JP6710508B2 - Active energy ray curable resin composition for hard coat, transparent plastic sheet with hard coat, and optical member - Google Patents

Description

The present invention relates to a resin composition for active energy ray-curable hard coat, a transparent plastic sheet with a hard coat, and an optical member.

Conventionally, a transparent base material has been used as a base material of an electrode for a capacitive touch panel. This base material is provided with a conductive film such as ITO on one surface, and a hard coat layer having antiblocking property is provided on the other surface so as to prevent blocking during winding. The anti-blocking property is realized by, for example, a method of roughening the film surface to reduce the contact area, or allowing a fine powder filler to be present on the surface of the plastic film (for example, Patent Documents 1 and 2).
On the other hand, when such a base material is incorporated into various devices, a transparent adhesive layer (OCA layer) is formed on the surface of the hard coat layer, but the transparent adhesive layer exhibits anti-blocking property on the surface of the hard coat layer. Therefore, the lack of recoatability that causes poor adhesion to the hard coat layer is a problem.

JP, 2014-162154, A JP, 2014-141617, A

The present invention includes a Anchiburo' king of the hard coat layer surface, relieve tradeoff with the relationship between the adhesion to the adhesive layer, effectively to perform its function in a situation where the function of one is required, the other function It is an object of the present invention to provide an active energy ray-curable resin composition for a hard coat, which can achieve a good balance so as not to hinder it and can provide a hard coat layer having high performance and high reliability for a long period of time.

This application includes the following inventions.
[1] (A) a urethane prepolymer comprising a structural unit derived from a chain aliphatic hydrocarbon diisocyanate and a structural unit derived from a hydroxyl group-containing (meth)acrylate,
(B) silica filler having an average primary particle size of less than 30 nm,
(C) A resin composition for an active energy ray-curable hard coat, which contains a silica filler having an average primary particle size difference of 20 nm or more from the component (B) silica filler.
[2] The active energy ray-curable resin composition for hard coat, further comprising (D) the urethane prepolymer represented by the formula (I).
[3] The active energy ray-curable resin composition for hard coat, wherein the component (D) is 10 parts by weight or less with respect to 100 parts by weight of the component (A).
[4] The active energy ray-curable resin composition for hard coat, wherein the total amount of the component (B) and the component (C) is 30 to 150 parts by weight with respect to 100 parts by weight of the component (A).
[5] The active energy ray-curable resin composition for hard coat, wherein the component (C) is 20 to 50 parts by weight with respect to 100 parts by weight of the component (B).
[6] The active energy ray-curable resin composition for hard coat, containing no fluorine compound or silicone compound and having a contact angle of water with the cured film surface of less than 70°.
[7] The active energy ray-curable resin composition for hard coat, wherein the difference in average primary particle diameter between the silica filler of the component (B) and the silica filler of the component (C) is 20 nm to 60 nm.
[8] The active energy ray-curable resin composition for hard coat, further containing a photopolymerization initiator or a solvent.
[9] A transparent plastic sheet and a transparent plastic sheet with a hard coat, which comprises a cured layer of the active energy ray-curable resin composition for a hard coat laminated on one surface of the transparent plastic sheet.
[10] An optical member using the above transparent plastic sheet.

According to the present invention, it is possible to provide a resin composition for active energy ray-curable hard coat, which enables each function to be maximized without each function interfering with each other. ..
Further, according to the present invention, it is possible to provide a transparent plastic sheet and an optical member at low cost by a simple process of forming a single layer with one resin composition.

In the present specification, “(meth)acrylic” means “methacrylic” and/or “acrylic”, and “(meth)acrylate” means “methacrylate” and/or “acrylate”.
Each of the following components may be used alone or in combination of two or more.

