KR101492307B1 - Hard coat film and resin molded product - Google Patents

Abstract

[PROBLEMS] To provide a hard coat film having sufficient hard coat property and crack resistance.
A hard coat film (10) of the present invention has a hard coat layer (12) laminated on one side of a base film (11), and the hard coat layer (12) , A Martens hardness (HM) of 250 N / mm 2 or more, a bending hardness (Hupl) of 800 N / mm 2 or more, and an indentation elastic modulus (EIT) of 5,000 MPa or less.

Description

Technical Field [0001] The present invention relates to a hard coat film and a resin molded product,

The present invention relates to a hard coat film and a resin molded article using the same.

There has been known a hard coat film for insert molding in which a metal vapor deposition film or a print layer is formed on one side of a base film and a hard coat layer serving as a surface protective layer is formed on the other side of the base film (Patent Documents 1 and 2) .

Patent Document 1: Japanese Patent Application Laid-Open No. 2005-288720

Patent Document 2: Japanese Patent Application Laid-Open No. 2005-305786

In general, however, hard coat properties are required for the hard coat layer used for surface protection of a molded article. For example, a pencil hardness of H or higher and a hardness of 300 g or more are required for a steel wool test. For this reason, the hard coat layer is usually composed of a hardening type resin excellent in hard coat properties such as electron beam hardening type resin and ultraviolet ray hardening type resin.

However, when the hard coat film described in Patent Documents 1 and 2 is used for actual insert molding, the surface of the hard coat layer tends to be cracked, whitened or cracked at the time of molding. In general, since the surface of the molded article is a curved surface or has an angle, occurrence of cracks or the like is difficult to avoid.

On the contrary, it is considered that the flexibility of the hard coat layer is enhanced by adding a thermoplastic resin to the resin component constituting the hard coat layer. However, in this case, there is a problem that the hard coat property of the hard coat layer is deteriorated and it can not withstand the load of the steel wool test described above.

It is an object of the present invention to provide a hard coat film having sufficient hard coatability and crack resistance. It is also an object of the present invention to provide a resin molded article in which the hard coat film is integrated.

The present invention solves the above problems by appropriately adjusting the hard coat property of the hard coat layer formed on at least one side of the base film.

According to the present invention, since the hard coat property of the hard coat layer is appropriately adjusted, sufficient hard coat property and crack resistance can be provided.

1 is a cross-sectional view showing a hard coat film of an example of the invention.
2 is a graph showing an example of the hF curve.
Explanation of symbols
10 ... Hard coat film, 11 ... Base film, 12 ... Hard coat layer, 13 ... Metal deposition layer, 14 ... Printed layer, 15 ... Adhesive layer.

Best Mode for Carrying Out the Invention Hereinafter, embodiments of the present invention will be described based on the drawings.

"Hardcoat film"

As shown in Fig. 1, the hard coat film 10 of the present embodiment has a hard coat layer 12 laminated on one surface of a base film 11. Fig.

The hard coat layer 12 of this example has its hard coat property adjusted appropriately. More specifically, the Martens hardness (HM) and the bending hardness (Hupl) are larger than a specific value, and the indentation modulus (corresponding to Young's modulus) EIT is adjusted to be smaller than a specific value.

The inventors of the present invention have studied a specific index relating to the hard coat property of the hard coat layer 12 in order to achieve both the hard coat property and the cracking resistance and found that the martens hardness and the firing hardness are larger than a specific value And the hard coat properties of the hard coat layer 12 are adjusted so that the indentation modulus becomes smaller than a specific value, the above-mentioned hard coat property and crack resistance can be compatible with each other. Since the hard coat layer 12 of this example is appropriately adjusted in its hard coat property, it can be provided with sufficient hard coat property and crack resistance.

The Martens hardness HM is a hardness hardness (hard to lose) of the hard coat layer 12 determined by a test load when the surface of the hard coat layer 12 is pushed by a Vickers indenter and a pressing surface area, And is an index of the surface hardness of the hard coat layer 12.

In this example, the value of HM of the hard coat layer 12 is adjusted to preferably not less than 250 N / mm 2, more preferably not less than 280 N / mm 2, and still more preferably not less than 300 N / mm 2. The occurrence of scratches on the hard coat layer 12 is effectively prevented by adjusting the HM of the hard coat layer 12 to a predetermined value or more. On the other hand, if the HM of the hard coat layer 12 is excessively large, a problem such as film warpage may occur. Therefore, in the present embodiment, the HM of the hard coat layer 12 is preferably adjusted to 500 N / mm 2 or less, more preferably 400 N / mm 2 or less.

The value of HM in this example was measured in accordance with ISO-14577-1 by a micro-miniatureness tester (Fisher Instruments, trade name: Fisher-Scope HM2000) under an atmosphere of a temperature of 20 degrees and a relative humidity of 60% The surface hardness of the hard coat layer 12 is measured. However, the maximum test load is 1 mN.

