a polymerization initiator in a solvent and 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 said solvent, what melt | dissolves acrylic resin (A) and can mix with the below-mentioned epoxy-group-containing silicate oligomer (B) is preferable. For example, alcohols such as methanol, ethanol, 2-propanol, 1-methoxy-2-propanol, ketones such as 2-propanone, 4-methyl-2-pentanone, cyclohexanone, ethyl acetate, butyl acetate, 1-methoxy- Esters such as 2-propyl acetate and 1,2-diacetoxypropane are preferred. 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.

  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 content of the polymerization initiator used and the polymerization temperature conditions, and can be further finely adjusted if necessary by adding a chain transfer agent. 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.

<< Epoxy group-containing silicate oligomer (B) >>
The epoxy group-containing silicate oligomer (B) is preferably obtained by hydrolytic condensation of the epoxy group-containing silane coupling agent (b1) under basic conditions.

  The epoxy group-containing silane coupling agent (b1) may be a compound having an epoxy group and an alkoxysilyl group. Examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Specifically, Shin-Etsu Chemical Co., Ltd. Trade name “KBM-403” (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd., trade name “KBE-402” (3-glycidoxypropylmethyldiethoxysilane), Shin-Etsu Chemical A trade name “KBM-303” [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane] manufactured by Kogyo Co., Ltd. can be mentioned. These can be used alone or in combination.

  Furthermore, you may use together the silane coupling agent (b2) which does not have an epoxy group with the said epoxy group containing silane coupling agent (b1).

  Examples of the silane coupling agent (b2) having no epoxy group include methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and the like. Specifically, products manufactured by Shin-Etsu Chemical Co., Ltd. Name “KBM-13” (methyltrimethoxysilane), trade name “KBE-13” (methyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-22” (dimethyldiethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane). These can be used alone or in combination.

  The blending ratio [(b1) :( b2)] of the epoxy group-containing silane coupling agent (b1) and the silane coupling agent (b2) having no epoxy group is (b1) :( b2) based on weight. ) = 100: 0 to 50:50, particularly preferably (b1) :( b2) = 100: 0 to 70:30.

<Method for producing epoxy group-containing silicate oligomer (B)>
The epoxy group-containing silicate oligomer (B) is a base obtained by mixing an epoxy group-containing silane coupling agent (b1) and, if necessary, a silane coupling agent (b2) having no epoxy group. It can be produced by hydrolytic condensation under neutral conditions. As a method for producing the epoxy group-containing silicate oligomer (B), specifically, an epoxy group-containing silane coupling agent (b1), and if necessary, a silane coupling agent having no epoxy group ( There is a method in which b2) is mixed with an organic solvent, a basic compound is added, and a hydrolysis condensation reaction is performed under heating conditions (for example, 40 to 80 ° C.). Examples of methods for obtaining a silicate oligomer by hydrolytic condensation of such an epoxy group-containing silane coupling agent (b1) include, for example, JP-A-10-324749, JP-A-6-32903, and JP-A-6-298940. As described in Journal of Adhesion Society of Japan, Vol. 46, No. 6, p. 203 (2010), it can be hydrolyzed and condensed under basic conditions. A method for obtaining a rusesquioxane structure is simple and preferable. By taking this polysilsesquioxane structure, it is presumed that the crosslinking density of -SiO- increases, which is advantageous for the effect of improving the scratch resistance.
In order to promote the hydrolysis condensation reaction, water may be added.

  The specific silicate oligomer (B) thus obtained preferably has a number average molecular weight of 500 to 5000, more preferably 600 to 4500. When the number average molecular weight is too large, the viscosity tends to be too high, and when the number average molecular weight is too small, the cured product tends to be insufficient in altitude.

  In addition, the said number average molecular weight can be calculated | required similarly to the measurement of the weight average molecular weight mentioned above.

  The compounding amount of the specific silicate oligomer (B) is preferably 50 to 250 parts by weight, particularly preferably 80 to 200 parts by weight, more preferably 110 to 100 parts by weight with respect to 100 parts by weight of the acrylic resin (A). 180 parts by weight. If the amount of the specific silicate oligomer (B) 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 active energy There is a tendency that it becomes difficult to exhibit the effect of improving the scratch resistance to a film obtained by photocuring the linear curable resin composition.

