JP2020203383A - Production method of film and laminate - Google Patents

Abstract

To provide a film and a laminate which have excellent anti-fouling property and the function of which is maintained even after transfer to a molded product.SOLUTION: Provided is a production method of a film having a hard coat layer containing an anti-fouling compound with a fluorine atom and/or a silicon atom and a hard coat material and a primer layer arranged on a surface of the hard coat layer, which includes a step to form the primer layer by applying a primer layer composition including a primer layer component and a solvent to the surface of the hard coat layer, in which the solvent includes at least one selected from a group consisting of propylene glycol monomethyl ether, butyl acetate and propylene glycol monomethyl ether acetate, or includes at least one selected from solvents with molecular weight of 80 g/mol or more, boiling point of 120°C or more, and viscosity at 20°C of 2 mPa s or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing a film and a laminate having antifouling properties.

As one of the methods for decorating the surface of members such as vehicle interior / exterior parts, home appliances, notebook PCs, mobile phones, and furniture, there is a method of attaching a decorative film to a base material. This method using a decorative film is superior in design and durability as compared with conventional methods such as painting, and has been widely used.

It is being considered to give various functions to the decorative film as well as to decorate it. For example, the addition of functions such as antifouling property, heat retention property, scratch resistance, fingerprint adhesion property, antibacterial property, and transparency of electricity and infrared rays is being studied.
As a film having a hard coat layer having excellent antifouling properties, a film having an antifouling layer containing a compound containing a fluorine atom or a silicon atom is disclosed (Patent Document 1).

JP-A-2010-243700

However, the invention described in Patent Document 1 requires a large amount of a compound containing an expensive fluorine atom or silicon atom in order to exert sufficient antifouling property, and cannot be said to be economically appropriate. ..
Therefore, an object of the present invention is to provide a method for producing a film and a laminate having a hard coat layer having an inexpensive and excellent antifouling property.

As a result of examination in view of the above problems, the present inventors provided a hard coat layer containing at least one element selected from the group consisting of fluorine atoms and silicon atoms, and the surface of the hard coat layer. By using a specific solvent in the primer layer composition in a method for producing a film having a primer layer and a laminate having the hard coat layer and a primer layer provided on the surface of the hard coat layer. It has been found that a film and a laminate which are excellent in antifouling property and whose function is maintained even after transfer to a molded product can be obtained.

That is, the gist of the present invention lies below.
[1] A hard coat layer containing an antifouling compound having a fluorine atom and / or a silicon atom and a hard coat material, and
A primer layer provided on the surface of the hard coat layer and
Is a method for producing a film having
A step of applying a primer layer composition containing a primer layer component and a solvent to the surface of the hard coat layer to form a primer layer is included.
A method for producing a film, wherein the solvent contains at least one selected from a solvent having a molecular weight of 80 g / mol or more, a boiling point of 120 ° C. or more, and a viscosity at 20 ° C. of 2 mPa · s or less.
[2] A hard coat layer containing an antifouling compound having a fluorine atom and / or a silicon atom and a hard coat material, and
A primer layer provided on the surface of the hard coat layer and
A resin base material layer provided on the surface of the primer layer opposite to the surface on which the hard coat layer is provided, and a resin base material layer.
It is a manufacturing method of a laminated body having
(A) A step of applying a hard coat layer composition containing an antifouling compound and a hard coat material to the surface of the release material layer to form a hard coat layer.
(B) A primer layer composition containing a primer layer component and a solvent is applied to a surface of the hard coat layer obtained in the step (a) opposite to the surface on which the release material layer is provided. The process of forming
(C) A step of laminating a resin base material layer on a surface of the primer layer obtained in the step (b) opposite to the surface on which the hard coat layer is provided.
(D) At least one selected from a solvent having a molecular weight of 80 g / mol or more, a boiling point of 120 ° C. or more, and a viscosity at 20 ° C. of 2 mPa · s or less, including a step of peeling off the release material layer. A method for producing a laminate, including.
[3] (e) The method for producing a laminate according to [2], further comprising a step of irradiating the surface of the hard coat layer with energy rays.
[4] The production method according to any one of [1] to [3], wherein the solvent contains at least one selected from the group consisting of propylene glycol monomethyl ether, butyl acetate, and propylene glycol monomethyl ether acetate.
[5] The solvent is any one of [1] to [4], which is a mixed solvent of at least one selected from the group consisting of propylene glycol monomethyl ether, butyl acetate, and propylene glycol monomethyl ether acetate and methyl ethyl ketone. The manufacturing method described.

According to the present invention, there is provided a film and a laminate which are excellent in antifouling property and whose function is maintained even after transfer to a molded product.

It is the schematic which shows the manufacturing process of the laminated body of this invention.

The present invention will be described in detail below, but the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as the gist of the present invention is not exceeded. It can be arbitrarily modified and carried out without departing from the gist of the invention.