The firing hardness Hupl indicates the hardness (hard indentation) of the hard coat layer 12 determined by the indentation depth after the removal of the Vickers indenter and is an index of the hardness of the hard coat layer 12 .

In this example, the Hupl of the hard coat layer 12 is adjusted to preferably 800 N / mm2 or more, more preferably 900 N / mm2 or more, and still more preferably 1000 N / mm2 or more. By adjusting the Hupl of the hard coat layer 12 to a predetermined value or more, occurrence of scratches on the hard coat layer 12 is effectively prevented. On the other hand, if the Hupl of the hard coat layer 12 is excessively large, a problem such as film warpage may occur. Therefore, in this example, it is preferable that the Hupl of the hard coat layer 12 is adjusted to preferably not more than 3000 N / mm 2, more preferably not more than 2000 N / mm 2.

The value of Hupl can be calculated by the following formula (3) after measurement by the method in accordance with ISO-14577-1. In the following formula, equations (1) and (2) of universal hardness (Hu) are also shown together with Hupl.

Here, in the equations (1) to (3), "F" is the test load (unit: N), " _Fmax " is the maximum value of the test load (unit: N) (Unit: mm 2) where the indenter is in contact with the object to be measured.

A (h) is calculated from the shape of the indenter and the indentation depth. When the indenter is a Vickers indenter, the angles a (136 °) of the facing surface of the pyramid-shaped intrusive body (26.43 × h ² ) . Further, "h" is the indentation depth at the time of the test load is applied (unit: ㎜), "h _max" is the indentation depth (unit: ㎜) of the test load is applied up to the value, "hr" for are the hF curve (h _max , _Fmax ) is the h coordinate value (unit: mm) of the intersection of the t-axis and the t-axis at the point.

The hF curve is shown, for example, in Fig. (1) in FIG. 2 is a hF curve when the weight load from 0 to F _max, (2) will continue to a hF curve when unloading a load from F _max to zero, and, (3) Is the tangent line at the (h _max , F _max ) point of the hF curve.

The value of Hupl in this example is the value obtained by measuring the surface hardness of the hard coat layer 12 by the method according to ISO-14577-1 under the measurement conditions to be described later by using the same apparatus as in the HM case to be.

The measurement conditions include, for example, indenter shape: Vickers indenter (a = 136 °), measurement environment: temperature 20 캜, relative humidity 60%, maximum test load 1 mN, load speed 1 mN / 20 seconds, Creep time: 5 seconds, Unloading speed: 1 mN / 20 seconds. Further, in each of the samples, a total of 15 points were measured in five points at an equal interval in the axial direction and three points at an equal angle in the circumferential direction, and the average value was determined as the firing hardness (Hupl) in this example.

The indentation elastic modulus (Young's modulus) EIT indicates the flexibility (flexibility) of the hard coat layer 12 and serves as an index of the brittleness of the hard coat layer 12.

In this example, the EIT of the hard coat layer 12 is adjusted to preferably not more than 5000 MPa, more preferably not more than 4900 MPa. By adjusting the EIT of the hard coat layer 12 to a predetermined value or less, the hard coat layer 12 becomes easy to bend, contributing to improvement in crack resistance. On the other hand, if the EIT of the hard coat layer 12 is too small, the hard coat property tends to deteriorate. Therefore, in this example, it is preferable that the EIT of the hard coat layer 12 is adjusted to preferably 4000 MPa or more, and more preferably 4300 MPa or more.

The EIT value is a value corresponding to the Young's modulus measured in accordance with ISO-14577-1 using the same apparatus as in the case of HM and Hupl described above, and the hard coat layer 12 is formed on the stainless steel plate And the Young's modulus of the hard coat layer 12 itself measured by using the obtained hard coat layer 12, that is, in a state in which it is not affected by the modulus of elasticity of the base film 11. However, like HM and Hupl, the maximum test load is 1 mN.

The value of the bending resistance test of the hard coat film 10 of the present example varies depending on the thickness of the hard coat layer 12 and the type and thickness of the base film 11 but is preferably 5 mm or less, It is preferable to adjust it to 4 mm or less. When the value of the bending test is adjusted to a predetermined value or less, cracking resistance of the hard coat layer 12 can be improved. The value of the bending test is a value measured by a cylindrical mandrel method in accordance with JIS-K5600-5-1 (1999).

It is preferable that the hard coat layer 12 of this example is adjusted so as not to cause scratches when the steel wool # 0000 with a load of 300 g is reciprocated for 10 times. By adjusting in this manner, it becomes possible to secure necessary hard coat properties.

In the hard coat layer 12 of this embodiment, it is also preferable that the pencil scratching value (pencil hardness) is adjusted to H or higher. And more preferably 2H or more. It is possible to effectively prevent scratches on the surface of the hard coat layer 12 by adjusting the pencil scratch value to a predetermined value or more. The pencil scratching value is a value measured by a method in accordance with JIS-K5400 (1990).

