JP2018176536A - Antiglare antireflective film for insert molding and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antiglare antireflection film for insert molding, which is excellent not only in antiglare and antireflection functions but also in scratch resistance and durability. SOLUTION: An antiglare hardcoat layer formed by curing a composition for forming an antiglare hardcoat layer and an antireflection layer are provided on one surface of a thermoplastic transparent base film. The composition for forming an antiglare hard coat layer contains (a) 25 to 85% by mass of an acrylic resin having a glass transition temperature of 84 ° C. or higher, and (b) 3 (meth) acrylic groups in one molecule as essential components. Acrylic compounds having one or more weight molecular weights of 15,000 or less or urethane acrylates having three or more (meth) acrylic groups in one molecule and having a weight molecular weight of 15,000 or less 1 to 70% by mass, and (c) translucency. It contains 1 to 40% by mass of the organic fine particles and (e) 1 to 10% by mass of the photopolymerization initiator. If necessary, (d) inorganic fine particles may be blended. [Selection diagram] None

Description

  The present invention relates to, for example, an antiglare antireflective film for insert molding used in an image display device such as a touch panel display, and a resin molded article and an image display device using the antiglare antireflective film for insert molding.

  BACKGROUND OF THE INVENTION In the process of designing automotive parts, cellular phones and the like, insert molding in which a decorative film subjected to hard coating treatment or printing is applied to a molded article by a heat fusion method is used in part. With the spread of car navigation systems and mobile phones, there is an increasing opportunity for insert molding to be used for the covers of these displays (image display devices), and reflection of external light on the display surface can be prevented to improve visibility. There has been a demand for an antiglare antireflective film for insert molding.

  At present, an antiglare antireflective film for insert molding that meets such a demand is provided. For example, Patent Document 1 discloses an antiglare film having an antiglare coating layer on one side of a thermoplastic transparent substrate film. An article adhered to the surface by insert molding has been proposed.

JP 2008-105420 A

  However, since car navigation systems and mobile phones equipped with a capacitive touch panel having a multi-touch function have become widespread in recent years, the trend of the required performance for a decorative film used for insert molding changes, and the antiglare property and reflection Not only the demand for the prevention function but also the need for scratch resistance and durability are increasing. However, these physical properties are not sufficient in the conventional antiglare film for insert molding.

  Therefore, an object of the present invention is to provide an antiglare antireflective film for insert molding, which is excellent not only in antiglare property and antireflective function but also in abrasion resistance and durability, and antiglare reflection for the insert molding. It is providing the resin molded product and image display apparatus which used the prevention film.

As means for that purpose, the present invention takes the following means.
[1] An antiglare hard coat layer obtained by curing a composition for forming an antiglare hard coat layer on one surface of a thermoplastic transparent base film, and an antireflective layer, said thermoplastic transparent base film Prepare in this order from the side,
The composition for forming an antiglare hard coat layer is
(A) 25 to 85 mass% of an acrylic resin having a glass transition temperature of 84 ° C. or higher,
(B) Acrylic compounds having a weight average molecular weight of 15,000 or less having three or more (meth) acrylic groups in one molecule, or 15,000 weight average molecular weights having three or more (meth) acrylic groups in one molecule 1 to 70% by mass of the following urethane acrylate,
(C) 1 to 40 mass% of translucent organic fine particles,
(E) 1 to 10% by mass of a photopolymerization initiator,
Including
The upper limit of the total content of the components (a), (b), (c) and (e) is 100% by mass.
Antiglare antireflective film for insert molding.
[2] The antiglare antireflection film for insert molding as described in [1], wherein the component (a) is polymethyl methacrylate.
[3] The antiglare antireflection film for insert molding according to [1] or [2], wherein the composition for forming the antiglare hard coat layer further comprises (d) inorganic fine particles.
[4] The antiglare antireflection film for insert molding according to any one of [1] to [3], comprising a primer layer between the antiglare hard coat layer and the antireflective layer.
[5] The thermoplastic transparent substrate film has a two-layer structure of a polycarbonate layer and a polymethyl methacrylate layer,
The antiglare antireflective film for insert molding according to any one of [1] to [4], wherein the antiglare hard coat layer is formed on the polymethyl methacrylate layer.
[6] A resin molded article provided with the antiglare antireflection film for insert molding as described in any one of [1] to [5] on the surface thereof.
[7] An image display device comprising the antiglare antireflection film for insert molding according to any one of [1] to [5] or the resin molded product according to [6].

  In the present invention or in the specification, “○ to ××” indicating a numerical range means “○ or more to ×× or less” unless otherwise specified.

  In the present invention, by forming the antiglare hard coat layer by the composition for forming a special antiglare hard coat layer, not only the antiglare property and the antireflective function but also the abrasion resistance and the durability can be obtained. It is possible to obtain an excellent antiglare antireflective film for insert molding, a resin molded product using the antiglare antireflective film for insert molding, and an image display device.

  The polycarbonate layer is polymethyl methacrylate if the antiglare hard coat layer is formed on the polymethyl methacrylate layer after forming the thermoplastic transparent base film into a two-layer structure of a polycarbonate layer and a polymethyl methacrylate layer Since the glass transition point (Tg) is higher than that of the layer, ink flow is less likely to occur when insert molding after decoration printing on the antiglare film. On the other hand, the polymethyl methacrylate layer is excellent in light resistance, and by mixing the UV absorber into the polymethyl methacrylate layer, it is possible to cut the ultraviolet rays incident from the polymethyl methacrylate layer side, and the polycarbonate layer is deteriorated by the ultraviolet rays. (Yellowing) can be prevented.

It is a schematic diagram of the image by SEM of the cross section of a glare-proof hard coat layer. It is a schematic diagram of the image by SEM of the cross section of a glare-proof hard coat layer. It is a schematic diagram which shows the shape of dumbbell shape No. 3.

«Composition for forming an antiglare hard coat layer»
The composition for forming an antiglare hard coat layer used for the antiglare antireflective film for insert molding of the present invention comprises (a) an acrylic resin and (b) three (meth) acrylic groups in one molecule. An acrylic compound having the above or a urethane acrylate having three or more (meth) acrylic groups in one molecule, (c) translucent organic fine particles, and (e) a photopolymerization initiator as essential components, further optionally It is also possible to contain (d) inorganic fine particles as a component.

  In addition, a (meth) acryl group means an acryl group or methacryl group. The following (meth) acryloyl group, (meth) acrylic acid and (meth) acrylate also mean an acryloyl group or methacryloyl group, acrylic acid or methacrylic acid, acrylate or methacrylate, respectively.

<(A) Acrylic resin>
The (a) acrylic resin can be used by selecting one or two or more kinds from among a polymer having a (meth) acryloyl group, a styrene / (meth) acrylic resin, and the like. For example, acrylic polymers comprising acrylic monomers as essential monomer components can be mentioned.

  As a monomer component which comprises acrylic resin (acrylic polymer), (meth) acrylic-acid alkylester which has a linear or branched alkyl group, a carboxyl group-containing polymerizable unsaturated compound, or its anhydride, A hydroxyl group containing (meth) acrylic acid ester is mentioned. As the (meth) acrylic acid alkyl ester having a linear or branched alkyl group, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate Butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) Examples thereof include 2-ethylhexyl acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, and dodecyl (meth) acrylate. Among these, methyl (meth) acrylate is preferable because the transparency of the polymer is high. Examples of the carboxyl group-containing polymerizable unsaturated compound or the anhydride thereof include crotonic acid, itaconic acid, fumaric acid and maleic acid. Examples of hydroxyl group-containing (meth) acrylic acid esters include 2-hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, Diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, etc. can be mentioned.

  The glass transition temperature (Tg) of the acrylic resin is at least 84 ° C. or more, preferably 100 ° C. or more. If the Tg is less than 84 ° C., the durability of the antiglare antireflective film for insert molding in a high temperature and high humidity environment (for example, 85 ° C., 85%) may be deteriorated. On the other hand, the upper limit of Tg is not limited, but from the viewpoint of formability, 160 ° C. or less is preferable, and 140 ° C. or less is more preferable.

  The weight average molecular weight of the acrylic resin is preferably 15,000 to 500,000, and more preferably 20,000 to 200,000. If the weight average molecular weight is less than 15,000, tackiness may occur in the dried coating. On the other hand, if it exceeds 500,000, the solubility of the acrylic resin in the composition may be deteriorated.