[Film and laminate]
The film produced by the present invention has at least a hard coat layer and a primer layer. The thickness of the film produced by the present invention is not particularly limited, and can be appropriately adjusted according to the intended use. It is preferably 0.5 μm or more, and more preferably 1 μm or more. Further, it is preferably 50 μm or less, and more preferably 30 μm or less. Within these ranges, the film has sufficient surface hardness, warpage of the film can be suppressed even when a coating layer is further provided on the film, and the appearance tends to be improved. In the present invention, the primer layer is a layer that adheres and adheres between layers for multi-layer structure, and refers to an intermediate layer that adheres the hard coat layer and the transfer base material.

Regarding the transmittance and YI value of the film, when the active energy ray-curable composition is used as a material, it is necessary to have transparency that does not interfere with the transparency of the energy ray to a specific wavelength. The transmittance for energy rays is preferably 10% or more, and more preferably 20% or more. In such a range, there is a tendency that the curing time can be shortened and efficient manufacturability can be maintained.

Further, the laminate produced by the present invention includes (1) a laminate having a hard coat layer, a primer layer and a resin base material layer, and (2) a release base material layer, a hard coat layer and a primer layer. Examples thereof include, but are not limited to, a laminate having a release base material layer, a hard coat layer, a primer layer, and a resin base material layer.

<Hard coat layer and hard coat layer composition>
The hard coat layer used in the present invention contains at least a hard coat material and an antifouling compound as an antifouling component. Further, the hard coat layer composition used in the present invention contains a hard coat material, an antifouling compound, a polymerization initiator, other additives, a diluting solvent and the like.

(Hard coat material)
The hard coat material used in the present invention is not particularly limited, and a material such as a monomer polymer generally used for the hard coat layer can be used. For example, a compound having a plurality of curable (meth) acryloyloxy groups in the molecule, a compound having an epoxy group, a compound having an isocyanate group, and the like can be mentioned. Among these, a compound having at least two (meth) acryloyloxy groups in the molecule is preferable for the reason of stabilizing the film structure and improving durability by polymerization and crosslink formation. For example, an esterified product obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or a derivative thereof, polyvalent carboxylic acid or an anhydride thereof, polyhydric alcohol and (meth) acrylic acid or a derivative thereof. Examples thereof include esterified products obtained from. In addition, in this specification, "(meth) acrylic" means "methacryl" or "acryl".

Specific examples of the esterified product obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or a derivative thereof include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol. Polyethylene glycol di (meth) acrylates such as di (meth) acrylates; 1,4-butanediol di (meth) acrylates, 1,6-hexanediol di (meth) acrylates, 1,9-nonanediol di (meth) acrylates. Alkyldiol di (meth) acrylates such as, and trimethylolpropanthry (meth) acrylate, trimethylol ethanetri (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth). ) Acrylate, glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra Examples thereof include trifunctional or higher functional polyol poly (meth) acrylates such as (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, and tripentaerythritol hepta (meth) acrylate.

In the esterified product obtained from polyvalent carboxylic acid or its anhydride, polyhydric alcohol and (meth) acrylic acid or a derivative thereof, a combination of polyvalent carboxylic acid or its anhydride, polyhydric alcohol and (meth) acrylic acid ( Examples of polyvalent carboxylic acid or its anhydride / polyhydric alcohol / (meth) acrylic acid) include malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, and the like. Maronic acid / glycerin / (meth) acrylic acid, malonic acid / pentaerythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (meth) acrylic acid, succinic acid Acid / glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / (meth) acrylic acid, adipic acid / trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolpropane / (meth) acrylic acid, adipic acid / Glycerin / (meth) acrylic acid, adipic acid / pentaerythritol / (meth) acrylic acid, glutaric acid / trimethylolethane / (meth) acrylic acid, glutaric acid / trimethylolpropane / (meth) acrylic acid, glutaric acid / Glycerin / (meth) acrylic acid, glutaric acid / pentaerythritol / (meth) acrylic acid, sebacic acid / trimethylolethane / (meth) acrylic acid, sebacic acid / trimethylolpropane / (meth) acrylic acid, sebacic acid / glycerin / (Meta) acrylic acid, sebacic acid / pentaerythritol / (meth) acrylic acid, fumaric acid / trimethylolethane / (meth) acrylic acid, fumaric acid / trimethylolpropane / (meth) acrylic acid, fumaric acid / glycerin / (Meta) Acrylic Acid, Fumaric Acid / Pentaerythritol / (Meta) Acrylic Acid, Itaconic Acid / Trimethylol Ethan / (Meta) Acrylic Acid, Itaconic Acid / Trimethylol Propane / (Meta) Acrylic Acid, Itaconic Acid / Glycerin / ( Meta) Acrylic acid, Itaconic acid / Pentaerythritol / (Meta) Acrylic acid, Maleic anhydride / Trimethylolethane / (Meta) acrylic acid, Maleic anhydride / Trimethylolpropane / (Meta) acrylic acid, Maleic anhydride / Glycerin / (Meta) acrylic acid and maleic anhydride / pentaerythritol / (meth) acrylic acid.