<< Photocationic polymerization initiator (C) >>
The photocationic polymerization initiator (C) has a catalytic action of initiating a cationic polymerization reaction upon receiving light irradiation, 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 preferably used. These may be used alone or in combination of two or more.

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

  The content of the cationic photopolymerization initiator (C) is preferably 0.1 to 10 parts by weight, particularly preferably 1 to 5 parts by weight, based on 100 parts by weight of the acrylic resin (A). If the content of the cationic photopolymerization initiator (C) is too high, it is not economical, and the cationic photopolymerization initiator (C) approaches the surface of the silicate oligomer (B) in the active energy ray-curable resin composition. The pot life tends to be reduced. Moreover, when there is too little content, the tendency for the abrasion resistance of the anti-reflective film formed to fall will be seen.

<< Sensitizer (D) >>
Furthermore, in the active energy ray-curable resin composition of the present invention, a sensitizer (D) that promotes cationic polymerization can be used in combination with the photocationic polymerization initiator (C) 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 content of the sensitizer (D) 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 (C).

《Other additives》
A leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer and the like can be appropriately added to the active energy ray-curable resin composition of the present invention, if necessary, in addition to the above-described 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 Aromatic glycols 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.

  When using the said organic solvent, it can apply | coat to a base material as an active energy ray curable resin composition normally diluted to 3 to 60 weight%, Preferably it is 5 to 40 weight%.

<< Method for producing active energy ray-curable resin composition >>
The active energy ray-curable resin composition of the present invention is an essential component, which is an acrylic resin (A), an epoxy group-containing silicate oligomer (B), a photocationic polymerization initiator (C), and optional components. The above sensitizer (D), and further each component of other additives can be obtained by appropriately mixing in any order.

  The cationic photopolymerization initiator (C), which is a potentially strong acid, tends to aggregate the epoxy group-containing silicate oligomer (B) that is poorly stable with respect to the acid. It is preferable not to contact the silicate oligomer (B) and the cationic photopolymerization initiator (C) in a high concentration state. As a preferable mixing method, for example, an epoxy group-containing silicate oligomer (B) is added to a solution in which an acrylic resin (A) is dissolved in a solvent, or a specific silicate oligomer (B) is added thereto. The cationic photopolymerization initiator (C) is gradually added to a place where a uniform solution state is maintained by adding a solution in which the acrylic resin (A) is dissolved in a solvent. In addition, if necessary, a mixing procedure of adding a sensitizer (D) can be mentioned. By taking such a mixing procedure, the cationic photopolymerization initiator (C) is added to the state in which the acrylic resin (A) and the epoxy group-containing silicate oligomer (B) are familiar with each other. It becomes possible to avoid contact at a high concentration between the silicate oligomer (B) and the photocationic polymerization initiator (C). And since a photocationic polymerization initiator (C) and a sensitizer (D) are a small amount as a compounding quantity, the measurement of a compounding quantity needs attention, but by taking the said procedure, it is easy to expect. It has the advantage that the compounding amount can be mixed.

  Further, as described above, the epoxy group-containing silicate oligomer (B) is obtained by hydrolytic condensation of the epoxy group-containing silane coupling agent (b1) under basic conditions. After the reaction, it is preferable to neutralize with an acid, and then take the above-described addition procedure to avoid aggregation.

"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 400 to 800 nm, more preferably 520 to 650 nm. It is preferable to do.

  As a condition for applying the coating agent, it is preferable to set the humidity to be low because the cationic polymerization by irradiation with active energy rays proceeds smoothly. Specifically, the relative humidity is 40% or less. It is preferable that

  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 said ultraviolet irradiation, it can also aim at perfection by heating as needed.

