TW202228998A - Molding film capable of suppressing the occurrence of differences in anti-reflection properties depending on molding position - Google Patents

Abstract

Provided is a molding film capable of suppressing the occurrence of differences in anti-reflection properties depending on molding position. A molding film (1) includes a substrate (11), a hard coat layer (12) provided on one side of the substrate (11), and an anti-reflection layer (13) provided on the hard coat layer (12) on the side opposite to the substrate (11). The thickness of the anti-reflection layer (13) is 0.15 [mu]m or more and 1.00 [mu]m or less, and the pencil hardness of the surface on the anti-reflection layer (13) side is 2H or less.

Description

forming film

The present invention relates to a molding film used in molding applications, and particularly, to a molding film having antireflection properties. .

Films having desired functions are used in various displays (display devices) including automotive displays, but the films may be used in two-dimensional or three-dimensional shapes depending on the type of display and the location in which it is used. As such a molding type, insert molding etc. are mentioned, for example.

On the other hand, in various displays, light is incident on the screen from the outside, and the light is reflected, making it difficult to see the displayed image, especially the displays used in vehicles such as automobiles, trains, and airplanes. Since visibility in various environments is required, solving the above-mentioned problems has become an important issue. In order to solve such a problem, it is proposed to impart an antireflection function or an antiglare function to a film used in a display.

For example, Patent Document 1 discloses an anti-glare anti-reflection film for insert molding, which includes on one side of a thermoplastic transparent base film, in order from the thermoplastic transparent base film side: an anti-glare hard film having a predetermined composition. An anti-glare hard coat layer obtained by hardening the composition for coating layer formation, and an anti-reflection layer. [Prior Art Literature] [Patent Documents]

[Patent Document 1] Japanese Patent Laid-Open No. 2018-176536

[Problems to be solved by the invention]

However, in the anti-glare anti-reflection film for insert molding of Patent Document 1, after molding, some parts have good anti-reflection properties, but some parts have low anti-reflection properties due to the problem of different anti-reflection properties depending on the molding position. .

The present invention has been made in view of such a situation, and an object of the present invention is to provide a film for molding capable of suppressing a difference in antireflection properties depending on the molding position. [Means for solving problems]

In order to achieve the above object, the present invention first provides a forming film comprising a base material, a hard coat layer provided on one side of the base material, and an antireflection film provided on the opposite side of the base material to the hard coat layer The layer forming film is characterized in that the thickness of the antireflection layer is 0.15 μm or more and 1.00 μm or less, and the pencil hardness of the surface on the antireflection layer side is 2H or less (Invention 1).

In the above-mentioned invention (Invention 1), since the thickness of the anti-reflection layer is in the above-mentioned range, when the forming film is formed in a two-dimensional or three-dimensional manner, the anti-reflection layer can also maintain a thickness that exerts anti-reflection properties. resulting in differences in antireflection. Moreover, since the pencil hardness is in the said range, the formability of this film for shaping|molding is excellent.

In the above invention (Invention 1), when the above-mentioned forming film is stretched at a speed of 0.3 m/min to 2 times the length at 130° C., the color difference ΔE of the CIE1976L*a*b* colorimetric system before and after the stretching is calculated by the following formula * _ab , preferably below 1.0 (Invention 2). ΔE* _ab =[(ΔL*) ² +(Δa*) ² +(Δb*) ² ] ^1/2 ΔL*=|after extension L*-before extension L*| Δa*=|after extension The chromaticity a*-the chromaticity before extension a*| Δb*=|the chromaticity after extension b*-the chromaticity before extension b*|

In the above inventions (Inventions 1 and 2), it is preferable that the reflectance of one surface on the side of the antireflection layer in the forming film is 4% or less (Invention 3).

In the above inventions (Inventions 1 to 3), it is preferable that the hard coat layer and the antireflection layer are made of a material that cures a composition containing an active energy ray curable component (Invention 4).

In the above inventions (Inventions 1 to 4), the antireflection layer is composed of a single layer, and the refractive index of the antireflection layer is preferably lower than the refractive index of the hard coat layer (Invention 5). [Inventive effect]

The film for forming of the present invention can suppress the difference in antireflection properties depending on the forming position after forming.

Hereinafter, embodiments of the present invention will be described. Fig. 1 is a cross-sectional view of a molding film 1 according to an embodiment of the present invention. As shown in FIG. 1 , the forming film 1 of the present embodiment includes a substrate 11 , a hard coat layer 12 provided on one side of the substrate 11 , and a hard coat layer 12 provided on the opposite side of the substrate 11 . Anti-reflection layer 13 .

The thickness of the antireflection layer 13 in the film 1 for molding of the present embodiment is 0.15 μm or more. Thereby, even when the film 1 for molding is molded two-dimensionally or three-dimensionally, the anti-reflection layer 13 can maintain a thickness that exhibits anti-reflection properties, thereby suppressing the occurrence of differences in anti-reflection properties depending on the molding position. For example, the anti-reflection property in the extended portion is almost indistinguishable from the anti-reflection property in the non-extended portion. Thereby, the difference in appearance due to the molding position is also suppressed. Moreover, the thickness of the antireflection layer 13 in the film 1 for molding of this embodiment is 1.00 micrometers or less. Thereby, the antireflection property is maintained favorably. That is, by setting the thickness of the antireflection layer 13 of the molding film 1 of the present embodiment to be within the above-mentioned range, the uniformity of the antireflection property after molding and the good balance of the antireflection property are achieved.

The thickness of the anti-reflection layer 13 is preferably 0.18 μm or more, particularly preferably 0.26 μm or more, more preferably 0.30 μm or more, and most preferably 0.46 μm or more, from the viewpoint of the uniformity of anti-reflection properties after molding. good.

The thickness of the antireflection layer 13 is preferably 0.80 μm or less, particularly preferably 0.60 μm or less, more preferably 0.54 μm or less, and most preferably 0.43 μm or less, from the viewpoint of antireflection property.