[Active energy ray curable resin composition for hard coat]
The active energy ray-curable hard coat resin composition of the present invention (hereinafter sometimes simply referred to as the “resin composition of the present invention”) is mainly as described above.
(A) a urethane prepolymer containing a structural unit derived from a chain aliphatic hydrocarbon diisocyanate and a structural unit derived from a hydroxyl group-containing (meth)acrylate,
(B) silica filler having an average primary particle size of less than 30 nm,
(C) It contains a silica filler having a difference in average primary particle diameter of 20 nm or more from the silica filler of the component (B).
The resin composition of the present invention further comprises (D) a polycondensation product of a diisocyanate compound or a diisocyanate monomer and a structural unit derived from a polyalkylene glycol compound having one terminal hydroxyl group or a (meth)acrylic acid alkylene oxide addition compound. It is preferable to contain a urethane prepolymer containing a structural unit derived from a certain polyisocyanate compound and a structural unit derived from a hydroxyl group-containing (meth)acrylate compound.
Further, the resin composition of the present invention preferably contains a photopolymerization initiator, a solvent and the like.

The resin composition of the present invention can be cured by irradiation with active energy rays such as visible light, ultraviolet rays, radiation, infrared rays, X rays, α rays, β rays, γ rays and electron rays. The cured polymer of this resin composition can exhibit both a hard coat function and an anti-blocking function on its surface.

<Urethane prepolymer>
The urethane prepolymer is a reaction product of a chain aliphatic hydrocarbon diisocyanate and a hydroxyl group-containing (meth)acrylate, and is derived from a structural unit derived from the chain aliphatic hydrocarbon diisocyanate and a hydroxyl group-containing (meth)acrylate. And structural units. Hereinafter, this urethane prepolymer may be referred to as (A) urethane prepolymer.
In the urethane prepolymer (A), the chain aliphatic hydrocarbon diisocyanate is a compound in which two isocyanate groups are substituted in the chain aliphatic hydrocarbon.
The chain aliphatic hydrocarbon may be a straight chain or a branched chain, and examples of the aliphatic hydrocarbon include saturated hydrocarbons. In this case, the carbon number is, for example, preferably about 2 to 10 and more preferably about 3 to 8.
Examples of the saturated hydrocarbon include ethane, n-propane, isopropane, n-butane, sec-butane, tert-butane, pentane, hexane, octane and 2-ethylhexyl.

Examples of the chain aliphatic hydrocarbon diisocyanate include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

The hydroxyl group-containing (meth)acrylate may be one having at least one hydroxyl group in the molecule, but it is easy to obtain a desired urethane prepolymer by controlling crosslinking and gelation by reaction with diisocyanate. From the viewpoint, those containing one hydroxyl group are preferable.

Examples of the hydroxyl group-containing (meth)acrylate include hydroxyalkyl (meth)acrylates, polyol (meth)acrylates, alkylene oxide-added polyol (meth)acrylates, and those derived from an epoxy resin and a carboxylic acid.
The hydroxyalkyl (meth)acrylates contain an alkyl group having about 2 to 12 carbon atoms, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyphenoxypropyl ( Examples thereof include (meth)acrylate.

The polyol (meth)acrylates are, for example, divalent to tetravalent polyol (meth)acrylates having 2 to 10 carbon atoms, specifically, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, Examples thereof include ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

The alkylene oxide-added polyol (meth)acrylates contain an alkylene oxide having about 2 to 10 carbon atoms (preferably about 2 to 8 carbon atoms), for example, alkylene oxide-added trimethylolpropane di(meth)acrylate, Examples thereof include alkylene oxide-added pentaerythritol tri(meth)acrylate and alkylene oxide-added dipentaerythritol penta(meth)acrylate.

Examples of those derived from an epoxy resin and a carboxylic acid include (meth)acrylic acid adducts of glycidyl (meth)acrylate.

The urethane prepolymer (A) is obtained by reacting hexamethylene diisocyanate or trimethylhexamethylene diisocyanate with hydroxyalkyl (meth)acrylates or polyol (meth)acrylates, that is, hexamethylene diisocyanate or trimethylhexamethylene diisocyanate. Those containing a structural unit derived from (1) and a structural unit derived from hydroxyalkyl (meth)acrylates or polyol (meth)acrylates are preferable.