  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-1)>
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 18 parts of fluoroethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name “M-3F”), 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Chemical Industries, Ltd.) as an epoxy group-containing (meth) acrylic acid ester monomer (a2) , Trade name "Cyclomer M100"), 6 parts of hydroxyl group-containing (meth) acrylic acid ester monomer (a3), 6 parts of 2-hydroxyethyl methacrylate, 1.2 parts of lauryl mercaptan as a chain transfer agent, 1- 90 parts of methoxy-2-propyl acetate is charged, and further a polymerization initiator Te 2,2'-bis dimethyl valeronitrile added (Otsuka Chemical Co., Ltd., trade name "ADVN") 0.125 parts, 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 50,000) solution containing a fluorine atom-containing structural site, an epoxy group 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 20 weight % Was estimated.
Furthermore, when the ratio which an epoxy group and a hydroxyl group occupy to acrylic resin (A-1) were all calculated | required from preparation monomer weight ratio, they were 1020 as an epoxy equivalent, and 82 KOHmg / g as a hydroxyl value, respectively.

<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 epoxy group-containing silicate oligomer (B-1)>
A 300 mL flask equipped with a stirrer, a cooler, and a thermometer was charged with 96 parts of 3-glycidoxypropyltrimethoxysilane (trade name “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.) and 192 parts of 2-butanone. While stirring, 10 parts of a 0.1% aqueous potassium hydroxide solution was added, and a hydrolysis reaction was performed at 70 ° C. for 4 hours. After cooling to room temperature (25 ° C.), the mixture is neutralized by adding acetic acid, and the solvent is removed with a rotary evaporator, thereby removing an epoxy group-containing silicate oligomer (B-1) (number) Average molecular weight: 4000). In addition, the number average molecular weight of the obtained epoxy group-containing silicate oligomer (B-1) was measured according to the above-mentioned method.

<Preparation of active energy ray-curable resin composition>
2.3 parts (0.58 parts solids) of the acrylic resin (A-1), 0.96 parts of silicate oligomer (B-1), and adekatopomer SP- as the photocationic polymerization initiator (C-1) An active energy ray-curable resin composition was obtained by mixing 0.065 parts of 170 (manufactured by ADEKA Corporation) and 4.5 parts of 1-methoxy-2-propanol 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 0.53 micrometer.

[Comparative Example 1]
<Preparation of silicate oligomer (B′-1) having no epoxy group>
A 300 mL flask equipped with a stirrer, a cooler, and a thermometer was charged with 96 parts of methyltrimethoxysilane (trade name “KBM-13” manufactured by Shin-Etsu Chemical Co., Ltd.) and 192 parts of 2-butanone. A 10% aqueous 1% potassium hydroxide solution was added, and a hydrolysis reaction was carried out at 70 ° C. for 4 hours. After cooling to room temperature (25 ° C.), neutralization is performed by adding acetic acid, and the silicate oligomer (B′-1) which is a hydrolyzate of alkoxysilane containing no epoxy group is removed by removing the solvent with a rotary evaporator (several Average molecular weight: 4000).

  In Example 1, instead of the hydrolyzate of epoxy group-containing alkoxysilane (B-1), the hydrolyzate of alkoxysilane not containing the epoxy group (B′-1) was used, and Example 1 was used. Similarly, an active energy ray-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 hardening layer which consists of this active energy ray curable resin composition after hardening was 0.53 micrometer.

[Comparative Example 2]
<Preparation of acrylic resin (A'-1)>
In the preparation of the acrylic resin (A) of Example 1, 3,4-epoxycyclohexylmethyl methacrylate which is an epoxy group-containing (meth) acrylic acid ester monomer (a2) (trade name “Cyclocycling” manufactured by Daicel Chemical Industries, Ltd. The acrylic resin (A′-1) (solid) containing a fluorine atom-containing structural moiety and a hydroxyl group and having no epoxy group, except that methyl methacrylate was used instead of the monomer M100 ”) Min 25%; weight average molecular weight 50,000) solution. The weight average molecular weight of the obtained acrylic resin (A′-1) was measured according to the same method as described above.

  In Example 1, instead of the acrylic resin (A-1) containing a fluorine atom-containing structural part, an epoxy group and a hydroxyl group, the above acrylic atom-containing structural part and a hydroxyl group-containing acrylic having no epoxy group An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that the system resin (A′-1) was used.