The thickness of the hard coat layer 12 of this embodiment is preferably 10 占 퐉 or less, and more preferably 5 占 퐉 or less. If the thickness exceeds 10 탆, cracks are likely to occur. On the other hand, if the thickness is excessively thin, sufficient hard coatability may not be exhibited. Therefore, the thickness of the hard coat layer 12 is preferably 0.5 占 퐉 or more, more preferably 1 占 퐉 or more, and further preferably 2 占 퐉 or more.

The hard coat layer 12 of the present example can be obtained by preparing a coating material, coating it on the base film 11, and curing it.

The coating material usable in this example contains a resin component. The resin component includes an ionizing radiation curable resin.

As the ionizing radiation curable resin contained in the resin component, a photopolymerizable prepolymer which is crosslinked and cured by irradiation with ionizing radiation (ultraviolet ray or electron beam) can be used. In the present example, the photopolymerizable prepolymer described later may be used alone, or two or more kinds of them may be used in combination.

Examples of the photopolymerizable prepolymer include a cationic polymerization type and a radical polymerization type.

Examples of the cationic polymerization type photopolymerizable prepolymer include epoxy resins and vinyl ether resins. Examples of the epoxy resin include bisphenol-based epoxy resin, novolak-type epoxy resin, alicyclic epoxy resin, and aliphatic epoxy resin.

As the radical polymerization type photopolymerizable prepolymer, an acrylic type prepolymer (hard prepolymer) having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used from the viewpoint of hard coatability.

Examples of the acrylic prepolymer include urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate, polyfluoroalkyl acrylate, and silicone acrylate.

The urethane acrylate prepolymer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of a polyether polyol or polyester polyol with a polyisocyanate by reaction with (meth) acrylic acid. Examples of the polyester acrylate-based prepolymer include a polyester oligomer obtained by esterifying a hydroxyl group of a polyester oligomer having hydroxyl groups at both terminals obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, Can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The epoxy acrylate-based prepolymer can be obtained by, for example, esterifying a bisphenol-type epoxy resin having a relatively low molecular weight or an oxirane ring of a novolac epoxy resin with a (meth) acrylic acid.

The acrylic-based prepolymer can be appropriately selected depending on the kind and application of the object (substrate film 11) to be coated. The acrylic prepolymer can be used alone, but it is preferable to add a photopolymerizable monomer in order to impart various performances such as improvement of crosslinking curability and adjustment of curing shrinkage.

Examples of the photopolymerizable monomer include monofunctional acrylic monomers (e.g., 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, butoxyethyl acrylate and the like), bifunctional acrylic monomers For example, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalic acid ester neopentyl glycol diacrylate, etc.), trifunctional or higher acryl And monomers (e.g., dipentaerythritol hexaacrylate, trimethyl propane triacrylate, pentaerythritol triacrylate, etc.). The term " acrylate " also includes methacrylate in addition to the literally acrylate. These photopolymerizable monomers may be used alone, or two or more of them may be used in combination.

The total content (in terms of solid content) of the photopolymerizable prepolymer and the photopolymerizable monomer in the paint of this example is preferably 40 to 99% by weight, more preferably 60 to 95% by weight, By weight is 80 to 90% by weight.

Particularly, in this example, it is preferable to contain at least any one of the specific photopolymerizable prepolymer (A) and the photopolymerizable monomer (B) in the ionizing radiation curable resin in order to make both the hard coat property and the crack resistance of the formed coating film compatible Do.

Specific examples of the photopolymerizable prepolymer (A) include a polyfunctional oligomer having a dendrimer structure in the molecule and having three or more (meth) acrylate functional groups.

The dendrimer structure means a form in which the monomers are polymerized while being branched, and the multifunctional oligomer having a dendrimer structure is represented by the formula (1).

Specifically, it has a functional group such as an amino group, a hydroxyl group, a carboxyl group, a phenyl group, an ethylene oxide group, a vinyl group and a propylene oxide group and has a (meth) acrylate functional group at the terminal. Among them, those having an ethylene oxide group and having a (meth) acrylate functional group at the terminal are preferable from the viewpoints of solubility in solvents and handleability and compatibility with other ionizing radiation curing resins .

As the number of the (meth) acrylate functional groups and the molecular weight of the oligomer become larger, the hardness of the hard coat layer 12 formed by the ionizing radiation curable resin composition increases, and cracks are less likely to occur during molding. However, if the number of the (meth) acrylate functional groups is excessively large, crack resistance during molding is lowered. Also, if the molecular weight of the oligomer is too large, the hard coat property of the hard coat layer 12 is lowered. Accordingly, the number of (meth) acrylate functional groups is preferably 3 to 10, more preferably 5 to 8. The molecular weight is preferably 1000 to 3000, more preferably 1500 to 2000.

The content of the photopolymerizable prepolymer (A) in the paint of this example is preferably 10 to 160 parts by weight, more preferably 20 to 100 parts by weight, per 100 parts by weight of the total amount of the photopolymerizable monomer and the other photopolymerizable prepolymer , And more preferably 30 to 70 parts by weight. By setting the content of the photopolymerizable prepolymer (A) to 10 parts by weight or more, it is possible to prevent cracks or the like from being generated in the edge portion when pressed at the time of molding. By setting the amount to 160 parts by weight or less, hard coatability can be maintained.