  As a commercial item of acrylic resin, for example, SIGMA-ALDRICH Co., Ltd. product "Poly (Methyl methacrylate)" (Tg = 105 ° C), Toagosei Co., Ltd. product "ARUFONUH-UC-3920" (Tg: 102) C) and the like. Moreover, Mitsubishi Rayon Co., Ltd. product "Dianal" series are also mentioned. Specifically, Mitsubishi Rayon Co., Ltd. “Dianal BR-50 (Tg: 100 ° C.), BR-52 (Tg: 105 ° C.), BR-73 (Tg: 100 ° C.), BR-80 (Tg: 105 ° C.), BR-83 (Tg: 105 ° C.), BR-88 (Tg: 105 ° C.), MB-2389 (Tg: 90 ° C.), MB-7033 (Tg 84 ° C.), BR-2952 (Tg: 84 ° C.) And the like.

  Among the acrylic resins, polymethyl methacrylate (PMMA, Tg: 105 ° C.) is preferable in view of high glass transition temperature and transparency. As commercially available products, “Poly (Methyl methacrylate)” manufactured by SIGMA-ALDRICH and “BR-80”, “BR-83”, and “BR-88” of “Dianal” series manufactured by Mitsubishi Rayon Co., Ltd. are applicable. Do.

  The content of the (a) acrylic resin in the composition for forming an antiglare hard coat layer is 25 to 85% by mass, preferably 40 to 80% by mass. When the content of the (a) acrylic resin is less than 25% by mass, the formability of the antiglare antireflective film for insert molding deteriorates. On the other hand, if it exceeds 85% by mass, the abrasion resistance of the antiglare antireflective film for insert molding deteriorates.

<(B) acrylic compound or urethane acrylate>
As an acrylic compound, it is possible to use acrylic esters having three or more (meth) acrylic groups in one molecule and curing with active energy rays such as ultraviolet rays. For example, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylates, glycerin tri (meth) acrylates, and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these starting alcohols, oligo esters having three or more (meth) acryloyl groups in the molecule ( Examples include meta) acrylates, oligoether (meth) acrylates, oligourethane (meth) acrylates, and oligoepoxy (meth) acrylates. Among them, more multifunctional dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, three or more (in the molecule Oligourethane (meth) acrylates having a (meth) acryloyl group are preferred.

  As urethane acrylate, what has 3 or more of (meth) acryl groups in 1 molecule can be used. As urethane acrylates having three or more (meth) acrylic groups in one molecule, compounds obtained by known synthetic methods in which polyhydric alcohols, polyhydric isocyanates and hydroxyl group-containing acrylates are reacted can be used.

  As commercial products of the component (b), KAYARAD TMPTA, KAYARAD T-1420 (T), KAYARAD DPHA, KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd., purple light UV-1700B, manufactured by Japan Synthetic Chemical Co., Ltd., Violet light UV-6300B, violet light UV-7600B, violet light UV-7605B, violet light UV-7610B, violet light UV-7620EA, violet light UV-7630B, violet light UV-7640B, Art Resin Art Resin UN-3320HA manufactured by KONAMI KOGYO CO., LTD. Art resin UN-3320HC, Art resin UN-3320HS, NK ester A-9300 made by Shin-Nakamura Chemical Co., Ltd., NK oligo U-6 HA, NK oligo U-15 HA, NK oligo UA-33H etc. are mentioned.

  The weight average molecular weight of the (b) acrylic compound or urethane acrylate is 15,000 or less, preferably 100 to 10,000. When the weight average molecular weight exceeds 15,000, the crosslink density decreases, and the scratch resistance decreases.

  The content of the (b) acrylic compound or urethane acrylate in the antiglare hard coat layer-forming composition is 1 to 70% by mass, preferably 4 to 65% by mass. When the content is less than 1% by mass, the abrasion resistance of the antiglare antireflective film for insert molding is deteriorated. On the other hand, if it exceeds 70% by mass, the formability of the antiglare antireflective film for insert molding deteriorates.

<(C) translucent organic particles>
(C) The light transmitting organic fine particle is for expressing a light diffusion function in the antiglare hard coat layer, an antiglare function by forming a surface asperity, and the like. Translucent resin fine particles are styrene-acrylic monomer copolymer resin (styrene-acrylic copolymer resin), (meth) acrylic resin (refractive index 1.49), vinyl chloride resin (refractive index 1.54), polystyrene Forming with resin including resin (refractive index 1.59), polyethylene resin (refractive index 1.53), melamine resin (refractive index 1.57 to 1.60), polycarbonate resin (refractive index 1.59), etc. Can. Among them, from the viewpoint of easy adjustment of the refractive index, it is preferable to be formed of a styrene-acrylic copolymer resin or a crosslinked product thereof. In the case of a styrene-acrylic copolymer resin, the refractive index can be arbitrarily adjusted by changing the copolymer composition of both monomers. The above-mentioned refractive index is a refractive index at a wavelength of 589 nm of light.

  (C) The translucent organic fine particles are preferably monodisperse particles having uniform particle sizes in order to uniformly diffuse or scatter light in the antiglare hard coat layer and on the surface thereof. Specifically, the average particle diameter of (c) translucent organic fine particles is preferably 0.5 to 10 μm, more preferably 0.8 to 5 μm. If the average particle size is less than 0.5 μm, the antiglare property on the surface of the antiglare hard coat layer tends to be insufficient. In addition, the aggregation of particles may be excessive, and the formed uneven shape may be large. On the other hand, when it exceeds 10 μm, the unevenness (surface roughness Ra) of the antiglare hard coat layer tends to be too large, and the transparency tends to be impaired.

  The average particle diameter in the present specification is a value calculated from the particle number distribution obtained by measuring the Coulter counter method, converting the measured distribution into a particle number distribution. The Coulter Counter method is a particle size measurement method using electrical resistance, and is a method of measuring an average particle size by measuring a change in electrical resistance between two electrodes generated when particles pass through pores.

  (C) The ratio X / Y of the average particle diameter (X) of the translucent organic fine particles to the film thickness (Y) of the antiglare hard coat layer is preferably 0.01 to 50, more preferably 0.1 to 20. preferable. When this ratio X / Y exceeds 50, the light-transmitting organic fine particle particle fixing power to the antiglare hard coat layer is lowered, which may lower the strength of the antiglare antireflective film for insert molding. is there. On the other hand, if X / Y is less than 0.01, in order to form the desired unevenness on the surface of the antiglare hard coat layer, (c) it is necessary to excessively increase the addition amount of the translucent organic fine particles, The haze value of the antiglare antireflective film for insert molding tends to increase and the image definition tends to decrease.

  The refractive index difference (Δnab) between the refractive index (nab) of the cured product of the components (a) and (b) to be a binder of the antiglare hard coat layer and the refractive index (nc) of the translucent organic fine particles (c) -Nc) is preferably as small as possible. Specifically, it is preferable that Δnab−nc <0.02. When the refractive index difference Δnab-nc is 0.02 or more, the haze of the antiglare antireflective film for insert molding tends to be high, and the image visibility tends to be deteriorated. The refractive index of (c) translucent organic particles is obtained by dispersing equal amounts of translucent organic particles in a solvent in which the refractive index is changed by changing the mixing ratio of two types of solvents having different refractive indexes. The turbidity is measured, and the refractive index of the solvent when the turbidity is minimized is measured with an Abbe refractometer, or by a method such as using a Cargill reagent.

  The content of (c) translucent organic fine particles in the composition for forming an antiglare hard coat layer is 1 to 40% by mass, preferably 5 to 20% by mass. When the content of the (c) translucent organic fine particles is less than 1% by mass, the function of the (c) translucent organic fine particles can not be sufficiently exhibited, and a satisfactory antiglare property can not be obtained. On the other hand, if it exceeds 40% by mass, the haze value of the antiglare hard coat layer becomes too high to cause whitening and the like, and the image recognition property is lowered.

  (C) The translucent organic fine particles may be used alone or in combination of two or more. In this case, two or more translucent organic particles having a specific gravity difference of 0.1 or more may be used in combination, or two or more translucent organic particles having a different particle diameter of 0.5 μm or more in average particle diameter may be used. Also by using in combination, using two or more kinds of translucent organic particles having a refractive index difference of 0.01 or more in combination, or using a combination of spherical translucent organic particles and amorphous translucent organic particles, It is possible to adjust the diffuse reflection intensity.

  The specific gravity can be measured by a liquid phase substitution method, a vapor phase substitution method (pycnometer method) or the like, and the particle diameter can be measured by a Coulter counter method, a light diffraction scattering method or the like. Or it can measure by observing the cross section of an optical laminated body with microscopes, such as SEM and TEM. The refractive index can be measured directly with an Abbe refractometer. Alternatively, the refractive index can be quantitatively evaluated by a method using Cargill reagent, measuring a spectral reflectance spectrum or spectral ellipsometry, or the like.