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 0.53 micrometer.

[Comparative Example 3]
<Preparation of acrylic resin (A'-2)>
In the preparation of the acrylic resin (A) of Example 1, Example 1 was used except that methyl methacrylate was used instead of 2-hydroxyethyl methacrylate which is a hydroxyl group-containing (meth) acrylic acid ester monomer (a3). Similarly, an acrylic resin (A′-2) (solid content 25%; weight average molecular weight 50,000) solution containing a fluorine atom-containing structural moiety and an epoxy group and having no hydroxyl group was obtained. The weight average molecular weight of the obtained acrylic resin (A′-2) was measured according to the same method as described above.

  In Example 1, instead of the acrylic resin (A-1) containing a fluorine atom-containing structural part, an epoxy group and a hydroxyl group, the above acrylic atom-containing structural part and an epoxy group-containing acrylic having no hydroxyl group An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that the system resin (A′-2) was used.

  It was confirmed that the obtained active energy ray-curable resin composition was phase-separated 7 days after preparation. For this reason, it did not use for formation of a coating-film hardening layer.

  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 the above examples and comparative examples, haze values were 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 the above examples and comparative examples, the test was conducted according to ASTM D1044 (Standard Test Method for Resistance of Transparent Plastics to Surface Abrasion), and the difference in haze values before and after the test is shown as Δhaze. 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 coating film cured layer (cured film) of the example formed using the active energy ray-curable resin composition containing (A) to (C) has a low refractive index, It can be seen that the cured film is excellent in transparency and scratch resistance. Furthermore, it turns out that the active energy ray-curable resin composition which is an example product is excellent in pot life.

  On the other hand, the comparative example formed using the active energy ray curable resin composition produced by mix | blending the silicate oligomer (B'-1) which is a hydrolyzate of the alkoxysilane which does not contain an epoxy group. It can be seen that the cured film 1 is inferior in scratch resistance.

  Moreover, the comparison formed using the active energy ray curable resin composition produced by mix | blending the acrylic resin (A'-1) which does not have an epoxy group by a fluorine atom containing structural site | part and hydroxyl group containing The cured film of Example 2 was inferior to the scratch resistance of Comparative Example 1.

  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 (9)

  It contains an acrylic resin (A) containing a fluorine atom-containing structural site, an epoxy group and a hydroxyl group, an epoxy group-containing silicate oligomer (B), and a photocationic polymerization initiator (C). An active energy ray-curable resin composition.   The acrylic resin (A) is a fluorine atom-containing (meth) acrylic acid ester monomer (a1), an epoxy group-containing (meth) acrylic acid ester monomer (a2), and a hydroxyl group-containing (meth) acrylic acid ester monomer (a3). The active energy ray-curable resin composition according to claim 1, which is an acrylic resin obtained by copolymerizing a copolymerization component [I] containing   The active energy according to claim 2, wherein the proportion of the fluorine atom-containing (meth) acrylic acid ester monomer (a1) is 40 to 80 parts by weight with respect to 100 parts by weight of the copolymer component [I]. A linear curable resin composition.   The proportion of the epoxy group-containing (meth) acrylic acid ester monomer (a2) is 10 to 30 parts by weight with respect to 100 parts by weight of the copolymer component [I]. An active energy ray-curable resin composition.   The ratio of the hydroxyl group-containing (meth) acrylic acid ester monomer (a3) is 10 to 30 parts by weight with respect to 100 parts by weight of the copolymer component [I]. The active energy ray-curable resin composition according to one item.   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 1-5 characterized by the above-mentioned. Amount of the epoxy group-containing silicate oligomer (B) is, according to any one of claims 1 to 6, characterized in that 50 to 250 parts by weight of the acrylic resin (A) 100 parts by weight of An active energy ray-curable resin composition. A coating agent comprising the active energy ray-curable resin composition according to any one of claims 1 to 7 . A laminate comprising an antireflection film formed on the surface of a transparent substrate using the coating agent according to claim 8 .