Specific examples of the photopolymerizable monomer (B) include a photopolymerizable monomer having a cyclic ring together with a polymerizable reactive group in the molecule.

The cyclic ring is preferably composed of at least one element selected from the group consisting of carbon, nitrogen, oxygen and silicon, and is preferably a 5-membered ring or a 6-membered ring. Specific examples of the cyclic ring structure include cycloolefins such as cyclopentene and cyclohexene, tetrahydrofuran, 1,3-dioxane, epsilon -caprolactone, epsilon -caprolactam, silacyclo pentene, cyclodecane, isobonyl . Examples of such monomers having a cyclic ring structure include ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, ε-caprolactone-modified tris- (2-hydroxyethyl) isocyanurate, dimethylol Acrylate, tricyclodecane di (meth) acrylate, isobonyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and 2-acryloyloxyethyl hexahydrophthalic acid.

The content of the photopolymerizable monomer (B) in the coating material of the present example is preferably 1 to 70% by weight, more preferably 1 to 70% by weight, based on the solid content, of the photopolymerizable prepolymer and the photopolymerizable monomer constituting the ionizing radiation curable resin By weight is 5 to 50% by weight. When it is 1% by weight or more, occurrence of cracks or the like at the time of pressurization can be prevented. When the content is 70 wt% or less, the hard coat property of the hard coat layer 12 can be prevented from deteriorating.

When the photopolymerizable prepolymer (A) is contained together with the photopolymerizable prepolymer (A), the total content of (A) and (B) is preferably 100 parts by weight or more based on 100 parts by weight of the total amount of the other photopolymerizable monomer and the other photopolymerizable prepolymer Preferably 20 to 200 parts by weight, more preferably 30 to 160 parts by weight, still more preferably 40 to 140 parts by weight. The total content of the hard coat layer 12 and the hard coat layer 12 varies depending on the thickness of the hard coat layer 12 and the like. For example, when the thickness of the hard coat layer 12 is in the range of 2 to 5 占 퐉 (B) is preferably 10 to 90% by weight, more preferably 15 to 60% by weight, and still more preferably 20 to 40% by weight based on the total content of (A) and (B). When the content of the component (B) is 10% by weight or more, it is possible to make cracks or the like less likely to occur in the edge portions when pressed at the time of molding. When the content is 80% by weight or less, the hard coat property can be prevented from deteriorating.

When the hard coat layer 12 of this embodiment is formed by curing by irradiation with ultraviolet rays, it is preferable to incorporate additives such as a photopolymerization initiator, a photopolymerization accelerator, and an ultraviolet sensitizer into the coating material of this example.

As the photopolymerization initiator, examples of the radical polymerization type photopolymerizable prepolymer and the photopolymerizable monomer include, for example, acetophenone, benzophenone, Michler's ketone, benzoin, benzyl methyl ketal, benzoyl benzoate, And the like. Examples of the photopolymerization initiator for the cationic polymerization type photopolymerizable prepolymer include an onium such as an aromatic sulfonium ion, an aromatic oxosulfonium ion, and an aromatic iodonium ion, and a photopolymerization initiator such as tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate Monoethers, hexafluoroarsenates, and the like. These may be used alone or in combination of two or more kinds. Examples of the photopolymerization accelerator include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester. Examples of ultraviolet sensitizers include n-butylamine, triethylamine, tri-n-butylphosphine and the like.

In addition, the coating material of this example can contain other resin such as thermoplastic resin or thermosetting resin in an amount of 30 wt% or less of the resin constituting the hard coat layer 12, in addition to the ionizing radiation curable resin as the binder component. Depending on the kind of the ionizing radiation curable resin, the amount of other resin that can be contained may be different. When a thermosetting resin is contained, a thermosetting monomer or a prepolymer may be used alone or in combination, and a thermal polymerization initiator, that is, a compound which generates an active radical species by heating, etc., is contained. Examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples thereof include benzoyl peroxide, t-butyl-peroxybenzoate, and azobisisobutyronitrile.

The coating material of this example may be appropriately added with an additive component as required. Examples of the additive component include a matting agent, a colorant, an antistatic agent, and an ultraviolet absorber for imparting an antiglare function.

When the paint of this example is used as the organic solvent-based paint, it may be appropriately selected according to the kind of the resin component. Alternatively, the resin component (additionally added components as required) may be dissolved or dispersed in a diluent solvent such as an organic solvent , And if necessary, an additive is added, whereby the paint of this example can be produced. Examples of the organic solvent include, but are not limited to, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol, ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, Etc.), esters (e.g., ethyl acetate, butyl acetate, ethyl lactate,? -Butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like), ethers (such as ethylene glycol monomethyl Ether, diethylene glycol monobutyl ether, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene), amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.) . In the case of a solvent-based paint, the paint of this example can be prepared by adding an additive component to the resin component as required.