The urethane prepolymer (A) having a molecular weight of about 500 to 5,000 is suitable. If the molecular weight is too large, the hardness tends to decrease. Such urethane prepolymer (A) can be produced, for example, by the method described in JP-A-2000-264936.
In the present specification, the molecular weight represents a weight average molecular weight calculated in terms of styrene, and such a molecular weight is determined by gel permeation chromatography (for example, carrier: THF, column: Shodex GPC-LF804×2, detection. Part: differential refractometer).

In the urethane prepolymer (A), the molar ratio of the chain aliphatic hydrocarbon diisocyanate is preferably 1/2 or less of the molar ratio of the hydroxyl group-containing (meth)acrylate. The greater the number of functional groups in the hydroxyl group-containing (meth)acrylate, the higher the hardness when cross-linked and polymerized. Conversely, the smaller the number, the lower the hardness. Therefore, a cured polymer having an appropriate hardness can be obtained by adjusting these. Specifically, a chain aliphatic hydrocarbon diisocyanate:hydroxyl group-containing (meth)acrylate (molar ratio)=about 1.0:1.8 to 2.5 can be mentioned, and 1.0:1.8 to 2 It is preferably about 0.2.

Further, the resin composition of the present invention preferably contains a urethane prepolymer different from (A) the urethane prepolymer. Hereinafter, this urethane prepolymer may be referred to as (D) urethane prepolymer.
The urethane prepolymer (D) has a structure represented by the formula (I).
_{^{(R 1 O-CONH-) m}} -R 2 - (- NHCO-OR 3) n (I)
(In the formula, R ¹ O- represents a dehydrogenation residue of a compound having a polyether polyol as a main chain, -R ^2- represents a deisocyanate group residue of a polyisocyanate compound which is a polycondensation product of a diisocyanate monomer, and R ³ O- is a dehydrogenation residue of a hydroxyl group-containing (meth)acrylate compound, m+n = an integer of 1 to 50)

Examples of the compound having a polyether polyol as a main chain include alkoxypolyalkylene glycols, (meth)acryloxy polyethylene glycol, and (meth)acryloxy polypropylene glycol. Specifically, methoxy polyethylene glycol, methoxy polypropylene glycol, methoxy polytetramethylene glycol, ethylene oxide adduct of 2-hydroxyethyl acrylate (for example, the number of moles added is about 1 to 20), alkylene oxide (for example, carbon number). (About 2 to 6) is added to (meth)acrylic acid.

Examples of the polyisocyanate compound, which is a polycondensation product of diisocyanate monomers, include, for example, isophorone diisocyanate, hexamethylene diisocyanate, norbornane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, hydrogenated xylylene diisocyanate and Examples thereof include bifunctional isocyanates such as hydrogenated diphenylmethane diisocyanate, and trifunctional or higher functional isocyanates which are nurate. Among them, a polyisocyanate compound having three or more isocyanate groups in one molecule, for example, a polyisocyanate compound containing a chain or cyclic alkyl or aryl group (for example, having about 6 to 12 carbon atoms), particularly hexamethylene diisocyanate, Nurates such as isophorone diisocyanate and tolylene diisocyanate are preferred.

<Silica filler>
The resin composition of the present invention contains silica filler having two types of average primary particle diameters. The silica filler as used herein refers to silicon dioxide that has been mixed into a resin for the purpose of improving its function and is in the form of fine particles having a particle size of micro to nano level. The average primary particle diameter of the two kinds of silica fillers may be, for example, several nm to several μm, but among them, several nm to several hundred nm is preferable, and several nm to 100 nm is more preferable. More preferably, it is about 5 nm to 80 nm.