1. Each component 1-1. Anti-reflection layer The antireflection layer 13 is composed of a single layer, and preferably has a refractive index lower than that of the hard coat layer 12 . Thereby, the reflection light interference with the refractive index difference of the hard-coat layer 12 arises, and the antireflection property of the film 1 for shaping|molding is excellent. As a result, in the display using the film 1 for molding, the reflection of external light can be reduced, and the visibility of the displayed image can be improved. However, the antireflection layer 13 may also have antireflection properties by itself. In this case, for example, the antireflection layer 13 may be a multilayer structure.

The anti-reflection layer 13 of the present embodiment is preferably formed from a composition for an anti-reflection layer. The composition for an anti-reflection layer usually contains a binder resin, and may further contain low-refractive index particles, additives, etc. as required, but it does not limited to this. For example, it may be formed from the composition for antireflection layers which does not contain low-refractive-index particles but contains a low-refractive-index binder resin.

(1) Each ingredient (1-1) As the binder resin, a conventionally known light-transmitting resin or the like can be used. For example, examples of the resin include polyolefin-based resins, acrylic resins, polyester-based resins, styrene-based resins, ABS-based resins, vinyl chloride-based resins, fluorine-based resins, silicone-based resins, and polycarbonates. series resin, polyester urethane series resin, urethane series resin, phenol series resin, urea series resin, melamine series resin, unsaturated polyester series resin, epoxy series resin, polyurethane series resin, polystyrene , polyvinyl alcohol, polyvinylidene chloride, etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the binder resin, it is preferable to use a curable component. The curable component may be a component that is cured by triggering an active energy ray, heat, or the like, and examples thereof include an active energy ray curable component, a thermosetting component, and the like. In the present embodiment, it is preferable to use an active energy ray curable component from the viewpoints of the hardness and scratch resistance of the antireflection layer 13 to be formed.

As a specific active energy ray-curable component, in addition to a polyfunctional (meth)acrylate-type monomer and a (meth)acrylate-type prepolymer, an active energy ray-curable polymer, etc. are mentioned. Among them, polyfunctional (meth)acrylate-based monomers or (meth)acrylate-based prepolymers are preferred. The polyfunctional (meth)acrylate-based monomer and the (meth)acrylate-based prepolymer may be used alone or in combination. In addition, in this specification, (meth)acrylate may represent both acrylate and methacrylate. The same applies to other similar terms.

As the polyfunctional (meth)acrylate-based monomer, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyldiol may be mentioned. Alcohol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxytrimethylacetate, neopentyl glycol di(meth)acrylate ) acrylate, dicyclopentyl di(meth)acrylate, caprolactone-modified di(meth)acrylate dicyclopentenyl, ethylene oxide-modified phosphoric acid di(meth)acrylate, isotriacrylate Polycyanate di(acrylooxyethyl) ester, allylated cyclohexyl di(meth)acrylate, ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2- 2-functional type of acrylyloxyethoxy)phenyl] fluorene, etc.; Neotaerythritol tri(meth)acrylate, neotaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, isocyanuric acid ginseng (propylene Tri-functional type of acyloxyethyl) ester, ε-caprolactone-modified isocyanurate (2-(meth)acryloyloxyethyl) ester, etc.; diglycerol tetra(meth)acrylic acid 4-functional type of ester, neopentaerythritol tetra(meth)acrylate, etc.; 5-functional type of propionic acid-modified dipeutaerythritol penta(meth)acrylate, etc.; ) 6-functional type of acrylate, caprolactone-modified dipivalerythritol hexa(meth)acrylate, etc. These may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, from the viewpoint of the hardness of the antireflection layer 13 to be formed, trifunctional or more is preferable, tetra-functional or more is more preferable, penta-functional or more is particularly preferable, and hexa-functional or more is more preferable.

On the other hand, as a (meth)acrylate type prepolymer, prepolymers, such as polyester acrylate type, epoxy acrylate type, urethane acrylate type, polyol acrylate type, are mentioned, for example. Among them, urethane acrylate-based prepolymers are preferred from the viewpoint of moldability. Among the (meth)acrylate-based prepolymers (especially urethane acrylate-based prepolymers), from the viewpoint of the hardness of the antireflection layer 13 to be formed, trifunctional or higher is preferable, and Four or more functionalities are preferred, five or more functionalities are particularly preferred, and six or more functionalities are more preferred. The upper limit is not particularly limited, but is preferably 20 or less functional, particularly preferably 10 or less functional, and more preferably 8 or less functional.

As a polyester acrylate-based prepolymer, for example, the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol can be (meth)acrylated, or polyvalent The hydroxyl group at the terminal of the oligomer obtained by adding alkane oxidation to a valent carboxylic acid is obtained by (meth)acrylate esterification.

The epoxy acrylate-based prepolymer can be obtained by, for example, reacting and esterifying the oxirane ring of a relatively low molecular weight bisphenol-type epoxy resin or novolak-type epoxy resin with (meth)acrylic acid .

The urethane acrylate-based prepolymer can be obtained by (meth)acrylate esterification of, for example, a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate.

The polyol acrylate-based prepolymer can be obtained, for example, by esterifying the hydroxyl group of the polyether polyol with (meth)acrylate.

The weight average molecular weight of the (meth)acrylate-based prepolymer (preferably, the urethane-acrylate-based prepolymer) is preferably 300 or more from the viewpoint of the moldability of the antireflection layer 13 . 1000 or more is preferred, 2000 or more is particularly preferred, and 3000 or more is more preferred. In addition, the weight average molecular weight of the urethane acrylate-based prepolymer is preferably 100,000 or less, particularly preferably 10,000 or less, and more preferably 6,000 or less, from the viewpoint of hardness and the like. The weight-average molecular weight in this specification is a value in terms of standard polystyrene measured by gel permeation chromatography (GPC).

The above prepolymers may be used alone or in combination of two or more.