<(D) Inorganic fine particles>
As the inorganic fine particles, silicon oxide particles (for example, silica particles) can be used. As a silicon oxide particle, colloidal silica or powder silica is mentioned. As colloidal silica, as a commercial product, Nissan Chemical Industries, Ltd. trade name: methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned. Moreover, as powder silica, commercially available products include Nippon Aerosil Co., Ltd. trade name: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT 600, Aerosil OX 50, Asahi Glass Co., Ltd. trade name: Shildex H31, H32, H51, H52, H121, H122, trade name: E220A, E220, manufactured by Nippon Silica Corporation, trade name: SYLYSIA 470, manufactured by Futo Silysia Co., Ltd., trade name: SG flakes, manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  (D) Inorganic fine particles include, in addition to silica particles, zirconium oxide, zinc oxide, zinc antimonate (AZO), antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), tin-doped indium oxide (ITO), etc. Particulates can also be applied.

  As the inorganic fine particles, it is preferable to use those whose surface is modified with a silane coupling agent. If the surface of the inorganic fine particle is not modified, the inorganic fine particle having adsorbed water forms an aggregate with the translucent organic fine particle, which may cause many defects.

  (D) As an effect of blending inorganic fine particles, while high hardness can be imparted in a temperature range of about room temperature to about 85 ° C., an antiglare hard coat layer in a temperature range of about 130 ° C. added at the time of preform or injection molding Flexibility (130 ° C elongation) can be increased.

  (D) The average particle diameter of the inorganic fine particles is preferably 100 nm or less. (D) If the average particle diameter of the inorganic fine particles is larger than 100 nm, the scattering intensity is increased and the haze is increased, leading to the deterioration of visibility such as the image becoming whitish. (D) The lower limit of the average particle size of the inorganic fine particles is not particularly limited, but may be 5 nm or more as a standard. Moreover, when adding (d) inorganic fine particle to the composition for anti-glare hard-coat layer formation, about 5-30 mass% is preferable, and, as for the content, 10-25 mass% is more preferable.

<(E) Photopolymerization initiator>
A photoinitiator is used as a polymerization initiator at the time of hardening the composition for anti-glare hard-coat layer formation with active energy rays, such as an ultraviolet-ray (UV), and forming a coating film. The photopolymerization initiator is not particularly limited as long as it initiates polymerization by active energy ray irradiation, and known compounds can be used. For example, an acetophenone-based polymerization initiator, a benzoin-based polymerization initiator, a benzophenone-based polymerization initiator, and a thioxanthone-based polymerization initiator can be mentioned. Examples of acetophenone-based polymerization initiators include 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one. Examples of the benzoin polymerization initiator include benzoin, 2,2-dimethoxy 1,2-diphenylethane-1-one and the like. Examples of benzophenone-based polymerization initiators include benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4'-tetra (t- Butyl peroxy carbonyl) benzophenone etc. are mentioned. As a thioxanthone type polymerization initiator, 2-chloro thioxanthone, a 2, 4- diethyl thioxanthone etc. are mentioned, for example. Among these, 1-hydroxycyclohexyl phenyl ketone is preferable in terms of resistance to yellowing.

  The photopolymerization initiator is contained in an amount of 1 to 10% by mass, preferably 3 to 7% by mass, in the composition for forming an antiglare hard coat layer. When the content of the photopolymerization initiator is less than 1% by mass, the curing of the antiglare hard coat layer becomes insufficient. On the other hand, when the content exceeds 10% by mass, the amount of the photopolymerization initiator is unnecessarily increased, which is not preferable.

  To the resin composition for an antiglare hard coat layer, if necessary, conventionally known additions such as a surface preparation agent, a leveling agent, an ultraviolet light absorber, an ultraviolet light stabilizer, an antioxidant, an antistatic agent, an antifoaming agent, etc. You may contain a thing in the range (For example, about 0.01-5 mass parts with respect to a total of 100 mass parts of said (a)-(e)) which does not impair the effect of this invention.

  The dilution solvent used for preparation of the composition for forming a hard-coating antiglare layer is not particularly limited as long as it is used to adjust the viscosity and is non-polymerizable. As the dilution solvent, for example, toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, Diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, 3-methoxy butanol and the like can be mentioned. These solvents can be used singly or in combination.

  In addition, when it does not mix | blend a component (d) with the composition for anti-glare hard-coat layer formation, and it comprises by component (a), (b) (c), (e), the total content of these is 100 It is mass%. On the other hand, when the component (d) is blended in the composition for forming an antiglare hard coat layer, the total content of the components (a) to (e) is 100 mass including the content of the component (d). And%.

«Antiglare antireflective film for insert molding»
The antiglare antireflective film of the present invention is a film to be used for insert molding, and the antiglare hard coat layer and the antireflective layer are thermoplastically transparent on one surface of the thermoplastic transparent substrate film. It comprises in this order from the base film side. The antiglare hard coat layer here is formed by curing the composition for forming the antiglare hard coat layer.

<Thermoplastic transparent substrate film>
The thermoplastic transparent substrate film is made of a transparent thermoplastic resin, and for example, a film made of polycarbonate resin or polymethyl methacrylate resin can be used. In particular, a film having a two-layer structure in which a polycarbonate layer and a polymethyl methacrylate layer are laminated is preferable. In this case, the polymethyl methacrylate layer is preferably on the antiglare hard coat layer side.

  The thickness of the thermoplastic transparent substrate film may be the same as that of a general substrate film conventionally used in this type of antiglare film for insert molding of this type, and is usually 30 to 300 μm, preferably 75 to 250 μm. It is.

<Anti-glare hard coat layer>

  The antiglare hard coat layer can be formed by applying the above composition for forming an antiglare hard coat layer on a thermoplastic transparent substrate film and then curing by irradiation with an active energy ray. As a method of applying the composition for forming an antiglare hard coat layer on a thermoplastic transparent substrate film, a roll coating method, a spin coating method, a dip coating method, a brush coating method, a spray coating method, a bar coating method, a knife Any known method such as a coating method, a die coating method, a gravure coating method, a curtain flow coating method, a reverse coating method, a kiss coating method, and a comma coating method may be employed. At the time of application, in order to improve adhesion, it is preferable to pre-treat the surface of the thermoplastic transparent base film in advance such as corona discharge treatment.

As an active energy ray source used for irradiation of an active energy ray, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, an electron beam accelerator, a radioactive source and the like are used. It is preferable that the irradiation amount of an active energy ray is 50-5000 mJ / cm < ² > as an integrated light quantity in wavelength 365nm of an ultraviolet-ray. If the irradiation amount is less than 50 mJ / cm ² , the curing of the composition for forming an antiglare hard coat layer becomes unfavorably insufficient. On the other hand, when it exceeds 5000 mJ / cm ² , the amount of heat applied to the film is large, and thus the film tends to be wrinkled, which is not preferable.

  Film thickness of antiglare hard coat layer (Y) (Y: film thickness that becomes the most thin film in the absence of particles. Layer thickness in the absence of particles is the surface F of the antiglare hard coat layer ( Measured from an SEM image of the cross section in the vicinity of Fig. 1. When the boundary between the particle and its periphery is unclear and the boundary between the thermoplastic transparent substrate film and the antiglare hard coat layer is unclear, As shown in Fig. 2, the curvature diameter particle d1 (see Fig. 2) of the translucent organic fine particle is determined from the curve of the raised portion in the shape of the surface F. From the vertex S of the surface and the curvature diameter d1 to the base point a. The bottom points a are determined at a plurality of locations, and a line B connecting the plurality of bottom points a is defined as the boundary between the thermoplastic transparent substrate film and the antiglare hard coat layer. The film thickness d2 corresponding to the distance between the bottom of the recessed portion and the line B is determined as the film thickness Y That) is preferably 0.05~5μm, preferably 0.1~1.5μm. When the film thickness (Y) of the antiglare hard coat layer exceeds 5 μm, the elongation (for example, the elongation at 130 ° C.) of the antiglare hard coat layer tends to decrease, and the moldability tends to deteriorate. As the film thickness of the antiglare hard coat layer becomes thinner, the elongation (for example, the elongation at 130 ° C.) tends to increase, so the formability tends to improve, but the film thickness (Y If the value of (c) is less than 0.05 μm, (c) the adhesive power of the light-transmitting organic fine particles may be insufficient to lower the strength.