The base film 11 is preferably excellent in transparency, heat resistance and mechanical strength, and specifically, it is preferable that the base film 11 is made of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, triacetylcellulose , Acryl, polyvinyl chloride, norbornene compounds, and the like. In particular, from the viewpoint of good dimensional stability by heat, it is preferable to use a biaxially stretched polyethylene terephthalate film.

The base film 11 is preferably subjected to easy adhesion treatment or the like in order to improve adhesion of the hard coat layer 12 or the metal vapor deposition layer 13 or the print layer 14 or the adhesive layer 15 May be subjected to surface treatment.

The base film 11 may contain the same additive as the additive that can be contained in the paint of this example, including the pigment and the ultraviolet absorber.

The thickness of the base film 11 is not particularly limited, but it is about 20 to 200 占 퐉, preferably about 50 to 150 占 퐉 in consideration of handleability and mechanical strength.

The coating (coating) of the coating material on the base film 11 may be carried out by a conventional method and may be carried out by any suitable method such as bar coating, die coating, blade coating, spin coating, roll coating, gravure coating, , Spray coating, screen printing, brush coating, and the like.

In this example, the thickness of the coated film after coating is applied to the thickness described above after drying and curing described later. When the coating material of this example is applied to the base film 11, it is preferable to dry the coated film at about 50 to 120 캜.

Curing of the coating can be performed by irradiating curing by heat and / or ionizing radiation (light) on the coated film after coating.

When heat is generated, for example, electric heaters, infrared lamps, hot wind, etc. may be used as the heat source.

In the case of ionizing radiation (light), the source is not particularly limited as long as it can cure the coating film applied to the base film 11 in a short time. For example, a source of infrared rays includes a lamp, a resistance heating plate, and a laser. Examples of a source of visible light include daylight, a lamp, a fluorescent lamp, and a laser. As a source of ultraviolet rays (ionizing radiation), ultrahigh pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, metal halide lamps and the like can be mentioned. Ultraviolet rays of a wavelength range of 100 nm to 400 nm, preferably 200 nm to 400 nm, emitted from such a source of ultraviolet rays are irradiated. As a source of an electron beam (ionizing radiation), an electron beam accelerator of a scanning type or a curtain type can be given. An electron beam in a wavelength region of 100 nm or less emitted from such an electron beam accelerator is irradiated.

The dose of ionizing radiation differs depending on the type of ionizing radiation. For example, in the case of ultraviolet rays, the dose is preferably about 100 to 500 mJ / cm 2, and in the case of electron beam, about 10 to 1000 krad.

The hard coat layer 12 of the present example manufactured as described above has both hard coatability (scratch resistance) and crack resistance. The reason why the crack resistance is exhibited while maintaining the hard coat property is that the pressure is absorbed by the dendrimer structure in the molecule when external pressure (bending force or tensile force) is applied, It is considered that the structure is deformed to absorb the pressure, and cracks are prevented from being generated in the surface of the layer in any case.

Since the hard coat film 10 of the present embodiment has both hard coat property and crack resistance, the hard coat film 10 of the present embodiment can be used as an operating portion (keypad portion) of a device such as a touch panel of a home appliance, a portable telephone, a game machine, (Especially for resin molding), and for surface protection (suitable for insert molding applications).

Further, since the hard coat film 10 has hard coatability and crack resistance, the hard coat film 10 can be used not only for integral molding at the time of insert molding but also for other purposes such as glass scattering prevention and punching processing such as membrane switch And can be used for applications requiring processes such as bending. When the hard coat film 10 is used at the time of punching, cracks, gold, and the like do not occur at the edge portions, and cracks, whitening, cracks, and the like do not occur even when used at the time of bending.

Further, for example, even when the keypad portion of the cellular phone is constituted by a hard coat film rather than a resin molded article, the hard coat film 10 is useful. This is because it combines hard coat and crack resistance.

In this embodiment, for example, when a molded article made of a resin or the like is molded into a mold, the resin and the hard coat film are integrally molded by molding, Or a hard coat film used for obtaining a resin molded article having a surface protective layer formed thereon is referred to as " insert molding film ".

When the hard coat film 10 of this embodiment is used for insert molding, its basic structure is the same as that of the above-described base film 11 and hard coat layer 12, A decorative layer for decorating a molded article may be laminated.

The decorative layer may be composed of a metal deposition layer 13 formed on the other side of the substrate film 11 and a print layer 14 laminated on the metal deposition layer 13, for example. An adhesive layer 15 may be laminated on the decorative layer.