Here, as the binder resin, if one having a low refractive index is used, it is not necessary to use the low-refractive index particles described later. As a binder resin with a low refractive index, an active energy ray-curable fluororesin is preferably used, for example. Examples of active energy ray-curable fluororesins include fluororesins having structural units derived from fluorine-containing monomers and structural units derived from crosslinkable monomers. Specific examples of the fluorine-containing monomer unit include vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-di Fluoroolefins such as perfluoro-2,2-dimethyl-1,3-dioxole; fluorinated alkyl ester derivatives of (meth)acrylic acid; fluorinated vinyl ethers, etc. As a crosslinkable monomer, other than a (meth)acrylate monomer, the (meth)acrylate monomer etc. which have a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc. are mentioned.

(1-2) Low refractive index particles The composition for an antireflection layer of the present embodiment preferably contains low refractive index particles. By containing the low-refractive index particles, the refractive index of the anti-reflection layer 13 can be effectively lowered, so that the anti-reflection property is more excellent.

As the low-refractive index particles, for example, hollow silica particles, porous silica particles, etc. are preferably used, and among them, hollow silica particles are preferred. The hollow silica particles can be modified with organic substances for the purpose of improving dispersibility. In addition, the hollow silica particles are also preferably in the form of an organosol (colloidal) (hollow silica sol).

The hollow silica particles have fine voids in an open state or a closed state in the particles. The hollow silica particles are filled with gas (air) in the above-mentioned voids, so the refractive index is relatively low. Therefore, by using the fine particles, the refractive index of the anti-reflection layer 13 can be effectively lowered without impairing the transparency of the anti-reflection layer 13 . The hollow silica particles may have independent pores, continuous cells, or both independent cells and continuous cells.

The refractive index of the low-refractive-index particles is preferably 1.45 or less, more preferably 1.40 or less, particularly preferably 1.35 or less, and more preferably 1.30 or less. Thereby, the difference in refractive index between the antireflection layer 13 and the hard coat layer 12 becomes larger, so that the antireflection property is more excellent. The lower limit of the refractive index of the low-refractive index particles is not particularly limited, but is usually preferably 1.00 or more, particularly preferably 1.10 or more, and more preferably 1.15 or more. In addition, the refractive index of the low-refractive-index particle in this specification is measured by the minimum deflection angle method.

The average particle diameter of the low refractive index particles is preferably 5 nm or more, particularly preferably 10 nm or more, more preferably 30 nm or more, and most preferably 50 nm or more, from the viewpoint of exerting a low refractive index. The average particle diameter of the low-refractive-index particles is preferably 300 nm or less, particularly preferably 200 nm or less, and more preferably 100 nm or less, from the viewpoint of less light scattering and excellent transparency. In addition, the average particle diameter of the low-refractive-index particle in this specification is measured by the centrifugal sedimentation light transmission method.

When the composition for an antireflection layer of the present embodiment contains low-refractive-index particles, the content of the low-refractive-index particles is 10 parts by mass relative to 100 parts by mass of the binder resin from the viewpoint of exerting a low refractive index. part or more, preferably 40 parts by mass or more, particularly preferably 60 parts by mass or more. In addition, the content of the above-mentioned low-refractive index particles is preferably 400 parts by mass or less, preferably 200 parts by mass or less, relative to 100 parts by mass of the binder resin, from the viewpoint of increasing the hardness of the antireflection layer 13 obtained. Preferably, 100 parts by mass or less is particularly preferred.

(1-3) Other ingredients The composition for an antireflection layer in the present embodiment may contain various additives in addition to the above-mentioned components. As various additives, for example, photopolymerization initiators, surface conditioners, leveling agents, antifouling agents, dispersants, ultraviolet absorbers, antioxidants, light stabilizers, antistatic agents, silane coupling agents, antifouling agents, etc. Aging agent, thermal polymerization terminator, colorant, refractive index modifier, surfactant, storage stabilizer, plasticizer, lubricant, defoamer, organic filler, wettability improver, coating surface improver, etc.

The composition for an antireflection layer contains an active energy ray curable component, and when an ultraviolet ray is used as an active energy ray, the composition for an antireflection layer preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2 ,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- Ketone, 1-Hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌olinyl-propan-1-one, 4-(2-hydroxyethyl ketone) Oxy)phenyl-2 (hydroxy-2-propyl) ketone, diphenyl ketone, p-phenyl benzophenone, 4,4'-diethylamino benzophenone, dichlorodiphenyl ketone ketone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tertiary butyl anthraquinone, 2-aminoanthraquinone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2 -Chlorothiaxanthone, 2,4-Dimethylthioxanthone, 2,4-Diethylthioxanthone, Benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethyl ketal Amine benzoates, etc. These may be used alone or in combination of two or more.

The content of the photopolymerization initiator in the composition for an antireflection layer is preferably 0.01 part by mass or more, particularly preferably 0.1 part by mass or more, as the lower limit, relative to 100 parts by mass of the active energy ray curable component, and More than 1 serving is better. Moreover, as an upper limit, 20 mass parts or less is preferable, 15 mass parts or less is especially preferable, and 10 mass parts or less is more preferable.

The composition for an antireflection layer of the present embodiment preferably contains a surface conditioner from the viewpoint of lowering the coefficient of kinetic friction of the surface of the antireflection layer 13 (surface of the molding film 1 ) and improving scratch resistance. As a surface conditioner, a silicone type surface conditioner, a fluorine type surface conditioner, and an acrylic surface conditioner are mentioned, for example. In the present embodiment, it is preferable to use a silicone-based surface conditioner or a fluorine-based surface conditioner from the viewpoint that the coefficient of kinetic friction of the surface of the molding film 1 can be easily set to a preferred range described later. More specifically, silicone-based oligomers (including reactive ones), silicone oils (including modified ones), fluorine-based oligomers (including reactive ones), and the like can be mentioned. Among them, it is preferable to use a reactive fluorine-based oligomer or a reactive silicone-based oligomer, and a fluorine-based oligomer or silicone having a (meth)acryloyl group as an active energy ray reactive group is preferably used Oligomers are particularly preferred.