<Antireflection layer>
The antireflective layer is a layer that exhibits an antireflective effect in the antiglare antireflective film for insert molding by adjusting the refractive index. As the antireflective layer in this case, a layer formed as a so-called low refractive index layer can be employed in a known antireflective film attached to the surface of an image display device such as a liquid crystal display, and the refractive index thereof Is preferably set to 1.30 to 1.45. When the refractive index is less than 1.30, it is difficult to form a sufficiently hard layer, and when the refractive index exceeds 1.45, the antireflection property may not be sufficiently exhibited.

  The thickness of the antireflective layer is preferably 70 to 140 nm. When the film thickness is out of this range, the interference balance of light with other layers is lost, and sufficient anti-reflection properties can not be obtained.

<Composition for forming antireflective layer>
The antireflective layer is formed by applying a coating liquid comprising the composition for forming an antireflective layer and then curing it by ultraviolet irradiation. The coating method, the curing conditions, and the dilution solvent for viscosity adjustment may be the same as in the antiglare hard coat layer.

  As the composition for forming an antireflective layer, although a general composition for forming a low refractive index layer conventionally known in the film of this type can be used, (a) a fluorine-containing ultraviolet-curable resin, (a) Polyether-modified polydimethylsiloxane having an acryl group or polyester-modified polydimethylsiloxane having an acryl group, (c) a binder copolymerizable with (a) and (a), (d) translucent organic fine particles, It is preferred to use one containing a photopolymerization initiator. As the light-transparent organic fine particles and the photopolymerization initiator (d), those similar to those used in the composition for forming an antiglare hard coat layer can be used.

(A) Fluorine-Containing UV-Curable Resin The fluorine-containing UV-curable resin is for exhibiting an antifouling function, and can weaken the adhesion of a fingerprint to be attached when the film surface is touched. The fluorine-containing UV-curable resin includes (meth) acrylates containing a C2 to C7 perfluoroalkyl chain. As a commercial item, Daikin Industries Ltd. "optool DAC-HP" and DIC Corporation "Megafuck RS-75" can be used. It is preferable that 0.2-15 mass% of fluorine-containing ultraviolet curable resin is contained in the composition for anti-reflective layer formation.

(I) Polyether-modified polydimethylsiloxane having an acrylic group or polyester-modified polydimethylsiloxane having an acrylic group Polyether-modified polydimethylsiloxane having an acrylic group or a polyester-modified polydimethylsiloxane having an acrylic group adhered to the film surface Improve the wipeability of fingerprints. As a commercial item, BYK-Chemie Japan KK "BYK-UV 3500", "BYK-UV 3530" (polyether modified polydimethylsiloxane having an acrylic group), or BYK-Chemie Japan KK "BYK-UV 3570" (Polyester-modified polydimethylsiloxane having an acryl group) can be used. The component (i) is preferably contained in an amount of 0.1 to 8% by mass in the composition for forming an antireflective layer.

(C) Binder Copolymerized with (A) and (A) The binder herein can impart hardness and followability to a mold in insert molding to an antiglare antireflective film for insert molding. The binder is preferably contained in an amount of 40 to 85% by mass in the composition for forming an antireflective layer. As such a binder, an acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (α) and an ultraviolet curable resin (β) are contained, and as a commercial product, Nippon Kayaku Co., Ltd. Ltd. “KAYARADDPHA” (dipentaerythritol hexaacrylate), “OD 2 H 2 A” (1, 10-diacryloyloxy-2, 9-dihydroxy-4, 4, 5, 5, 6, 6, 7, 7-octa) (Fluorodecane), "Silver UV 7600B" manufactured by Nippon Gohsei Kagaku Co., Ltd., etc. can be used.

  In addition, a fluorine-containing reactive polymer having a polymerizable double bond can also be used. The fluorine-containing reactive polymer having a polymerizable double bond is solvent soluble, has a main chain derived from a fluorine-containing ethylenic monomer, and has a reactive group for crosslinking and curing. As a reactive group, a (meth) acryloyloxy group, an α-fluoroacryloyloxy group, an epoxy group and the like can be mentioned. Such a solvent-soluble fluorine-containing reactive polymer having a polymerizable double bond has a high molecular weight, so that it has good film forming property while containing fluorine, and cross-link curing using a reactive group after film formation Since a hardened layer can be obtained by carrying out, high strength and chemical resistance can be imparted. Furthermore, there is an advantage that the extensibility (followability) can be maintained high because the polymer structure is moderate.

The fluorine-containing reactive polymer having a polymerizable double bond has a content of a group having a polymerizable double bond of usually 1 to 20% by mass, preferably 5 to 15% by mass. The mass (weight) average molecular weight is usually 1,000 to 500,000, preferably 3,000 to 200,000. As a specific fluorine-containing reactive polymer, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanone represented by the following general formula (1) A product obtained by reacting α-fluoroacrylic acid fluoride: CH ₂ CFCFCOF with a homopolymer obtained by polymerizing with a peroxide represented by the following general formula (2): Can be mentioned.

<Primer layer>
In the antiglare antireflective film for insert molding, a primer layer may be provided between the antiglare hard coat layer and the antireflective layer, if necessary. By interposing the primer layer, the adhesion between the antiglare hard coat layer and the antireflective layer is improved, and the scratch resistance of the antiglare antireflective film for insert molding is further improved.

<Composition for forming primer layer>
The composition for forming a primer layer preferably comprises at least an acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A), an ultraviolet curable resin (B) and a photopolymerization initiator (C), respectively. One or more kinds are contained. By containing an acryl-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) together with a photopolymerization initiator (C), excellent adhesion to a material containing an acrylic resin can be exhibited. . Further, by containing at least one kind of the ultraviolet curable resin (B), appropriate fluidity can be provided.

  The acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) can be obtained from a polyolefin component, an unsaturated dicarboxylic acid (anhydride) component and an acrylic component, and a polyolefin-derived structural unit and an unsaturated dicarboxylic acid It consists of a structural unit derived from an acid (anhydride) and a structural unit derived from an acryl. In addition, each of these components (a polyolefin component, an unsaturated dicarboxylic acid (anhydride) component, an acrylic component) demonstrated below may be only 1 type, respectively, and may be 2 or more types.

  The polyolefin component constituting the acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is, for example, a copolymer having, as essential constitutional units, one or more of α-olefins of 4 to 12 carbon atoms and propylene. Coalescence is preferably mentioned. Here, as a C4-C12 alpha-olefin, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl- 1-pentene etc. are mentioned, for example. Among them, 1-butene, 1-pentene, 1-decene and 4-methyl-1-pentene are preferable, and 1-butene is most preferable. It is preferable that the ratio for which the C4-C12 alpha-olefin occupies in a polyolefin component is 15-70 mol%. However, in the case of a copolymer having also an α-olefin having 4 to 12 carbon atoms and an olefin other than propylene as a structural unit, for example, ethylene is also a structural unit (for example, propylene / 1-butene / ethylene copolymer In such cases, the proportion of ethylene in the polyolefin component is preferably 1 mol% or less, more preferably 0.5 mol% or less, and even more preferably 0.1 mol% or less. More preferable.

  The polyolefin component constituting acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is a thermally degraded polyolefin from high molecular weight polyolefin, that is, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin at high temperature Is preferred. In thermally degraded polyolefins from high molecular weight polyolefins, a relatively large number of double bonds are uniformly present at the end or in the molecule. Therefore, grafting of unsaturated dicarboxylic acid (anhydride) becomes easy. This makes it possible to improve the unsaturated dicarboxylic acid (anhydride) addition rate, which is generally considered difficult to increase, to a relatively high range described later. As a method of obtaining the thermally degraded polyolefin, for example, a high molecular weight polyolefin having a number average molecular weight of 15,000 to 150,000, in the presence of an organic peroxide at 180 to 300 ° C., in the absence of an organic peroxide The heating may be performed at 300 to 450 ° C. for 0.5 to 1 hour. Preferably, the method of heating in the absence of an organic peroxide is preferred.

  The number average molecular weight of the polyolefin component constituting the acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is preferably 500 to 40,000, and more preferably 1,500 to 30,000.

  Examples of the unsaturated dicarboxylic acid (anhydride) component constituting the acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) include, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, cyclohexene dicarbonide Unsaturated dicarboxylic acids such as acid, cycloheptene dicarboxylic acid and aconitic acid; unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride and itaconic acid, and unsaturated dicarboxylic acid anhydrides having 1 to 5 carbon atoms Esterified with an alkyl alcohol and the like. In particular, maleic anhydride is preferred from the viewpoint of high adhesion to the thermoplastic resin.