The decorative layer may be formed by, for example, forming a metal deposition layer 13 on the other surface of the base film 11, removing a part of the metal deposition layer 13 by etching, Printing is performed on the removed base film 11 or a desired character or shape is formed on the base film 11 by a known printing method, a silk screen method, a gravure method, an ink jet method, or the like, Or a metal deposition layer 13 is formed thereon. The printed layer 14 may be omitted and the metal deposition layer 13 may be formed directly on the base film 11 or the printed layer 14 may not be provided. In the case of providing the print layer 14, a receptive layer for containing the printing ink may be provided on the surface of the base film 11 on which the print layer 14 is provided.

The metal deposition layer 13 can be formed by a known method such as a method of forming a metal film by using a known method such as a method of forming a metal film of a metal such as aluminum, For example, by a vacuum deposition method, a sputtering method, an ion plating method, or the like.

The adhesive layer 15 is a layer provided for enhancing the adhesion between the molded product material and the metal deposition layer 13 and may be a polyurethane based material, a polyacrylic based material, a polyester based material, an epoxy based material, a polyvinyl acetate based material , A vinyl chloride-vinyl oxide copolymer, and a cellulose-based adhesive.

&Quot; Method of producing resin molded article "

Next, an example of a method of embossing or protecting the resin molded article by using the hard coat film 10 of the present embodiment as an insert molding film will be described.

First, when the hard coat film 10 of the present embodiment is formed into a resin molded article, the hard coat layer 12 is disposed so as to be located outside, and press-formed to be formed into a desired shape.

Next, in the state where the hard coat film 10 molded so that the hard coat layer 12 is in contact with the inner wall surface is placed in one of the molds, the mold is clamped to the other mold to form a cavity in the mold.

Next, a resin molded article obtained by heating the fluidized resin material in a cavity in the mold, then curing the resin material, and integrating it with the hard coat film 10 is obtained.

Molding conditions (temperature, mold clamping pressure, time) are appropriately selected according to the shape of the resin (molding material) and the shape of the molded product. Generally, the mold clamping pressure is calculated by the projected area of the molded product x the resin pressure in the mold. For example, when the resin to be injection molded is ABS resin and the dimension of the molded product (L x W x H) is 60 x 80 x 2 (mm), the mold temperature is 60 DEG C, the mold temperature is 60 DEG C, Mm / sec. The resin may be an injection-moldable resin. For example, a thermoplastic resin such as an acrylic resin, a polycarbonate resin, an ABS resin, and an AS resin or a thermosetting resin is used. The resin is cured and integrated with the hard coat film 10 to obtain a resin molded article of this example.

In this embodiment, since the hard coat film 10 of the present embodiment having the hard coat layer 12 excellent in crack resistance is used as the insert molding film, it is possible to prevent the hard coat film 10 from being pressed The resin molded article which is free from generation of cracks during molding by molding (decorative or surface-protected) has excellent aesthetic appearance and is excellent in hard coat property.

Examples of the resin molded article include an operation section (keypad section) of a device such as a touch panel of household electric appliances, a cellular phone, a game machine, a voice reproducing machine, and a notebook computer.

Example

Next, embodiments of the present invention will be described in further detail with reference to embodiments. "Parts" and "%" are on a weight basis unless otherwise specified.

&Quot; Experimental Example 1 &

First, a coating liquid for a hard coat layer was prepared.

≪ Coating liquid for hard coat layer >

· Dendrimer structure polyfunctional oligomer A1 8 parts

(100% solids) (Miramer SP1114: MIWON)

· Photopolymerizable prepolymer / photopolymerizable monomer 12 parts

(Solid content 100%) (Beam set 575: Arakawa Chemical Industries Co., Ltd.)

Photopolymerization initiator 0.6 part

(Irugacure 651: Cuba, Japan company)

Propylene glycol monomethyl ether 45 parts

Next, the coating liquid for the hard coat layer thus prepared was applied to one side of a polyester film (Cosmo Shine A4300: Toyo Boseki Co., Ltd.) having a thickness of 125 占 퐉 as the base film 11 by a bar coater method and dried, A hard coat layer 12 having a thickness of 3 탆 was formed by irradiating ultraviolet rays with a mercury lamp (irradiation amount: 400 mJ / cm 2) to obtain a film sample.

Hardness (HM), bending hardness (Hupl), indentation modulus (Young's modulus), hard coat property (hardness of steel wool (SW) property, and pencil hardness) of the hard coat layer (12) Hardness), crack resistance and pencil hardness were evaluated. The results are shown in Table 1.

(Fischer-Scope, manufactured by Fisher Instruments, Inc.) was used for all of the following: (1) "Hardness hardness (HM)"; "Hardness (Hupl) HM2000), the surface hardness or Young's modulus of the hard coat layer 12 was measured under the measurement conditions described later by a method in accordance with ISO-14577-1.

(1), (2) and (3), the measurement conditions were as follows.

Indenter shape: Vickers indenter (a = 136 deg.),

Measurement environment: temperature 20 캜, relative humidity 60%

Maximum test load: 1 mN,

Load speed: 1 mN / 20 sec,

Maximum load creep time: 5 seconds,

Unloading speed: 1 mN / 20 sec.