The content of the surface modifier in the composition for an antireflection layer is preferably 1 part by mass or more, particularly preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, relative to 100 parts by mass of the binder resin. In addition, the content of the above-mentioned surface conditioner is preferably 30 parts by mass or less, particularly preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, relative to 100 parts by mass of the binder resin.

(2) Physical properties of the anti-reflection layer The refractive index of the antireflection layer 13 is preferably 1.48 or less, more preferably 1.46 or less, particularly preferably 1.45 or less, and more preferably 1.44 or less. Thereby, the refractive index of the antireflection layer 13 is easily lower than the refractive index of the hard coat layer 12, so that the antireflection property of the film 1 for molding is more excellent. The lower limit of the refractive index is not particularly limited, but is usually preferably 1.30 or more, particularly preferably 1.35 or more. In addition, the refractive index of the antireflection layer in this specification can be measured by ellipsometry.

1-2 hard coat The hard coat layer 12 in the forming film 1 is preferably formed of a composition for a hard coat layer, which usually contains a binder resin, and may contain fine particles, additives, and the like as necessary.

(1) Each ingredient (1-1) Binder resin As the binder resin, the same components as those contained in the composition for an antireflection layer for forming the antireflection layer 13 described above can be used. Among them, from the viewpoint of being excellent in resistance to molding, a (meth)acrylate-based prepolymer is preferable, and a urethane acrylate-based prepolymer is particularly preferable.

Polyfunctional (meth)acrylate-based monomers or (meth)acrylate-based prepolymers (especially urethane acrylate-based prepolymers) to prevent damage to the hard coat layer 12 due to molding From a viewpoint, it is preferable that it is 5 or less functional, and it is especially preferable that it is tetrafunctional or less, and it is more preferable that it is trifunctional or less. The lower limit is not particularly limited, but it is preferably bifunctional or more.

The weight-average molecular weight of the urethane acrylate-based prepolymer, from the viewpoint of the uniformity of antireflection properties after molding, is preferably 500 or more, more preferably 1,000 or more, particularly preferably 3,000 or more, and 4,500 The above is better. In addition, the weight average molecular weight of the urethane acrylate-based prepolymer is preferably 100,000 or less, particularly preferably 10,000 or less, and more preferably 7,000 or less, from the viewpoint of excellent hardness.

The refractive index of the binder resin for the hard coat layer 12 is preferably 1.46 to 1.75, and 1.48 is preferable from the viewpoint of obtaining a hard coat layer 12 having an increased refractive index difference with the antireflection layer and excellent scratch resistance. ~1.65 is better, and 1.49~1.54 is particularly good.

(1-2) Microparticles The composition for a hard coat layer of the present embodiment may not contain fine particles, but may contain fine particles in order to obtain desired physical properties. For example, from the viewpoint of imparting glare suppressing properties or anti-glare properties to the hard coat layer 12, fine particles having light diffusing properties (light diffusing fine particles) may be contained.

Examples of the light-diffusing fine particles include inorganic fine particles such as silica, calcium carbonate, aluminum hydroxide, magnesium hydroxide, clay, talc, and titanium dioxide; polymethyl methacrylate. Organic light-transmitting particles of acrylic resin such as ester resin, polystyrene resin, polymethyl methacrylate-polystyrene copolymer, polyethylene resin, epoxy resin, etc.; Particles composed of silicon-containing compounds with an organic intermediate structure (eg, Tospearl series manufactured by Momentive Performance Materials Japan), etc. The above light-diffusing fine particles may be used alone or in combination of two or more.

The shape of the light-diffusing fine particles may be a spherical shape with uniform light diffusion, particularly a true spherical shape, or a random irregular shape. The average particle diameter of the light-diffusing fine particles measured by the laser diffraction method is preferably 0.5 μm or more, particularly preferably 1.0 μm or more, and more preferably 1.2 μm or more. The average particle size is preferably 10 μm or less, more preferably 5 μm or less, particularly preferably 3 μm or less, and more preferably 2 μm or less. By setting the average particle diameter to be within the above-mentioned range, it becomes easy to achieve both desired haze value expression and antireflection properties.

The refractive index of the light diffusing particles is preferably 1.40-1.80, preferably 1.42-1.60, and preferably 1.43-1.48. take this. It is easier to balance anti-reflection and anti-glare properties. In addition, the refractive index of the light-diffusion fine particle in this specification is the value measured as follows. The microparticles to be measured are placed on a glass slide, a refractive index standard is dropped on the microparticles, and then a cover glass is covered to prepare a sample. The sample was observed with a microscope in accordance with the B method of JIS K7142:2014, and the refractive index of the refractive index standard solution of the particle profile, which was the most difficult to observe, was defined as the refractive index of the particle.

Regarding the particle size distribution of the irregular light-diffusing fine particles, from the viewpoint of random light diffusion, the coefficient of variation (CV value) of the particle size represented by the following formula (1) is preferably 50% or more, and particularly 60% or more good, more preferably more than 70%. In addition, the above-mentioned CV value is preferably 200% or less, more preferably 175% or less, particularly preferably 150% or less, and more preferably 125% or less. Coefficient of variation of particle size (CV value) = (standard deviation particle size/average particle size) x 100...(1)

In addition, the average particle diameter of the light-diffusion fine particle in this specification is measured by the centrifugal sedimentation light transmission method. In this specification, the average particle size measured by the centrifugal sedimentation light transmission method is obtained by sufficiently stirring 1.2 g of fine particles and 98.8 g of isopropyl alcohol as a sample for measurement, and using a centrifugal automatic particle size distribution analyzer (HORIBA Manufacturing Co., Ltd., CAPA-700 )conduct. In this specification, the coefficient of variation (CV value) of the particle diameter of the light-diffusing fine particles is obtained by the dynamic light scattering method.