  As an acrylic component which constitutes acrylics denaturation unsaturated dicarboxylic acid (anhydride) grafting polyolefin (A), acrylics which have active hydrogen, such as hydroxyl group containing (meta) acrylates, such as 4-hydroxy butyl (meta) acrylate, for example And acrylic components containing an isocyanate group such as 2-acryloylethyl isocyanate, etc., and (meth) acrylic esters such as methyl (meth) acrylate can also be used as the acrylic component. .

  The method for obtaining the acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) from the polyolefin component, the unsaturated dicarboxylic acid (anhydride) component and the acrylic component is not particularly limited, and may be obtained by a conventionally known method. Be For example, it can be obtained by a method in which an acrylic component is reacted after graft addition of an unsaturated dicarboxylic acid (anhydride) component to a polyolefin component. The specific reaction conditions and the like may be appropriately set in accordance with the usual organic synthesis method. For example, when (meth) acrylic acid ester is used as an acrylic component when reacting an acrylic component, an organic peroxide having hydrogen extraction ability such as dicumyl peroxide may be used.

  It is preferable that melting | fusing point is 92-112 degreeC, and, as for acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A), it is 95-110 degreeC more preferably. As a result, excellent adhesion is exhibited even at high temperatures, and mold opening can occur immediately without cooling in a high mold temperature state without causing peeling between the antiglare hard coat layer and the antireflective layer. become able to. Conversely, if the melting point of the acryl-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is less than 92 ° C., the adhesion at high temperature becomes insufficient, and the mold temperature is high without cooling. If the mold is immediately opened, peeling may occur between the antiglare hard coat layer and the antireflective layer. On the other hand, when the melting point of the acryl-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) exceeds 112 ° C., the resulting coated film (primer layer) tends to be clouded. In addition, the water resistance of the primer layer to be obtained is lowered, and moisture is easily permeated into the primer layer, whereby the adhesion is lowered and there is a possibility that delamination may be caused between the antiglare hard coat layer and the antireflective layer. . The melting point is measured by differential scanning calorimetry (DSC).

  Acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is the proportion of structural units derived from unsaturated dicarboxylic acid (anhydride) in its structure (ie addition of unsaturated dicarboxylic acid (anhydride) 5-15 mass% is preferable, and 6-13 mass% is more preferable. Thereby, the compatibility with the ultraviolet curable resin (B) generally having high polarity is improved. As a result, a coating film without turbidity can be obtained. Conversely, when the addition rate of the unsaturated dicarboxylic acid (anhydride) in the acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is less than 5% by mass, the resulting coated film becomes hazy, Water resistance will also be reduced. On the other hand, even if the addition ratio of unsaturated dicarboxylic acid (anhydride) in acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) exceeds 15% by mass, the water resistance of the resulting coated film is lowered. become. The addition ratio of unsaturated dicarboxylic acid (anhydride) in acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) may be calculated, for example, from the peak ratio of carbonyl group in infrared analysis (IR) .

  The number average molecular weight of the acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is not particularly limited, but is preferably 600 to 50,000, for example, 1,600 to 30,000. More preferable. When the number average molecular weight is too small, the physical properties of the coating film tend to be lowered. On the other hand, if the size is too large, turbidity may occur in the resulting coated film, and at the same time, the fluidity may be reduced to impair the workability at the time of coating.

  Specific examples of the ultraviolet curable resin (B) include, for example, urethane (meth) acrylate (oligomer), epoxy (meth) acrylate (oligomer), polyester (meth) acrylate (oligomer), polyether (meth) acrylate (oligomer) And (meth) acrylates (oligomers) and the like. Among these, (urethane (meth) acrylate (oligomer) and (meth) acrylate (oligomer) are preferable.Acrylate (oligomer) and urethane acrylate (oligomer) are compared in terms of superior durability and thus acrylate ( On the other hand, urethane acrylates (oligomers) are preferred in that they have good flexibility, and monomers are preferred in terms of excellent adhesion when comparing monomers with oligomers. Oligomers are preferred in that they have high flexibility.

  As a commercial item of the ultraviolet curable resin (B), as (urethane (meth) acrylate (oligomer), “EBECRYL8402”, “EBECRYL8307”, “EBECRYL4491”, “EBECRYL8411”, “EBECRYL8410”, manufactured by Daicel-Cytec Co., Ltd. “EBECRYL 8465”, Shin-Nakamura Chemical Co., Ltd. “A-9300 (tris (2-acryloyloxyethyl) isocyanurate)”, “A-9300-1CL (ε-caprolactone modified tris- (2-acryloxyethyl) And (meth) acrylates (oligomers), for example, “KAYARAD DPCA-20”, “KAYARAD TMPTA”, “KAYARAD PEG400DA”, manufactured by Nippon Kayaku Co., Ltd. Company Chemical Co., Ltd. "Light Acrylate 1.9ND-A" includes "Light Acrylate DCP-A".

  In addition, an acrylate (oligomer) means that it is an acrylate monomer or an acrylate oligomer. The below-mentioned acrylate (oligomer) is also meant to be an acrylate monomer or acrylate oligomer.

  The ultraviolet curable resin (B) can be obtained by a conventionally known method. The weight average molecular weight of the ultraviolet curable resin (B) is preferably 100 to 50,000. When the weight average molecular weight is less than 100, the physical properties of the coating film tend to be lowered. On the other hand, if it exceeds 50,000, the flowability tends to be lowered, and the workability at the time of coating may be impaired.

  A photoinitiator (C) is used as a polymerization initiator at the time of hardening the composition for primer layer formation with active energy rays, such as an ultraviolet-ray (UV), and forming a coating film. The photopolymerization initiator (C) is not particularly limited as long as it initiates polymerization by active energy ray irradiation, and known compounds can be used. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morphorinopropane-1 Acetophenone-based polymerization initiators such as N-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy-1,2 Benzoin-based polymerization initiators such as diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4' Benzophenone-based polymerization initiators such as tetra- (t-butylperoxycarbonyl) benzophenone, 2-chlorothione Xanthone, such thioxanthone type polymerization initiators such as 2,4-diethyl thioxanthone, and the like.

  The compounding ratio of the photopolymerization initiator (C) is preferably (C) / [(A) + (B)] = 0.1 / 10 to 10/100 (mass ratio). When the photopolymerization initiator (C) is less than the above range, the polymerization becomes insufficient and adhesion can not be exhibited. On the other hand, when the content is more than the above range, the content is unnecessarily increased, which is not preferable.

  In the composition for forming a primer layer, conventionally known additives such as surface preparation agents, leveling agents, ultraviolet light absorbers, ultraviolet light stabilizers, antioxidants, antistatic agents, antifoaming agents, etc. You may contain in the range which does not impair the effect of invention.

  When preparing the composition for forming a primer layer, a dilution solvent is used to adjust the viscosity. The composition for forming a primer layer can be easily applied mainly on the antiglare hard coat layer by the dilution solvent. The dilution solvent is not particularly limited as long as it is non-polymerizable. For example, toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, diacetone alcohol, Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, 3-methoxy butanol and the like can be mentioned. These solvents can be used singly or in combination.

  As a method of applying the composition for forming a primer layer on the antiglare hard coat layer, a roll coating method, a spin coating method, a dip coating method, a brush coating method, a spray coating method, a bar coating method, a knife coating method, a die coating method Any known method such as a method, a gravure coating method, a curtain flow coating method, a reverse coating method, a kiss coating method, a comma coating method, etc. may be employed.

As an active energy ray source used for irradiation of an active energy ray, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, an electron beam accelerator, a radioactive source and the like are used. It is preferable that the irradiation amount of an active energy ray is 50-5000 mJ / cm < ² > as an integrated light quantity in wavelength 365nm of an ultraviolet-ray. When the irradiation amount is less than 50 mJ / cm ² , the curing of the composition for an antiglare hard coat layer is not preferable because it becomes insufficient. On the other hand, when it exceeds 5000 mJ / cm ² , the primer layer tends to be colored, which is not preferable.