(4) With respect to the "SW resistance", first, the surface of the hard coat layer 12 is rubbed with a steel wool # 0000 at a load of 300 g for 10 reciprocations. Next, the presence or absence of scratches on the surface of the hard coat layer 12 is visually observed. As a result, it was evaluated as "? &Quot; where scratches did not occur, "? &Quot; where scratches did not occur, and " X "

(5) For "pencil hardness", the pencil scratching value on the surface of the film sample was measured in accordance with JIS-K5400 (1990). A sample having a measured value of 2H or more was evaluated as "? &Quot;, a sample having a H value of less than 2H was evaluated as "? &Quot;, and a plurality of samples were prepared in the same experimental example. DELTA ", and those less than H were evaluated as " X ".

(6) The "crack resistance" was evaluated on the basis of the bending resistance (cylindrical mandrel method) in accordance with JIS-K5600-5-1 (1999) (12) are folded out so as to be outside, and whether or not a crack is generated in the hard coat layer (12) of the portion where the hard coat layer (12) is wound is visually observed. As a result, it was evaluated as " Good ", " Good ", " Good ", " Good ", and " Good ", respectively.

&Quot; Experimental Example 2 &

A coating liquid was prepared under the same conditions as in Experimental Example 1 except that the coating solution for hard coat layer prepared in the following formulation was used to obtain a film sample. The same measurement and evaluation as in Experimental Example 1 were carried out. The results are shown in Table 1.

≪ Coating liquid for hard coat layer >

· Ε-caprolactone-modified tris

- (2-hydroxyethyl) isocyanurate 5 parts

(SR368: Sato MUSA) (100% solids)

· Photopolymerizable prepolymer / photopolymerizable monomer 10 parts

(Beam set 575: Arakawa Chemical Industries) (solid content 100%)

Photopolymerization initiator 0.4 part

(Irugacure 651: Cuba, Japan company)

Propylene glycol monomethyl ether 30 parts

&Quot; Experimental Example 3 &

A coating liquid was prepared under the same conditions as in Experimental Example 1 except that dendrimer structure polyfunctional oligomer A2 (NK ester A-HBR5: Shin Nakamura Chemical Co., Ltd.) was used instead of dendrimer structure polyfunctional oligomer A1 to obtain a film sample. The same measurement and evaluation as in Experimental Example 1 were carried out. The results are shown in Table 1.

&Quot; Experimental Example 4 &

A coating liquid was prepared under the same conditions as in Experimental Example 1, except that the blending amount of the dendrimer-structured polyfunctional oligomer A1 was 12 parts and the blending amount of the photopolymerizable prepolymer / photopolymerizable monomer was 8 parts. The same measurement and evaluation as in Experimental Example 1 were carried out. The results are shown in Table 1.

&Quot; Experimental Example 5 &

A coating liquid was prepared under the same conditions as in Experimental Example 1 except that the blending amount of the dendrimer-structured polyfunctional oligomer A1 was 4 parts and the blending amount of the photopolymerizable prepolymer / photopolymerizable monomer was 16 parts. The same measurement and evaluation as in Experimental Example 1 were carried out. The results are shown in Table 1.

&Quot; Experimental Example 6 &

1 part of ε-caprolactone modified tris- (2-hydroxyethyl) isocyanurate (hereinafter referred to as "cyclic ring structure reactive monomer"), 14 parts of a photopolymerizable prepolymer / photopolymerizable monomer , A coating liquid was prepared under the same conditions as in Experimental Example 2 to obtain a film sample. The same measurement and evaluation as in Experimental Example 2 were carried out. The results are shown in Table 1.

&Quot; Experimental Example 7 &

A coating liquid was prepared under the same conditions as in Experimental Example 2 except that the blending amount of the cyclic ring structure reactive monomer was 10 parts and the blending amount of the photopolymerizable prepolymer / photopolymerizable monomer was 5 parts. The same measurement and evaluation as in Experimental Example 2 were carried out. The results are shown in Table 1.

&Quot; Experimental Example 8 &

A coating liquid was prepared under the same conditions as in Experimental Example 1, except that the dendrimer-structured polyfunctional oligomer A1 was not blended (0 part) and the blending amount of the photopolymerizable prepolymer / photopolymerizable monomer was 20 parts. The same measurement and evaluation as in Experimental Example 1 were carried out. The results are shown in Table 1.

"Experimental Example 9"

A coating liquid was prepared under the same conditions as in Experimental Example 1 except that the coating solution for hard coat layer prepared in the following formulation was used to obtain a film sample. The same measurement and evaluation as in Experimental Example 1 were carried out. The results are shown in Table 1.

≪ Coating liquid for hard coat layer >

· Thermoplastic acrylic resin (solid content 40%) 15 parts

(Acridic A195: Dainippon Ink & Chemicals)

· Photopolymerizable prepolymer / photopolymerizable monomer 14 parts

(Solid content 100%) (Beam set 575: Arakawa Chemical Industries Co., Ltd.)