The content of the light-diffusing fine particles in the composition for a hard coat layer is preferably 0.1 part by mass or more, preferably 1 part by mass or more, particularly preferably 5 parts by mass or more, preferably 10 parts by mass or more, relative to 100 parts by mass of the binder resin. The mass part or more is more preferable. Thereby, desired light diffusivity is easily obtained. In addition, the content of the light-diffusing fine particles is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and 20 parts by mass relative to 100 parts by mass of the binder resin from the viewpoint of the formability of the hard coat layer 12 The following is the best.

(1-3) Other ingredients The composition for hard coat layers in the present embodiment may contain various additives in addition to the above-mentioned components. As various additives, those contained in the above-mentioned composition for an antireflection layer for forming the antireflection layer 13 can be used.

For example. The composition for hard coat layers contains an active energy ray curable component, and when ultraviolet rays are used as active energy rays, the composition for hard coat layers preferably contains a photopolymerization initiator. The kind or content of the photopolymerization initiator is the same as that of the composition for an antireflection layer.

(2) Physical properties of hard coating The refractive index of the hard coat layer 12 is preferably higher than that of the antireflection layer 13 . Specifically, the refractive index of the hard coat layer 12 is preferably 1.46 or more, particularly preferably 1.48 or more, and more preferably 1.50 or more. Thereby, the difference in refractive index between the hard coat layer 12 and the antireflection layer 13 can be enlarged, and the antireflection property of the film 1 for molding can be made more excellent. The upper limit of the refractive index of the hard coat layer 12 is not particularly limited, but is usually preferably 1.75 or less, particularly preferably 1.65 or less, and more preferably 1.58 or less. In addition, the measuring method of the refractive index of the hard-coat layer 12 in this specification is shown in the test example mentioned later.

The thickness of the hard coat layer 12 is preferably 0.5 μm or more, more preferably 1 μm or more, particularly preferably 2 μm or more, and more preferably 3 μm or more. Thereby, the formability is further excellent. In addition, the thickness of the hard coat layer 12 is preferably 30 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less. Thereby, the occurrence of curling due to curing shrinkage can be suppressed.

1-3. Substrate The base material 11 is not particularly limited, and a resin film having desired formability is preferably used. As such a resin film, a polyester film, polyethylene film, polypropylene film, etc., such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. are mentioned, for example Polyolefin film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film (polyvinylidene chloride film), polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysilicon film, polyetheretherketone film, polyethersilver Film, polyetherimide film, fluororesin film, polyamide film, acrylic resin film, urethane resin film, norbornene polymer film, cyclic olefin polymer film, cyclic conjugated diene polymer A resin film such as a polymer film, a vinyl alicyclic hydrocarbon polymer film, or the like, or a laminate film of these. Among them, it is preferable to use a polycarbonate film, a polyvinyl chloride film, a urethane resin film, or the like in terms of formability and mechanical strength.

In addition, in the above-mentioned base material 11, in order to improve the adhesion with the layer provided on the surface, it is possible to perform plasma treatment, oxidation method, unevenness method, etc. on one side or both sides as needed. Surface treatment. Examples of the above-mentioned oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone/ultraviolet treatment, and the like, and examples of the concavo-convex method include sandblasting treatment and solvent treatment. Wait. These surface treatment methods can be appropriately selected according to the type of the base material 11 , but in general, the corona discharge treatment method is preferably used from the viewpoints of the effect of improving the adhesion, workability, and the like.

The thickness of the base material 11 is preferably 10,000 μm or less, more preferably 1,000 μm or less, particularly preferably 400 μm or less, and more preferably 200 μm or less, from the viewpoint of formability. Moreover, the thickness of the base material 11 is preferably 30 μm or more, more preferably 80 μm or more, particularly preferably 120 μm or more, and more preferably 160 μm or more, from the viewpoint of mechanical strength.

1-4. Other components The forming film 1 of the present embodiment may have an adhesive layer on the side of the substrate 11 opposite to the hard coat layer 12 . The adhesive constituting the adhesive layer is not particularly limited, and conventional adhesives such as acrylic adhesives, rubber-based adhesives, and silicone-based adhesives can be used, and those having predetermined transparency are preferably used. .

Moreover, when the forming film 1 of this embodiment includes the above-mentioned adhesive layer, the forming film 1 of this embodiment may have a release film laminated on the adhesive layer on the side opposite to the base material 11 . The release film is not particularly limited as long as it has desired releasability on its release surface (surface at the point of contact with the adhesive layer), and conventional release films such as peeling treatment with a release agent on one side of a resin film can be used.

2. Physical properties of the forming film, etc. (1) Haze value The upper limit value of the haze value of the forming film 1 of the present embodiment is not particularly limited, but from the viewpoint of high definition, it is preferably 40% or less, more preferably 20% or less, and 10% or less It is particularly good, and it is better to be less than 1%. On the other hand, the lower limit value of the haze value of the forming film 1 is not particularly limited, but may be 0%, or 0.1% or more. Moreover, when providing glare suppressing property or anti-glare property to the film 1 for molding, 1% or more is preferable, 3% or more is more preferable, and 5% or more is especially preferable. In addition, the measurement method of a haze value is shown in the test example mentioned later.

(2) Total light transmittance The total light transmittance of the forming film 1 of the present embodiment is preferably 80% or more, more preferably 85% or more, particularly preferably 88% or more, and more preferably 90% or more. When the total light transmittance is more than 80%, the transparency is very high, and it is especially suitable for optical applications (displays). In addition, the measuring method of the total light transmittance is shown in the test example mentioned later.