  Film thickness of primer layer (I) (I: in antiglare hard coat layer (c) total film thickness of antiglare hard coat layer and primer layer to be most thin film in the place where the light transmitting organic fine particles are not present (I + Y Value obtained by subtracting the film thickness (Y) of the antiglare hard coat layer, and (c) measuring the layer thickness of the place where the translucent organic fine particle is not present from the cross-sectional SEM image. When the boundary between the thermoplastic transparent substrate film and the antiglare hard coat layer is unclear, as shown in FIG. 2, the curve of the raised portion of the surface F is transparent. The curvature diameter particle d1 (see FIG. 2) of the light organic fine particle is determined The position of the bottom point a is calculated from the vertex S of the surface and the curvature diameter d1 The bottom points a are obtained at a plurality of locations A transparent transparent base film and antiglare hard coat layer In the surface F, the film thickness d2 corresponding to the distance between the bottom of the depressed portion and the line B is determined as the film thickness I), preferably 0.05 to 5 μm, preferably 0.1 to 1 .5 μm. When the film thickness (I) of the primer layer exceeds 5 μm, the elongation (for example, the elongation at 130 ° C.) of the primer layer tends to decrease and the moldability tends to deteriorate. As the film thickness of the primer layer is thinner, the elongation (for example, the elongation at 130 ° C.) tends to increase, so the formability tends to be improved, but the film thickness (I) is 0. If it is less than 05 μm, the adhesion can not be effectively exhibited.

  The film thickness (I) of the primer layer is such that (c) the ratio of the sum of the average particle diameter (X) of the translucent organic fine particles to the film thickness (Y) of the antiglare hard coat layer = X / (Y + I) It is preferably in the range of 0.1 to 50, and more preferably 0.1 to 20. When this ratio X / (Y + I) exceeds 50, the adhesion of the (c) translucent organic fine particle particles to the antiglare hard coat layer is reduced, so that the strength of the antiglare antireflective film for insert molding is reduced. May decrease. On the other hand, if X / Y is less than 0.01, in order to form the desired unevenness on the surface of the antiglare hard coat layer, (c) it is necessary to excessively increase the addition amount of the translucent organic fine particles, The haze value of the antiglare antireflective film for insert molding tends to increase and the image definition tends to decrease.

«Resin molded products»
The resin molded article is provided with the above-mentioned antiglare antireflective film for insert molding on the surface, and is obtained by insert molding. That is, by injecting the molten resin in a state in which the antiglare antireflective film for insert molding is held in advance in the cavity of the injection mold, a resin molded article having the antiglare antireflective film on the surface is obtained. be able to. The antiglare antireflection film is held in the cavity in the direction in which the antiglare hard coat layer is outside and the thermoplastic transparent substrate film is inside. Thereby, the antiglare antireflection film is attached to the surface of the resin molded product by heat-sealing the thermoplastic transparent base film at the time of insert molding. In addition, before an insert molding, the process of a decoration printing and a preform can be implemented to an anti-glare antireflective film by a well-known technique.

  A decorative layer (pattern layer) by printing, vapor deposition or the like can be applied as a decorative printing process, and gravure printing, offset printing, screen printing, flexo printing, inkjet, etc. can be applied as a printing method. Known printing methods can be used.

  A known preform technology can be applied as a preform process, and the antiglare antireflection film is subjected to preheating at about 80 ° C. to 160 ° C. to perform vacuum forming, pressure forming, press forming, and ultra high pressure The film may be made to follow the mold by a molding method such as molding, and the shape of the film may be deformed to conform to the shape of the mold before injection molding (molding in which the film and resin are integrated by insert molding). it can.

  The temperature of the molten resin is preferably 100 to 400 ° C. When the temperature of the molten resin is lower than 100 ° C., the heat-meltable resin forming the antiglare antireflection film can not be sufficiently melted. On the other hand, if the temperature is higher than 400 ° C., the decomposition temperature of the thermoplastic resin is exceeded, and problems such as foaming of the resin molded product occur.

  The form of the resin molded product is not particularly limited, and various ones are targeted. For example, it includes a plate or a case having a curved surface structure, which is difficult to form an application layer of uniform thickness, an object or support having poor flexibility, an object such as glass or ceramic, and the like.

«Image display device»
The antiglare antireflective film can be applied to the cover surface of a display (image display device) such as a car navigation system, a meter panel, and a mobile phone. In particular, when used for a touch panel display operated with a finger, the effects of the present invention can be maximally exhibited. Moreover, it can also be assembled | attached to an image display apparatus as a cover (resin molded article) by which the anti-glare anti-reflective film was previously stuck by insert molding on the surface.

(Preparation of composition for forming an antiglare hard coat layer)
(Composition 1)
(A) 65% by mass of PMMA (manufactured by SIGMA-ALDRICH Co., Ltd., “Poly (Methyl methacrylate)” weight-average molecular weight 97,000, Tg = 105 ° C.) as an acrylic resin having a glass transition temperature of 84 ° C. or higher, (B) 22 mass% of "purple light UV7600B" manufactured by Japan Synthetic Chemical Industry Co., Ltd. as a urethane acrylate having a weight average molecular weight of 15000 or less having three or more (meth) acrylic groups in one molecule, (c) transmission 9% by mass of “MX-150” (crosslinked acrylic monodispersed particles, average particle diameter 1.5 μm) manufactured by Soken Chemical Co., Ltd. as light organic fine particles, (e) Ciba Specialty Chemicals (a stock company as a photopolymerization initiator) 4) Mix “IRGACURE-184” manufactured by ) Were mixed and completely dissolved to obtain a coating liquid containing the antiglare hard coat layer forming composition. In addition, components other than (c) translucent organic fine particles “MX-150” (cross-linked acrylic monodispersed particles manufactured by Soken Chemical Co., Ltd., average particle diameter 1.5 μm) are completely dissolved in the coating solution, (c) 2.) It was confirmed that translucent organic fine particles "MX-150" (crosslinked acrylic monodispersed particles manufactured by Soken Chemical Co., Ltd., average particle diameter 1.5 μm) were uniformly dispersed in a paint.

(Composition 2 to Composition 28, Comparative Composition 1 to Comparative Composition 11)
The materials shown in Tables 1 and 2 were mixed in the proportions shown in Tables 1 and 2 in the same manner as in Composition 1 to prepare a coating solution containing the composition for forming an antiglare hard coat layer. In addition, each material shown to Table 1, 2 is as follows.
PMMA: manufactured by SIGMA-ALDRICH, Poly (Methyl methacrylate), weight average molecular weight 97,000, Tg = 105 ° C.
MB-2952: Mitsubishi Rayon Co., Ltd. “Dianal MB-2952”, thermoplastic acrylic resin, weight average molecular weight 82,000, Tg = 84 ° C.
UC-3920: "ARUFONUH-UC-3920" manufactured by Toagosei Co., Ltd., acrylic-styrene resin, weight average molecular weight 15,500, Tg = 102 ° C
BR-50: Mitsubishi Rayon Co., Ltd. “Dianal BR-50”, thermoplastic acrylic resin, weight average molecular weight 65,000, Tg = 100 ° C.
BR-52: Mitsubishi Rayon Co., Ltd. “BR-52”, thermoplastic acrylic resin, weight average molecular weight 85,000, Tg = 105 ° C.
BR-73: Mitsubishi Rayon Co., Ltd. “Dianal BR-73”, thermoplastic acrylic resin, weight average molecular weight 85,000, Tg = 100 ° C.
BR-80: Mitsubishi Rayon Co., Ltd. “Dianal BR-80”, thermoplastic acrylic resin, weight average molecular weight 95,000, Tg = 105 ° C.
BR-83: Mitsubishi Rayon Co., Ltd. "Dianal BR-83", thermoplastic acrylic resin, weight average molecular weight 40,000, Tg = 105 ° C
BR-88: Mitsubishi Rayon Co., Ltd. “BR-88”, thermoplastic acrylic resin, weight average molecular weight 480,000, Tg = 105 ° C.
MB-2389: Mitsubishi Rayon Co., Ltd. "Dianal MB-2389", thermoplastic acrylic resin, weight average molecular weight 30,000, Tg = 90 ° C
MB-7033: Mitsubishi Rayon Co., Ltd. “Dianal MB-7033”, thermoplastic acrylic resin, weight average molecular weight 92,000, Tg = 84 ° C.
BR-60: Mitsubishi Rayon Co., Ltd. “Dianal BR-60”, thermoplastic acrylic resin, weight average molecular weight 70,000, Tg = 75 ° C.
MB-2539: "Dianal MB-2539" manufactured by Mitsubishi Rayon Co., Ltd., thermoplastic acrylic resin, weight average molecular weight 82,000, Tg = 55 ° C
DPHA: Nippon Kayaku Co., Ltd. “KAYARAD DPHA”, dipentaerythritol hexaacrylate 7600 B: Nippon Gohsei Kagaku Co., Ltd. “purple light UV-7600 B”, hexafunctional urethane acrylate TMP-A: Kyoeisha Co., Ltd. “Light Acrylate TMP-A ", trimetyl propane triacrylate AM-90G:" Methoxy polyethylene glycol # 400 "manufactured by Shin-Nakamura Chemical Co., Ltd., acrylate A-200:" polyethylene glycol 200 "manufactured by Shin-Nakamura Chemical Co., Ltd., Diacrylate I-184: "Irgacure-184" manufactured by Ciba Specialty Chemicals Ltd., 1-hydroxycyclohexyl phenyl ketone MX-150: cross-linked acrylic monodispersed particles manufactured by Soken Chemical Co., Ltd., average particle diameter 1.5 μm
MX-80H3wT: Cross-linked acrylic monodispersed particles manufactured by Soken Chemical Co., Ltd., average particle diameter 0.8 μm
MX-300: Cross-linked acrylic monodispersed particles manufactured by Soken Chemical Co., Ltd., average particle size 3.0 μm
SSX-1055QXE: Cross-linked acrylic-styrene monodispersed particles manufactured by Sekisui Plastics Co., Ltd., average particle diameter 5.0 μm
Silica: “MIBK-ST” manufactured by Nissan Chemical Industries, Ltd., methyl isobutyl ketone dispersed silica sol Zirconium oxide: “ZRMEK 25% -F47” manufactured by CI Kasei Co., Ltd., zirconium oxide fine particle dispersion