Examples of commercially available silica fillers include the following. ELCOM V-8802, ELCOM V-8804 (manufactured by JGC Catalysts & Chemicals Co., Ltd.), MEK-AC-2140Z, PGM-AC-2140Y, PGM-AC-4130Y, MEK-AC-5140Z (manufactured by Nissan Chemical Industries, Ltd.), PL-2L-PGME, PL-2L-MEK, HSP-3C (made by Fuso Chemical Industry Co., Ltd.).

The average primary particle diameter of the one silica filler (B) is, for example, less than 30 nm, preferably 28 nm or less, more preferably 25 nm or less, still more preferably 20 nm or less. Further, the silica filler (B) preferably has a difference in average primary particle diameter of 20 nm or more from the other silica filler (C), and a difference in average primary particle diameter of 20 nm to 100 nm or 20 nm to 60 nm. Is more preferable, and it is further preferable that the average primary particle size difference is about 20 nm (±5 nm).

For example, the average primary particle diameter of the silica filler of (B) is less than 30 nm and the average primary particle diameter of the silica filler of (C) is 30 nm or more. The average primary particle diameter of the silica filler of (B) is 25 nm. The average primary particle diameter of the silica filler of (C) is 30 nm or more, the average primary particle diameter of the silica filler of (B) is 20 nm or less, and the average primary particle diameter of the silica filler of (C) is 35 nm or more. , The average primary particle diameter of the silica filler of (B) is 20 nm or less, the average primary particle diameter of the silica filler of (C) is 40 nm or more, the average primary particle diameter of the silica filler of (B) is 20 nm or less, and The average primary particle diameter of the silica filler of (C) is 50 nm or more, the average primary particle diameter of the silica filler of (B) is 20 nm or less, and the average primary particle diameter of the silica filler of (C) is 60 nm or more. Can be mentioned.

As described above, by using two kinds of silica fillers having different average primary particle diameters in combination, the small particle diameter fillers can improve the hardness of the hard coat film and reduce the curing shrinkage ratio, and can increase the large particle diameters. We have found that the filler can maximize the anti-blocking property. This is an unexpected effect in view of the fact that the anti-blocking property is not exhibited even when only the relatively large particle size filler is used.
The average primary particle diameter of the silica filler can be measured by, for example, particles observed by an electron microscope such as TEM. Alternatively, a commercially available product having a specified particle size may be used.

The average primary particle diameter of the silica filler is, for example, the characteristic unevenness of the hard coat film surface obtained by using a resin composition containing two kinds of silica fillers having different average primary particle diameters, and a contact-type surface roughness. It can be confirmed from the fact that the value of the maximum height: Rz (according to JIS B 0601:2001) in the roughness curve is larger than that of the conventional hard coat film when measured with a hardness measuring device. An example of the contact-type surface roughness measuring device is “SURFCOM 590A-3D-12 (trade name)” manufactured by TOKYO SEIMITSU CO., LTD.

The silica filler may be one whose surface is not organically modified, but is preferably one which is organically modified in order to improve dispersibility. The term "organic modification of the surface" as used herein means that the surface of the silica filler is in the form of a complex in which an organic compound or organic group is physically or chemically (preferably chemically) introduced. Examples of the organic compound or organic group to be introduced include those known in the art. Considering the improvement in strength of the cured film obtained by active energy ray curing, modification with a (meth)acryloyl group is preferable.

The total content of the components (B) and (C) is 10 to 200 parts by weight, preferably 30 to 180 parts by weight, more preferably 30 to 150 parts by weight, based on 100 parts by weight of the component (A). , 50 to 150 parts by weight, 70 to 130 parts by weight, 90 to 130 parts by weight or 100 to 130 parts by weight are more preferable.
Further, when the urethane prepolymer contains the urethane prepolymer of (D), the total content of the components (B) and (C) is 10 with respect to 100 parts by weight of the components (A) and (D). To 200 parts by weight, preferably 30 to 180 parts by weight, more preferably 30 to 150 parts by weight, further preferably 50 to 150 parts by weight, 70 to 130 parts by weight, 90 to 130 parts by weight or 100 to 130 parts by weight. preferable.