(3) Pencil hardness Pencil on the opposite surface of the antireflection layer 13 in the molding film 1 of the present embodiment to the hard coat layer 12 (surface on the side of the molding film 1 on the antireflection layer 13 side; hereinafter referred to as "the surface of the molding film 1") The hardness is preferably 2H or less, more preferably H or less. Thereby, the moldability of the film 1 for molding is excellent. In addition, the above-mentioned pencil hardness is preferably AB or more, particularly preferably F or more, and more preferably H or more. Thereby, the surface of the film 1 for shaping|molding has sufficient hardness, and can exhibit excellent scratch resistance. In addition, the measuring method of the pencil hardness is shown in the test example mentioned later.

(4) Reflectivity The reflectance of the surface of the forming film 1 of the present embodiment is preferably 4% or less, more preferably 3.5% or less, particularly preferably 3% or less, and more preferably 2.5% or less. Thereby, in the display panel using this film 1 for molding, the reflection of external light can be reduced, and the visibility of an image or a film can be improved. In addition, the lower limit value of the said reflectance is not specifically limited, About 1.4% or more is preferable. In addition, the measuring method of reflectance in this specification is shown in the test example mentioned later.

(5) Color difference ΔE ^* _ab When the forming film 1 of the present embodiment is stretched at 130° C. at a speed of 0.3 m/min to twice its length, the CIE1976L*a*b* color appearance calculated by the following formula before and after the stretching The color difference ΔE ^* _ab of the system is preferably 1.0 or less, more preferably 0.9 or less, particularly preferably 0.8 or less, and more preferably 0.7 or less. ΔE* _ab =[(ΔL*) ² +(Δa*) ² +(Δb*) ² ] ^1/2 ΔL*=|after extension L*-before extension L*| Δa*=|after extension The chromaticity a* - the chromaticity before stretching a* | Δb* = | the chromaticity after stretching b* - the chromaticity before stretching b*| There can be little difference between the anti-reflection and the anti-reflection in the non-extended portion.

The lower limit of the color difference ΔE* _ab is not particularly limited, but is preferably 0.1 or more, particularly preferably 0.2 or more, and more preferably 0.3 or more. In addition, the measuring methods of the lightness L*, the chromaticity a*, and the chromaticity b* in this specification are shown in the test example mentioned later.

3. Manufacturing method of film for forming The manufacturing method of the forming film 1 is not particularly limited. For example, after forming the hard coat layer 12 on one side of the base material 11, it is preferable to form the antireflection layer 13 on the opposite side of the base material 11 in the hard coat layer 12. . For example, the hard-coat layer 12 can be formed by apply|coating the coating liquid of the composition for hard-coat layers mentioned above to the base material 11, and hardening. After the hard coat layer 12 is formed on the substrate 11 , a coating liquid such as a composition for an antireflection layer is applied to the surface of the hard coat layer 12 on the opposite side to the substrate 11 and cured to form the antireflection layer 13 . The coating liquid of the said composition for hard-coat layers and the said composition for antireflection layers may contain a solvent as needed.

The solvent for preparing the composition for hard coat layers is not particularly limited and can be used as long as it can be used for improvement of coatability, adjustment of viscosity, adjustment of solid content concentration, etc., and for dissolving binder resin and the like.

Specific examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate and acetic acid Esters of butyl ester, ethyl lactate, γ-butyrolactone, etc; Ethers such as butyl ether (butyl celusol), propylene glycol monomethyl ether, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; dimethylformamide, dimethylacetamide, N-methylpyrrole amides such as pyridone and the like.

Coating of the composition for a hard coat layer may be carried out by a conventional method, for example, a bar coating method, a blade coating method, a meyer bar coating method, a roll coating method, a blade coating method, a die coating method, a What is necessary is just to carry out by a coating method or a gravure coating method. After the hard coat layer composition is applied, the coating film is preferably dried at 40° C. or higher and 120° C. or lower for 5 minutes or less.

The hardening of the coating film can be carried out depending on the type of binder resin used, and can be carried out, for example, by heat treatment or irradiation of active energy rays. In particular, in the case of using the aforementioned polyfunctional (meth)acrylate monomer or (meth)acrylate-based prepolymer as the binder resin, the hard coat composition is hardened so that in an air atmosphere, It is preferable to irradiate the coating film of the composition for hard coats with active energy rays such as ultraviolet rays and electron rays. Adhesion with the antireflection layer 13 can be improved by curing in an air atmosphere. Ultraviolet irradiation can be carried out by high pressure mercury lamp, Fusion H lamp, xenon lamp, etc. The irradiation amount of ultraviolet rays is 50mW/ ^cm2 or more and 1000mW/ ^cm2 or less, and the light amount is 50mW/ ^cm2 or more and 1000mW/ ^cm2 or less. good. On the other hand, the electron irradiation can be performed by an electron beam accelerator or the like, and the irradiation amount of the electron beam is preferably 10 krad or more and 1000 krad or less.

As the solvent for preparing the composition for an antireflection layer, the aforementioned solvent for preparing the composition for a hard coat layer can be used. Moreover, the coating method of the composition for antireflection layers, and the hardening method of forming a coating film can be performed by the same method as the coating method and the hardening method of the composition for hard coat layers, respectively. However, the hardening of the composition for an antireflection layer is preferably carried out in a nitrogen atmosphere. Thereby, the scratch resistance of the antireflection layer 13 can be further improved.

4. Use of forming film The molding film 1 of the present embodiment can be used for molding two-dimensionally or three-dimensionally, for example, in displays for vehicles such as automobiles, trains, and airplanes, displays in vehicles such as displays for navigation systems, and the like. The molding method is not particularly limited, and examples thereof include insert molding, three-dimensional overlay method (TOM) molding, and the like.

The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above-described embodiment is intended to include all design changes or equivalents that belong to the technical scope of the present invention.

For example, other layers may be interposed between the base material 11 and the hard coat layer 12 , or between the hard coat layer 12 and the antireflection layer 13 in the forming film 1 , or the antireflection layer 13 may be on the opposite side of the hard coat layer 12 Other layers may also be formed on the surface. [Example]

Hereinafter, the present invention will be described in more detail with examples and the like, but the scope of the present invention is not limited to these examples and the like.