(Manufacture of antiglare antireflective film)
Example 1-1
A coating solution containing the composition for forming an antiglare hard coat layer of composition 1 is applied to a roll coater on a polymethyl methacrylate layer of a transparent substrate comprising a two-layer laminate of a polycarbonate layer and a polymethyl methacrylate layer. The dry film was applied to a thickness of 0.2 μm and dried at 80 ° C. for 2 minutes. The dry film thickness is substantially the film thickness of the hard coat layer. Thereafter, ultraviolet rays were irradiated with a 120 W high pressure mercury lamp (manufactured by Nippon Battery Co., Ltd.) (accumulated light amount: 300 mJ / cm ² ) to cure the composition for forming a hard coat layer, thereby forming a hard coat layer.

  Subsequently, (a) 5% by mass of "Optool DAC-HP" manufactured by Daikin Industries, Ltd. as a fluorine-containing ultraviolet-curable resin, (i) polyether-modified polydimethylsiloxane having an acrylic group or polyester-modified having an acrylic group 4% by mass of “BYK3500” (Big Chemie Japan Co., Ltd.) as polydimethylsiloxane, and “OD 2 H 2 A” (1, 10) as a binder copolymerizable with (C), (A) and (B) -43% by mass of diacryloyloxy-2,9, -dihydroxy-4,4,5,5,6,6,7,7-octafluorodecane, (E) JGC catalyzer formed as translucent organic fine particles A composition for forming an antireflective layer containing 43% by mass of "Thrueria NAU" and 5% by mass of "IRGACURE-907" manufactured by BASF as a photopolymerization initiator (O) The coating solution (L-1) for forming an antireflective layer was obtained by diluting with IPA so that the solid content concentration was 5% by mass.

  The obtained coating liquid (L-1) for forming an antireflective layer was formed on the antiglare hard coat layer to a thickness of about 0.1 μm (when the reflection spectrum was measured, the minimum reflectance wavelength was about 600 nm) To a desired thickness) and dried at 80.degree. C. for 2 minutes. The composition for forming an antireflective layer is irradiated with ultraviolet light of 300 mJ by using an ultraviolet irradiator (120 W high-pressure mercury lamp manufactured by I-Graphics Co., Ltd.) in a nitrogen atmosphere to form an antireflective layer, thereby preventing insertion molding. An antiglare film was obtained.

The refractive index of the antireflective layer was measured by the following method to be 1.36.
(Measurement of refractive index)
(1) On a PET film (trade name "A4100" manufactured by Toyobo Co., Ltd.), using a bar coater, the coating liquid for each layer is dried and cured to a thickness of 100 to 500 nm. Was adjusted and applied. After drying, it was irradiated with ultraviolet light of 400 mJ and cured using a 120 W high pressure mercury lamp in a nitrogen atmosphere with an ultraviolet irradiation device (manufactured by Iwasaki Electric Co., Ltd.) to prepare a film for refractive index measurement.
(2) The back surface of the produced film was roughened with sand paper, and the reflection spectrum was measured with a reflection spectral film thickness meter [“FE-3000”, manufactured by Otsuka Electronics Co., Ltd.] filled with black paint.
(3) From the reflectance read from the reflection spectrum, the constant of the wavelength dispersion formula (Formula 1) of n-Cauchy shown below was determined, and the refractive index at a wavelength of 589 nm of light was determined.
N (λ) = a / λ4 + b / λ2 + c (Equation 1)
a, b, c: wavelength dispersion constant

(Example 1-2 to Example 1-30, Comparative Example 1-1 to Comparative Example 1-11)
In the same manner as in Example 1-1, an antiglare hard coat was formed using each composition for forming an antiglare hard coat layer of Composition 2 to Composition 30 and Comparative Composition 1 to Comparative Composition 11. A layer was formed, and an antireflective layer was formed in the same manner as in Example 1-1.

  In addition, in the antiglare antireflection film for insert molding of Examples 1-14 to 1-17, a primer layer was formed between the antiglare hard coat layer and the antireflection layer. The primer layer was formed as follows.

<Preparation of Primer Composition>
[(A) Synthesis of acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin]
A high molecular weight polyolefin (copolymer of propylene and 1-butene: "Tafmer XR110T" manufactured by Mitsui Chemicals, Inc.) is placed in a reaction vessel equipped with a stirrer and a thermometer, and heated to 360 ° C to melt it, By heating for 80 minutes under an air stream, a low molecular weight polyolefin (1) was obtained by thermal degradation.

  Next, 160 parts of low molecular weight polyolefin (1) is put into a reaction vessel equipped with a stirrer, a thermometer and a cooling pipe, heated to 180 ° C. under a nitrogen stream and melted, and then 25 parts of maleic anhydride and 20 parts of 1-dodecene were added and mixed uniformly. Next, a solution prepared by dissolving 1 part of dicumyl peroxide in 20 parts of xylene prepared beforehand is added dropwise over 2 hours while maintaining at 180 ° C., and after the addition, the mixture is further stirred at 180 ° C. for 2 hours, and grafting of maleic anhydride Reaction was performed. Thereafter, xylene and 1-dodecene were distilled off under reduced pressure to obtain maleic anhydride grafted polyolefin (2).

Next, 450 parts of maleic anhydride grafted polyolefin (2) is put into a reaction vessel equipped with a stirrer, a thermometer and a cooling pipe, and the temperature is raised to 105 ° C. under a nitrogen stream to maintain the temperature. 300 parts of toluene was gradually dropped under stirring. Then, 135 parts of a hydroxyl group-containing methacrylate ("Placel FM4" manufactured by Daicel Chemical Industries, Ltd.) represented by the following general formula (3) is added, reacted for 3 hours at the same temperature with stirring, and cooled. A solution of hydroxyl group-containing methacrylate modified maleic anhydride grafted polyolefin (α1) was obtained. The solid content concentration of the obtained solution was 66.1%.

（Ｒ１は下記一般式（５）で表される６価の基である。）

Subsequently, a solution of a hydroxyl group-containing methacrylate-modified maleic anhydride grafted polyolefin (α1) is converted to 19% by mass in terms of solid content, (B) a bifunctional aliphatic urethane acrylate (manufactured by Daicel Cytech Co., Ltd.) as an ultraviolet curable resin. EBECRYL8402 ", average molecular weight 1000) 33% by mass, Nippon Kayaku Co., Ltd. product" KAYARAD DPCA-20 "represented by the following general formula (4) 10% by mass 1,9-nonanediol diacrylate (Kyoeisha 34% by mass of "Light Acrylate 1.9 ND-A" manufactured by Kagaku Kogyo Co., Ltd., (C) 1-hydroxy-cyclohexyl phenyl ketone (Ciba Specialty Chemicals Co., Ltd. manufactured by I-184) as a photopolymerization initiator Of the composition for forming a primer layer containing 4% by mass of IP) to a solid content concentration of 5% by mass Was obtained by coating liquid for forming the primer layer a (P-1) diluted with.

(R1 is a hexavalent group represented by the following general formula (5).)

  The obtained coating liquid (P-1) for forming a primer layer was applied onto the antiglare hard coat layer to a thickness of about 0.4 μm and dried at 80 ° C. for 2 minutes. The composition for forming a primer layer is irradiated with ultraviolet light of 300 mJ using a UV irradiation device (120 W high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd.) under a nitrogen atmosphere to form a primer layer, and an antiglare property for insert molding An antireflective film was obtained.