The component (C) may be 10 to 200 parts by weight, preferably 20 to 200 parts by weight, more preferably 20 to 200 parts by weight, and 30 to 180 parts by weight, relative to 100 parts by weight of the component (B). Parts, 30 to 150 parts by weight, 35 to 150 parts by weight, 20 to 100 parts by weight, and 20 to 50 parts by weight are more preferable. The components (B) and (C) may be supplied as a solvent or an aqueous dispersion, but the above-mentioned weight ratio means the content of the solid content.

<Other ingredients>
(Photopolymerization initiator)
The resin composition of the present invention preferably contains a photopolymerization initiator. However, when a photopolymerization initiator is not needed, such as when an electron beam is used as an active energy ray for curing, it may not be necessarily contained.
The photopolymerization initiator is preferably a photopolymerization initiator that generates radicals by active energy rays.

The photopolymerization initiator is known in the art, for example, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone. , 2,4,6-Trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4- (Morpholinyl)phenyl]-2-phenylmethyl)-1-butanone and the like are preferable, and 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane are more preferable. -1-one, 2-(dimethylamino)-1-[4-(morpholinyl)phenyl]-2-phenylmethyl)-1-butanone and the like, for example, Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907 (all are BASF Corporation) and the like.

The photopolymerization initiator is contained in an amount of about 0.3 to 20 parts by weight based on 100 parts by weight of the solid content (total weight of all components other than the solvent) of the resin composition for active energy ray-curable hard coat of the present invention. It is preferable that the amount is about 0.4 to 8 parts by weight.

(solvent)
As the solvent, those usually used in resin compositions can be appropriately selected and used.
For example, alcohols, glycols, aliphatic cyclic ketones, acetic acid esters, and the like can be used. Among them, it is preferable to use a solvent other than alcohols.

Examples of glycols include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl acetate. Ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene Examples thereof include glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

Examples of the aliphatic cyclic ketones include cyclohexanone, ortho, meta, and para-methylcyclohexanone.
Examples of the acetic acid esters include ethyl acetate n-propyl acetate and n-butyl acetate.
Further, a saturated hydrocarbon solvent such as solvent naphtha, methyl ethyl ketone, methyl isobutyl ketone, n-octane and isooctane, ethyl cellosolve, butyl cellosolve and the like may be used.

The solvent is 100 parts by weight of the total of the above components (A), (B) and (C) or the components (A), (B), (C) and (D), and optionally other components. Usually, it is preferably contained in 10 to 2000 parts by weight, more preferably 50 to 500 parts by weight.

The resin composition of the present invention is mixed with a pigment, a dye, an inorganic filler, an organic filler, a polymerization initiator, a diluent, a leveling agent, a lubricity imparting agent, an ultraviolet stabilizer and an antioxidant, and other additives. May be. However, it is preferable that the resin composition of the present invention does not contain a fluorine-containing compound or a silicone compound. Here, "not included" means that they are not added positively, and those contained as impurities in each component or additive are acceptable. That is, even if the fluorine-containing or silicone compound is contained as an impurity, the total of the above-mentioned components (A), (B) and (C) or the components (A), (B), (C) and (D). Of 0.5% by weight or less, 0.3% by weight or less, 0.2% by weight or less, or 0.1% by weight or less.

Examples of the leveling agent and the lubricity imparting agent include a copolymer of polyoxyalkylene and polydimethylsiloxane, a copolymer of polyoxyalkylene and fluorocarbon, and the like.
As the pigment, dye, UV stabilizer, antioxidant, polymerization initiator and diluent, those known in the art can be used.

[Transparent plastic sheet with hard coat]
The transparent plastic sheet with a hard coat of the present invention mainly comprises a transparent plastic sheet and a hard coat layer, that is, a cured layer of the resin composition for active energy ray-curable hard coat described above.
For example, one obtained by coating or laminating the above-mentioned active energy ray-curable hard coat resin composition on one surface of a transparent plastic sheet, for example, obtained by applying the above-mentioned resin composition, drying and curing. The cured layer may be adhered or laminated on one surface of the transparent plastic sheet.