[Preparation Example 1] Composition for hard coat layer (HC-1) A trifunctional urethane acrylate prepolymer (A; manufactured by AICA Industries, Ltd., weight average molecular weight: 5500) as a binder resin 100 parts by mass (in terms of solid content; the same below), and a photopolymerization initiator 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone (F) was mixed and diluted using propylene glycol monoethyl ether (PGM) as a solvent to obtain a coating liquid of the hard coat layer composition (HC-1).

[Preparation Example 2] Composition for hard coat layer (HC-2) 100 parts by mass of trifunctional urethane acrylate prepolymer (A; manufactured by AICA Industrial Co., Ltd., weight average molecular weight: 5500) as binder resin, silica fine particles (E; material: silica, Shape: irregular, refractive index: 1.46, average particle diameter: 1.5 μm, coefficient of variation of particle diameter: 83%) 15 parts by mass, and 1-hydroxycyclohexyl phenyl ketone (F) 5 as a photopolymerization initiator parts by mass, mixed and diluted using propylene glycol monoethyl ether (PGM) as a solvent to obtain a coating liquid of the hard coat layer composition (HC-2).

[Preparation Example 3] Composition for hard coat layer (HC-3) 100 parts by mass of neotaerythritol hexaacrylate (C) as a binder resin, and 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone (F) as a photopolymerization initiator, propylene glycol monoethyl ether ( PGM) was mixed and diluted to obtain a coating liquid of the hard coat layer composition (HC-3).

[Preparation Example 4] Composition for antireflection layer (LR-1) 100 parts by mass of hexafunctional urethane acrylate prepolymer (B; manufactured by AICA Industries, Ltd., weight-average molecular weight: 4000) as binder resin, and hollow silica fine particles (D; average particle diameter) as low-refractive index particles : 60 nm, refractive index 1.25) 75 parts by mass, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌olinopropan-1-one (G) as a photopolymerization initiator ) 5 parts by mass, and 8 parts by mass of a reactive fluorine-based oligomer (H; manufactured by DIC Corporation, product name "Megafac RS-75") as a surface conditioner, methyl isobutyl ketone (MIBK) and propylene glycol were used A 1:2 (volume ratio) mixed solvent of monoethyl ether (PGM) was mixed and diluted to obtain a coating liquid of the antireflection layer composition (LR-1).

The compositions of Preparation Examples 1 to 4 are shown in Table 1. In addition, details such as the abbreviations shown in Table 1 are as follows. A: Trifunctional urethane acrylate prepolymer (manufactured by AICA Industries, Ltd., weight average molecular weight: 5500) B: 6-functional urethane acrylate prepolymer (manufactured by AICA Industries, Ltd., weight average molecular weight: 4000) C: Neopentaerythritol hexaacrylate D: Hollow silica particles (average particle size: 60 nm, refractive index: 1.25) E: Silicon oxide particles (Material: Silicon oxide, Shape: Irregular, Average particle size: 1.5μm, Coefficient of variation of particle size: 83%, Refractive index: 1.46) F: 1-Hydroxycyclohexyl phenyl ketone G: 2-Methyl-1-[4-(methylthio)phenyl]-2-𠰌olinopropan-1-one H: Reactive fluorine-based oligomer (manufactured by DIC Corporation, product name "Megafac RS-75")

[Example 1] The hard coating obtained in Preparation Example 1 was coated with a wire bar on one side of a polycarbonate film (S1; manufactured by Mitsubishi Gas Chemical Co., Ltd., product name "Iupilon DF02U", thickness 180 μm) with improved surface hardness as a substrate. The coating liquid of composition (HC-1) was dried. Then, the ultraviolet-ray was irradiated to this coating film in an air atmosphere, and the hard-coat layer of 10 micrometers in thickness was formed.

Next, the coating liquid of the composition for antireflection layers (LR-1) obtained in Preparation Example 4 was applied with a wire bar on the surface of the above-mentioned hard coat layer and dried. Then, in a nitrogen atmosphere, the coating film was irradiated with ultraviolet rays to form an antireflection layer with a thickness of 0.30 μm. Thereby, the film for shaping|molding formed by laminating|stacking a base material, a hard-coat layer, and an antireflection layer in this order is obtained.

[Examples 2 to 4, Comparative Examples 1 to 3] A film for molding was produced in the same manner as in Example 1, except that the type and thickness of the composition for hard coat layers and the type and thickness of the composition for antireflection layers were changed as shown in Table 2.

[Test Example 1] (Measurement of Refractive Index) The hard coat composition (HC-2) prepared in each preparation example was prepared from HC-2 with silica particles (E) removed (HC-2'). The respective coating liquids of the composition for hard coat layer (HC-1, HC-2', HC-3) and the composition for antireflection layer (LR-1) were applied to a single layer in the same manner as in Example 1. A polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name "Cosmo Shine A4100", thickness: 50 μm) with an easy-adhesion layer on the surface was hardened to form a layer with a thickness of 100 nm. The surface of the easy-adhesion layer was rubbed with sandpaper, and then blackened with a pen (manufactured by ZEBRA, product name "McKee Black").

The refractive index of each obtained layer was measured using a spectroscopic ellipsometer (manufactured by J.A. WOOLLAM, product name "M-2000") at a measurement wavelength of 589 nm and a measurement temperature of 23°C. The results are shown in Table 1. In addition, when calculating the refractive index of the hard coat layer obtained by considering the refractive index of the silicon oxide fine particles (E) and their respective composition ratios, the value to two decimal places is the same as the refractive index in Table 1.

[Test Example 2] (Measurement of haze value) The haze value (%) was measured according to JIS K7136:2000 using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "NDH5000") for the forming films produced in Examples and Comparative Examples. The results are shown in Table 2.