Photopolymerization initiator 0.4 part

(Irugacure 651: Cuba, Japan company)

Propylene glycol monomethyl ether 36 parts

"Experimental Example 10"

A coating liquid was prepared under the same conditions as in Experimental Example 9 except that 20 parts of Acridic Al95, 20 parts of Beam Set 575, and 33 parts of propylene glycol monomethylether were added. The same measurement and evaluation as in Experimental Example 9 were carried out. The results are shown in Table 1.

&Quot; Experimental Example 11 &

The coating solution of Experimental Example 4 was prepared to obtain a film sample having the hard coat layer 12 having a thickness of 1 占 퐉. The same measurement and evaluation as in Experimental Example 4 were carried out. The results are shown in Table 1.

From the results of Table 1, the following facts were confirmed.

Regarding the hard coat properties (resistance to SW and pencil hardness), hard coatability tends to decrease when HM or Hupl of the hard coat layer 12 is less than a predetermined value (Experimental Examples 9 to 11) . As in Experimental Example 9, when Hupl is less than a predetermined value even if HM is not less than a predetermined value, pencil hardness is better than Experimental Examples 10 and 11, but evaluation is lower than Experimental Examples 1 to 8, Are lower than those in Experimental Examples 1 to 8. Also, as in Experimental Example 11, when HM is less than the predetermined value even if Hupl is not less than the predetermined value, the SW resistance is good, but since the thickness of the hard coat layer 12 is thin, the pencil hardness is not sufficient. On the other hand, sufficient hard coatability was obtained for Experimental Examples 1 to 8.

Next, with respect to crack resistance, crack resistance tends to be lowered when the EIT of the hard coat layer 12 exceeds a predetermined value (Experimental Example 8). On the other hand, sufficient crack resistance was obtained for Experimental Examples 1 to 7 and 9 to 11.

From these results, it was confirmed in Experimental Examples 1 to 7 that sufficient hard coatability and crack resistance are possessed in this Experimental Example, and among these, Experimental Examples 1 to 3 were particularly excellent. That is, it was confirmed that in the film samples of Experimental Examples 1 to 3, the hard coat property and the crack resistance can be compatible with each other at a high level.

&Quot; Experimental Examples 12 to 14 "

A film sample having a hard coat layer thickness of 3 占 퐉 obtained in Experimental Example 1, Experimental Example 8 and Experimental Example 10 was molded into a resin molded product so that the mold for injection molding (mold for cover case of mobile phone, Size: about 50 mm x 100 mm), molded into a three-dimensional shape by vacuum molding, filled with a molten acrylic resin, and cooled to obtain an acrylic resin molded article integrally cured with the film sample . With respect to these resin molded articles, the edge portions (curved surface and corner portions) of the surface of the resin molded article were visually observed. The hard coat properties of the surface of these resin molded articles were evaluated in the same manner as the film samples described above.

As a result, for the resin molded article using the film sample of Experimental Example 1, cracks were not generated on the edge portion, whitening was not observed, and good results were obtained with respect to the hard coat property as in the above-mentioned film samples.

On the other hand, with respect to the resin molded article using the film sample of Experimental Example 8, good results were obtained with respect to hard coatability, but occurrence of cracks and whitening were observed at edge portions.

In the resin molded article using the film sample of Experimental Example 10, the edge portion was free from cracking and whitening, but hard coatability was lower than that of the resin molded article of Experimental Example 1.

Claims (8)

A hard coat film having a hard coat layer on at least one side of a base film, wherein the hard coat layer comprises an ionizing radiation curable type resin having a dendrimer structure in a molecule and a polyfunctional oligomer having at least three (meth) acrylate functional groups Wherein the hard coat film is formed of a cured product of a resin composition and has a Martens hardness of 250 N / mm2 or more, a bending hardness of 800 N / mm2 or more, and a press-fit elastic modulus of 5,000 MPa or less. The hard coat film of claim 1,
Wherein the polyfunctional oligomer having the dendrimer structure is contained in an amount of not less than 10 parts by weight and not more than 160 parts by weight based on 100 parts by weight of the ionizing radiation curable resin composition excluding the ionically polymerizable oligomer, Coat film. A hard coat film according to any one of claims 1 to 3,
And the value of the bending resistance test measured by a cylindrical mandrel method according to JIS-K5600-5-1 (1999) is 5 mm or less. The hard coat film of claim 3,
Wherein the hard coat layer does not cause scratches when the steel wool # 0000 subjected to a load of 300 g is reciprocated for 10 times. A hard coat film according to any one of claims 1 to 3,
Wherein the hard coat layer has a thickness of 0.5 to 10 mu m. A hard coat film according to any one of claims 1 to 3,
Wherein at least one layer including a metal deposition layer, a printing layer and an adhesive layer is formed on the other surface of the base film. As a molded article formed by molding a molding material and an insert molding film,
Wherein the insert molding film is the hard coat film of any one of claims 1 to 3. The resin molded article of claim 7,
Wherein the molding material is an acrylic resin or a polycarbonate resin.

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