As the transparent plastic sheet, for example, visible light or white light from a light source or a light source has a transmittance of 60% or more, 70% or more, or 80% or more, and a transparent plastic sheet having a light transmittance of 90% or more is preferable.
For example, polyurethane resin, polyepisulfide resin, (meth)acrylic polymer such as polymethylmethacrylate (PMMA), allyl polymer, diethylene glycol bisallyl carbonate, polycarbonate, MS resin, cyclic polyolefin, triacetyl cellulose (TAC) , A sheet made of various synthetic resins such as acrylic-butadiene-styrene (ABS) resin. The sheet material may have any shape such as a flat plate shape, a curved plate shape, and a film shape. Further, it may have an uneven surface, or may have a predetermined pattern formed thereon.

The coating is, for example, a dip coating method, a flow coating method, a spray coating method, a gravure coating method, a bar coating method, a spin coating method, a roll coating method, a flexographic printing method, a screen printing method, a die coating method, a gravure offset method, and a brush. It can be performed by a coating method or the like.
The coating thickness is preferably about 1.0 to 20 μm after curing.
The drying is not particularly limited, and may be air drying, heat drying, or the like.
The light irradiation is, for example, about 100 to 1,500 mJ/cm ^{2 with} ultraviolet rays or the like.

The active energy ray-curable resin composition for a hard coat of the present invention can have a simple structure by simple selection and combination of components, on the other hand, in addition to the hard coat function required in the hard coat layer. Therefore, it is possible to effectively exhibit the anti-blocking property during and during the winding, and further, to sufficiently exhibit the anti-blocking property without impairing the adhesiveness to the adhesive layer required in the subsequent application. Become. In order to secure such adhesion, it is possible to avoid the inhibition of the recoating property because the fluorine-containing compound or the silicone-containing compound that contributes to the development of the anti-blocking property is not contained.
This makes it possible to easily and inexpensively form a transparent plastic sheet with a hard coat and various members (for example, an optical member) without a complicated laminating process such as a multilayer structure forming a laminated structure.

In addition, the cured product of the obtained resin composition itself can be firmly adhered to various members which are the objects to be coated without separating/peeling into each functional layer, and the hard coat function can be stably provided for a long period of time. Can be demonstrated.

Further, since it is preferable that the water contact angle is small as an index showing the adhesiveness of the OCA layer, that is, the recoating property, this index is used in the evaluation of the obtained hard coat layer in the present application.

In order to improve the adhesion of the hard coat, a primer layer may be provided on the surface of the transparent plastic sheet in advance, or pretreatment such as alkali treatment, acid treatment, plasma treatment, corona treatment and flame treatment may be performed. ..
Examples of the primer layer include urethane resin and acrylic resin. The suitable thickness of the primer layer is about 2 to 50 nm. The primer layer can be formed by applying these resin solutions by any method such as a dipping method, a spray method, a flow coating method, a roll coating method and a spin coating method.

Molded articles to which the resin composition of the present application can be applied include not only the above-mentioned transparent plastic sheet but also plastic molded articles made of general-purpose resins such as polystyrene resin, polyolefin resin, ABS resin, AS resin, AN resin, and the like. You may stick and use it to the molded article shape|molded by various materials, such as wood, glass, metal, ceramics, paper, cement, these composites. As a result, a hard coat function can be imparted to these molded products.

[Optical member]
The optical member of the present invention is constituted using the active energy ray-curable resin composition for hard coat or the transparent plastic sheet with hard coat described above.
Examples of the optical member include optical plastic lenses such as a prism lens sheet, a Fresnel lens, a spectacle lens, and an aspherical lens, and members for optoelectronics such as optical disks, optical fibers, and optical waveguides. It can also be used as a printing ink, a paint, a clear coating agent, a varnish, etc. that can be used for these optical members and the like.