[Test Example 3] (Measurement of total light transmittance) The total light transmittance (%) was measured according to JIS K7361-1:1997 using a haze meter (manufactured by Nippon Denshoku Industries, product name "NDH5000") for the forming films produced in Examples and Comparative Examples. The results are shown in Table 2.

[Test Example 4] (Measurement of Pencil Hardness) The antireflection layer surface of the forming film was measured in accordance with JIS K5600 using an electric pencil scratch hardness tester (manufactured by Yasuda Seiki Co., Ltd., product name "No. 553-M1") for the forming films produced in the Examples and Comparative Examples. pencil hardness. The results are shown in Table 2.

[Test Example 5] (Measurement of Reflectance) The base material side surface of the molding films produced in the examples and comparative examples was pasted through an acrylic transparent adhesive (manufactured by LINTEC, product name "OPTERIA MO-3006C", refractive index 1.49, haze value: <1.0%) Attached to one side of a black acrylic sheet (manufactured by Mitsubishi Rayon, product name "ACRYLITE L502"). And, with respect to the surface of the antireflection layer in this forming film, using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by Shimadzu Corporation, product name "UV-3600"), the minimum reflectance in the visible light region of 360 to 830 nm was used as the reflectance. (%). The results are shown in Table 2.

In addition, the antireflection performance was evaluated according to the following criteria. The results are shown in Table 2. 3: Excellent anti-reflection performance with a reflectance of 2.0% or less 2: The anti-reflection performance with reflectivity exceeding 2.0% and below 4.0% is excellent 1: The anti-reflection performance with a reflectance exceeding 4.0% is poor

[Test Example 6] (Evaluation of Formability) A sample having a width of 10 mm x 75 mm in length was cut out from the films for molding produced in the Examples and Comparative Examples. The sample was set in a tensile tester (manufactured by ORIENTEC, product name "TENSILON"), and was stretched by 20% in the longitudinal direction of the sample at a tensile speed of 0.3 m/min in an environment of 150°C. After that, the appearance of the sample was visually observed, and the formability was evaluated according to the following criteria. The results are shown in Table 2. 2: It can be molded without defects 1: Problems such as breakage or breakage occur

[Test Example 7] (Measurement of Color Difference ΔE ^* _ab ) In the Examples and Comparative Examples, except that the base material was changed to a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name "Soft Shine A1597") which is easy to form , thickness: 25 μm), a molding film was produced in the same manner as in the Examples and Comparative Examples.

About the obtained film for molding, the lightness L* and chromaticity a specified by the CIE1976 L*a*b* color system were measured using a synchronous photometric spectrophotometer (manufactured by Nippon Denshoku Industries, Ltd., product name "SQ2000"). * and chromaticity b* (value before extension).

Next, samples having a width of 10 mm x 75 mm in length were cut out from the films for molding produced in Examples and Comparative Examples. This sample was set in a tensile tester (manufactured by ORIENTEC, product name "TENSILON"), and was stretched in the longitudinal direction of the sample at a tensile speed of 0.3 m/min in an environment of 130° C. to twice its length (100% stretch) . For the sample in this state, the lightness L*, the chromaticity a*, and the chromaticity b* (values after stretching) were measured in the same manner as described above.

From the obtained results, the color difference ΔE ^* _ab was calculated based on the following formula. The results are shown in Table 2. ΔE* _ab =[(ΔL*) ² +(Δa*) ² +(Δb*) ² ] ^1/2 ΔL*=|after extension L*-before extension L*| Δa*=|after extension The chromaticity a*-the chromaticity before extension a*| Δb*=|the chromaticity after extension b*-the chromaticity before extension b*|

In addition, the uniformity of antireflection properties before and after stretching was evaluated according to the following criteria. The results are shown in Table 2. 2: When ΔE ^* _ab is 1.0 or less, the difference in appearance before and after stretching is small. 1: When ΔE ^* _ab exceeds 1.0, the difference in appearance before and after stretching is large.

〔Table 1〕

〔Table 2〕

As can be seen from Table 2, the films for molding produced in the examples were excellent in antireflection properties and suppressed the difference in antireflection properties due to molding (stretching). [Industrial Availability]

The film for molding of the present invention is suitable as a film that is two-dimensionally or three-dimensionally formed and exhibits antireflection properties, for example, as a display used in a carrier.

1: Forming film 11: Substrate 12: Hard coating 13: Anti-reflection layer

[FIG. 1] A cross-sectional view of a film for molding according to an embodiment of the present invention.

1: Forming film

11: Substrate

12: Hard coating

13: Anti-reflection layer

Claims (5)

A film for forming, which is the film for forming with a base material, a hard coat layer arranged on one side of the aforementioned base material, and an anti-reflection layer that is arranged on the opposite side of the aforementioned hard coat layer with the base material, characterized in that The thickness of the aforementioned anti-reflection layer is 0.15 μm or more and 1.00 μm or less, The pencil hardness of the surface on the side of the antireflection layer is 2H or less. The film for forming according to claim 1, wherein when the film for forming is stretched to twice its length at 130° C. at a speed of 0.3 m/min, before and after the stretching, the CIE1976L*a*b* appearance color calculated by the following formula The color difference ΔE* _ab of the system is 1.0 or less, ΔE* _ab =[(ΔL*) ² +(Δa*) ² +(Δb*) ² ] ^1/2 ΔL*=|luminance L* after stretching - before stretching Lightness L*| Δa*=|chromaticity a* after stretching-chromaticity a* before stretching| Δb*=|chromaticity b* after stretching-chromaticity b*| before stretching. The film for forming according to claim 1, wherein the reflectance of the surface on the side of the antireflection layer in the film for forming is 4% or less. The forming film according to claim 1, wherein the hard coat layer and the antireflection layer are made of a material that hardens a composition containing an active energy ray curable component. The forming film according to any one of claims 1 to 4, wherein the antireflection layer is composed of a single layer, and the antireflection layer has a lower refractive index than the hard coat layer.

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