  The layer structure of the antiglare antireflective film for insert molding of each Example and Comparative Example is shown in Tables 3 and 4. Moreover, about the obtained antiglare antireflection film of each Example and comparative example, elongation rate, moldability, antiglare property, haze, luminous reflectance, abrasion resistance, and durability are respectively as follows. Measured and evaluated. The results are also shown in Tables 3 and 4.

(Growth rate)
A film sample is punched out in the shape of a dumbbell shape No. 3 (see FIG. 3), and at a temperature of 50 mm / minute in an atmosphere of 130 ° C. in a constant temperature chamber tensile testing device model TCR 2 L (manufactured by Shimadzu Corporation). The length of the coating layer was whitened (cracked) (L1) and the length of the film cut (L2) were measured. From the obtained L1 and L2, the elongation to whitening of the coating layer and the elongation at the time of film cutting were calculated from the following equation.
Elongation to whitening of coating layer = ((L1-initial length 20 mm) / initial length 20 mm) x 100%

(Anti-glare property)
Image sharpness measured at 45 ° reflection through an optical comb having a width of 1 mm using an image sharpness measuring device (imageability measuring device manufactured by Suga Test Instruments Co., Ltd., ICM-1T) based on JIS K 7105-1981 The degree value (reflection image sharpness) (%) was measured. The judgment criteria of the measurement result are as follows.
Reflected image sharpness 100% to 80%: no antiglare property Reflected image sharpness less than 80% 15% or more: good antiglare effect Reflected image sharpness less than 15% 0% or more: antiglare effect too strong

(Haze)
The haze value (%) as an optical characteristic was measured using a haze meter (NDH 2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

(Visual reflectance)
In order to remove the back surface reflection of the measurement surface, the back surface of the film was roughened with sandpaper and adjusted in the form of being filled with a black paint. The measurement surface of the adjusted film is measured by Nippon Denshoku Co., Ltd. “SD6000”, and the tristimulus value Y of the object color due to reflection in the XYZ color system (CIE standard illuminant D65) defined in JIS Z 8701 is used. Calculated.

(Abrasion resistant)
The surface of the antireflective film was subjected to a load of 250 gf on # 0000 steel wool, and after 10 cycles of friction at a stroke width of 25 mm and a speed of 30 mm / sec, the surface was visually observed and evaluated according to the following criteria. Steel wool was put together to about 10 mmφ, and cut and rubbed so as to make the surface uniform, and used.
○: 0 to 10 scratches Δ: 11 to 20 scratches ×: 21 or more scratches

(durability)
It was stored under an atmosphere of 85 ° C. and 85% RH for 1000 hours, and the appearance before and after the test, the antiglare property <transmission image definition, reflection image definition> was evaluated. Change in appearance change (change caused by blistering, floating or embrittlement), change in anti-glare property <transmission image definition, reflection image definition> (rate of change (change amount before and after test / initial characteristic x 100 (%)) is 20% ○: No change in appearance (changes that cause blistering, floating, or embrittlement), changes in antiglare <transmission image definition, reflection image definition> (rate of change (change before and after test / initial stage) The case where the characteristic x 100 (%) was 20% or more) was evaluated as x.

(Moldability)
Fusion bonding of an antiglare antireflective film to a molded article: An injection molding die such that the obtained antiglare antireflective film is in contact with a polycarbonate resin in which a thermoplastic transparent substrate film (non-coated surface side) is melted. The polycarbonate resin held in the inner cavity and melted at a temperature of about 360 ° C is injected into the mold at a pressure of 29400 kPa, allowed to cool, and the flat plate portion and radius R = 0.5 mm at both ends The resin molded product (Example 2-1 to 2-30, Comparative Example 2-1 to Comparative Example 2-11) which has a curved-surface-shaped part which becomes is obtained. That is, the antiglare antireflection film was fused by an insert molding fusion method of fusing simultaneously with molding, to obtain a resin molded product provided with the antiglare antireflection film on the surface. The presence or absence of a crack in the curved surface shape where the curvature radius R of this resin molded product is 0.5 mm was confirmed visually and with a microscope of 1400 times the curved surface portion of the molded product to confirm the presence or absence of cracks such as cracks. The evaluation criteria at that time are as follows.
:: no cracks such as cracks when observed with a microscope of 1,400 times ○: no cracks such as cracks visually: a crack such as cracks visually

  In the flat portions of the resin molded articles of Examples 2-1 to 2-30 and Comparative Examples 2-1 to 2-11 obtained, the antiglare property, haze, visual The reflectance, abrasion resistance, and durability were measured and evaluated, respectively. The results are also shown in Tables 5 and 6.

  From the results of Tables 3 and 5, all of the antiglare antireflection films of the examples and the resin molded products using the same have not only the antiglare property, the transparency, the antireflection function, but also the scratch resistance and the durability. It was also excellent.

On the other hand, according to the results of Tables 4 and 6, Comparative Examples 1-1 to 1-2 and 2-1 to 2-2 are the glass transition temperature (Tg) of the acrylic resin used for the antiglare hard coat layer (a) The durability was poor because of the low
In Comparative Examples 1-3 and 2-3, the content of the (a) acrylic resin used in the antiglare hard coat layer is too large, and the component (b) is not contained. The abrasion was bad.
In Comparative Examples 1-4 and 2-4, since the content of the (a) acrylic resin used in the antiglare hard coat layer was too small, the elongation rate was bad. In particular, since the moldability is bad and cracks occur, and the resin molded product becomes a defective product, it is not necessary to measure the optical characteristics.
In Comparative Examples 1-5 and 2-5, the content of the component (b) used in the antiglare hard coat layer was too large, and (a) the acrylic resin was not contained, so the elongation was poor. . In particular, since the moldability is bad and cracks occur, and the resin molded product becomes a defective product, it is not necessary to measure the optical characteristics.
In Comparative Examples 1-6 and 2-6, since (b) was one acrylic group in one molecule, the abrasion resistance and the durability were poor.
In Comparative Examples 1-7 and 2-7, the durability was poor because (b) had two acrylic groups in one molecule.
In Comparative Examples 1-8 and 2-8, since the photopolymerization initiator (e) was not blended in the composition for forming the antiglare hard coat layer, the abrasion resistance and the durability of the antiglare antireflection film were improved. It was bad.
In Comparative Examples 1-9 and 2-9, the content of the photopolymerization initiator (e) in the composition for forming an antiglare hard coat layer is too large, so the scratch resistance and durability of the antiglare antireflection film are The sex was bad.
In Comparative Examples 1-10 and 2-10, since the antiglare hard coat layer did not contain (c) translucent organic fine particles, the antiglare property was poor.
In Comparative Examples 1-1 and 2-1, the content of (c) translucent organic fine particles in the composition for forming an antiglare hard coat layer is too large, so the haze is high.

Claims (7)

An antiglare hard coat layer formed by curing a composition for forming an antiglare hard coat layer on one surface of a thermoplastic transparent base film, and an antireflective layer from the thermoplastic transparent base film side In order,
The composition for forming the antiglare hard coat layer is
(A) 25 to 85 mass% of an acrylic resin having a glass transition temperature of 84 ° C. or higher,
(B) Acrylic compounds having a weight average molecular weight of 15,000 or less having three or more (meth) acrylic groups in one molecule, or 15,000 weight average molecular weights having three or more (meth) acrylic groups in one molecule 1 to 70% by mass of the following urethane acrylate,
(C) 1 to 40 mass% of translucent organic fine particles,
(E) 1 to 10% by mass of a photopolymerization initiator,
Including
The upper limit of the total content of the components (a), (b), (c) and (e) is 100% by mass.
Antiglare antireflective film for insert molding.   The antiglare antireflection film for insert molding according to claim 1, wherein the component (a) is polymethyl methacrylate.   The antiglare antireflection film for insert molding according to claim 1 or 2, wherein the antiglare hard coat layer-forming composition further comprises (d) inorganic fine particles.   The antiglare antireflection film for insert molding according to any one of claims 1 to 3, further comprising a primer layer between the antiglare hard coat layer and the antireflective layer. The thermoplastic transparent substrate film has a two-layer structure of a polycarbonate layer and a polymethyl methacrylate layer,
The antiglare antireflective film for insert molding according to any one of claims 1 to 4, wherein the antiglare hard coat layer is formed on the polymethyl methacrylate layer.   A resin molded article provided with the antiglare antireflective film for insert molding according to any one of claims 1 to 5 on the surface.   An image display device comprising the antiglare antireflective film for insert molding according to any one of claims 1 to 5 or the resin molded article according to claim 6.

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