Examples of the active energy ray-curable resin composition for hard coat of the present invention will be described in detail below.
Urethane prepolymers of Examples and Comparative Examples (A),
(B) silica filler,
(C) silica filler,
In addition to the urethane prepolymer (D), a photopolymerization initiator and a solvent are kneaded at the composition ratios (parts by weight) shown in Table 1 and Table 2, respectively, and a resin containing a solid content of about 50% by weight. A composition was obtained.

()内の数字は有効成分の配合量を示す。

The numbers in parentheses indicate the amount of active ingredient compounded.

()内の数字は有効成分の配合量を示す。

The numbers in parentheses indicate the amount of active ingredient compounded.

The components of Table 1 are as follows.
(A)-1 Trade name: UA-306H, HDI-based urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd.)
(A)-2 Product name: UA-510H, HDI urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd.)
(D) Product name: WS-22, polyalkylene glycol-containing HDI urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd.)
(B) Product name: MEK-AC-2140Z (manufactured by Nissan Chemical Industries, Ltd.) (average primary particle diameter 10 nm)
(C)-1 Product name: PGM-AC-4130Y (manufactured by Nissan Chemical Industries, Ltd.) (average primary particle diameter 40 nm)
(C)-2 Product name: MEK-AC-5140Z (manufactured by Nissan Chemical Industries, Ltd.) (average primary particle diameter 70 nm)
Photopolymerization initiator Product name: IRGACURE 184 (manufactured by BASF)
Fluorine-containing compound Product name: LE-604, fluorine-containing acrylic polymer (manufactured by Kyoeisha Chemical Co., Ltd.)
Solvent MEK: Methyl ethyl ketone (manufactured by Tonen Kagaku K.K.)

The active energy ray-curable resin composition for hard coat obtained in Examples and Comparative Examples was applied on easy-adhesion PET (50 μm thick), and the solvent was dried at 90° C. for 60 seconds. This was loaded on a conveyor at a speed of 6 m/min, and was irradiated with ultraviolet rays twice from a position of 10 cm in height by a high pressure mercury lamp of 80 W/cm to crosslink and polymerize, and a hard coat of about 2 μm containing a cured polymer was formed. Formed.
The obtained hard coat was evaluated for adhesion, haze value, water contact angle, antiblocking property, and steel wool resistance.

<Adhesion>
Adhesion was confirmed by a cross-cut 1 mm cross-cut test according to the method of JIS K5600-5-6. XX in XX/100 represents the cells that are in close contact after the adhesion test (100 in the case of 100/100 are in close contact).

<Haze value>
According to the method of JIS K7136, it measured using the haze meter HZ-2 by Suga Test Instruments Co., Ltd.
<Water contact angle>
Using Kyowa Interface Science Co., Ltd. Drop Master 500, the contact angle when the distilled water was dropped onto the obtained coating layer was measured.

<Anti-blocking property>
According to the method of JIS P8147, the coated surfaces of the coated films were superposed on each other and gradually inclined with a certain load applied to a certain area, and the angle at which the superposed films slipped was defined as the sliding angle. It can be evaluated that the smaller the sliding angle, the higher the slipperiness, that is, the higher the antiblocking property. Therefore, when a test is performed by applying a load of 500 g with an overlapping area of 3 cm×5 cm and 15 cm ² , a sliding angle of 25° or less is considered good, and a sliding angle of more than 25° is evaluated as bad, and Table 1 and Table 2 are shown. It was shown to.

<Steel wool resistance>
The obtained coat layer was rubbed 10 times with steel wool (#0000) applied with a load of about 500 g and 1 kg. When visually inspected, those without scratches were evaluated as ◯, and those with scratches were evaluated as x.
A test was conducted by rubbing the surface of the obtained coat layer 10 times with a load of 1 kg on steel wool (#0000). When visually inspected, those without scratches were evaluated as ◯, and those with scratches were evaluated as x.

From Table 1, in Examples, by containing the components (A), (B), (C) and (D) described above in a ratio within a specific range, adhesion, haze value, anti-blocking property and resistance to Satisfactory results could be obtained in all evaluations such as steel wool property. Further, it was found that all the physical properties are expressed within the allowable range even when (D) is not used, although the contact angle with water is slightly inferior.
On the other hand, in the comparative example, the water contact angle and the anti-blocking property were not achieved at the same time.

Example 8
The active energy ray-curable resin composition for hard coat obtained in Example 1 was applied to a TAC film to form a coat layer in the same manner as for the evaluation of each property described above to form a hard plastic transparent plastic sheet. It was made.
The obtained sheet was sandwiched between injection molding dies and acrylic resin was injected by the simultaneous injection molding method. After cooling, a panel-shaped optical molded article having a hard coat layer was obtained.

As described above, the composition of the present invention can realize the water contact angle and the antiblocking property by forming a single layer of the resin composition, and in addition to the original function of the hard coat layer, and Anchiburo' King resistance, achieving a balance between adhesion to the adhesive layer, without inhibiting the other functions, effectively to perform its function in a situation where the function of one is required, high-performance and reliable hard coat layer Can be given.

The active energy ray-curable resin composition for a hard coat of the present invention can be imparted with various properties, that is, anti-blocking property, scratch resistance, transparency, hard coat property, adhesion with an adhesive layer, etc. A coating can be provided in which the properties of can be imparted by the formation of a single layer. Therefore, it can be used in parts requiring these characteristics, molded articles, and the like.

Claims (8)

(A) a urethane prepolymer comprising a structural unit derived from a chain aliphatic hydrocarbon diisocyanate and a structural unit derived from a hydroxyl group-containing (meth)acrylate,
(B) silica filler having an average primary particle size of less than 30 nm,
(C) An average primary particle size of 70 nm or less, and a silica filler which is not hollow particles having an average primary particle size difference of 20 nm or more from the silica filler of the component (B), and
(D) Urethane prepolymer represented by the following formula (I)
^{_{(R 1 O-CONH-) m}} -R 2 - (- NHCO-OR 3) n (I)
(In the formula, R ¹ O- represents a dehydrogenation residue of a compound having a polyether polyol as a main chain, -R ^2- represents a deisocyanate group residue of a polyisocyanate compound which is a polycondensation product of a diisocyanate monomer, and R ³ O- is a dehydrogenation residue of a hydroxyl group-containing (meth)acrylate compound, m+n = an integer of 1 to 50)
Containing
A resin composition for an active energy ray-curable hard coat, wherein the total amount of the component (B) and the component (C) is 30 to 150 parts by weight with respect to 100 parts by weight of the component (A). The active energy ray-curable resin composition for hard coat according to claim 1, wherein the amount of the component (D) is 10 parts by weight or less based on 100 parts by weight of the component (A). The resin composition for active energy ray-curable hard coat according to claim 1 or 2, wherein the component (C) is 20 to 50 parts by weight with respect to 100 parts by weight of the component (B). The active energy ray-curable hard material according to any one of claims 1 to 3, which does not contain a fluorine compound or a silicone compound and has a contact angle of water with respect to the surface of the cured film of less than 70°. A resin composition for coating. The active energy ray-curable hard according to any one of claims 1 to 4, wherein a difference in average primary particle diameter between the silica filler of the component (B) and the silica filler of the component (C) is 20 nm to 60 nm. A resin composition for coating. Furthermore, the resin composition for active energy ray-curable hard coats according to any one of claims 1 to 5, further comprising a photopolymerization initiator and a solvent. A transparent plastic sheet with a hard coat, comprising a cured layer of the active energy ray-curable resin composition for a hard coat according to any one of claims 1 to 6, which is laminated on one surface of the transparent plastic sheet. An optical member using the transparent plastic sheet according to claim 7.