Other examples of compounds having at least two (meth) acryloyloxy groups in the molecule include trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4'-methylenebis. 2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy- per 1 mol of polyisocyanate obtained by trimerization of diisocyanates such as (cyclohexylisocyanate), isophorone diisocyanate, and trimethylhexamethylene diisocyanate. 3-methoxypropyl (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, 15,3-propanetriol-1,3-di (meth) acrylate, 3-acryloyloxy-2-hydroxy Urethane (meth) acrylate obtained by reacting 3 mol or more of acrylic monomer having active hydrogen such as propyl (meth) acrylate; di (meth) acrylate or tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate. ) Poly [(meth) acryloyloxyethylene] isocyanurate such as acrylate; epoxy poly (meth) acrylate; and urethane poly (meth) acrylate. Examples other than the isocyanate compound include (meth) acrylate obtained by reacting a compound having an epoxy group copolymerized with glycidyl (meth) acrylate with the acrylic monomer having active hydrogen.

In addition, these components can be used alone or in combination of two or more kinds. The content of the hard coat material is preferably 5% by mass or more, more preferably 10% by mass or more in the total solid components of the hard coat layer composition. Further, 90% by mass or less is preferable, and 80% by mass or less is more preferable.

(Anti-fouling compound)
By containing a compound that exhibits an antifouling function (hereinafter referred to as "antifouling compound"), antifouling properties (water repellency, oil repellency, etc.) can be imparted to the hard coat layer. Examples of the antifouling compound include compounds having a curable (meth) acryloyloxy group containing a fluorine atom or a silicon atom in the molecule. Among these, a compound having at least one (meth) acryloyloxy group in the molecule is preferable because it tends to be immobilized by forming a covalent bond and improve durability.

Examples of the compound having a fluorine atom include a compound having a perfluoroalkylene ether group and a tetrafluoroethylene group. Among these, compounds having a perfluoroalkylene ether group are preferable because they tend to have low free energy and high affinity for non-polar solvents.

Examples of commercially available compounds having a fluorine atom include "Optur DAC-HP" (trade name) manufactured by Daikin Industries, Ltd., "KY1271" (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., "Fluorolink MD700" manufactured by SOLVAY, and "Fluorolink MD700". "Fluorolink AD1700", "Fublin D2", "Fublin D4000" (trade name), "RS-72", "RS-75", "RS-76", "RS-78" (trade name) manufactured by DIC, etc. Can be mentioned.

The amount of the compound having a fluorine atom added is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the hard coat material. Further, it is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less. When the amount of the compound having a fluorine atom added is not more than the above lower limit, the antifouling performance of the film of the present invention tends to be sufficient. Further, when the amount of the compound having a fluorine atom added is not more than the above upper limit value, the curability and transparency of the film of the present invention tend to be improved.

Examples of the compound having a silicon atom include a compound having a dimethylsiloxane group and a cyclosiloxane group. Among these, compounds having a dimethylsiloxane group are preferable because they tend to have low free energy and high affinity for non-polar solvents.

Examples of commercially available compounds having a silicon atom include "KP414", "KP418", "KP420", "KP423", "X-12-1048", and "X-12-1050" manufactured by Shin-Etsu Chemical Co., Ltd. "X-12-2475", "X-22-2445", "X-22-174ASX", "X-22-174BX", "KF2012" (trade name), "TEGO RAD2250" manufactured by EVONIK, "TEGO" Examples thereof include "RAD2300", "TEGO RAD2500" (trade name), "BYK-333" (trade name) manufactured by BYK, and "BYK-UV3570" (trade name) manufactured by BYK.

The amount of the compound having a silicon atom added is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the hard coat material. Further, it is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less. When the amount of the compound having a silicon atom added is at least the above lower limit value, the antifouling performance of the film of the present invention tends to be sufficient. Further, when the amount of the compound having a silicon atom added is not more than the above upper limit value, the curability and transparency of the water repellent layer tend to be improved.

Examples of the compound having a fluorine atom and a silicon atom include a compound having a perfluoroalkylene ether group, a tetrafluoroethylene group, a dimethylsiloxane group and a cyclosiloxane group. Among these, compounds having a perfluoroalkylene ether group and a dimethylsiloxane group are preferable because they have low free energy and tend to have a high affinity for non-polar solvents.

Commercially available products of compounds having a fluorine atom and a silicon atom include, for example, "KY1203" and "X-12-2430C" (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., "S10" (trade name) manufactured by SOLVAY Corporation, and DIC Corporation. Examples thereof include "RS-55", "RS-56", "RS-57", and "RS-58" (trade name) manufactured by Japan.

The amount of the compound having a fluorine atom and a silicon atom added is 0.01 part by mass, more preferably 0.1 part by mass or more, based on 100 parts by mass of the hard coat material. Further, it is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less. When the amount of the compound having a fluorine atom and a silicon atom added is at least the above lower limit value, the antifouling performance of the film of the present invention tends to be sufficient. Further, when the addition amount is not more than the above upper limit value, the curability and transparency of the water-repellent layer tend to be good.

(Polymer initiator)
The hard coat material used in the present invention can be cured by carrying out a polymerization reaction. The polymerization is not particularly limited, and may be active energy ray polymerization or thermal polymerization.
The active energy ray-decomposable polymerization initiator may be the same as that used in the ultraviolet curable mixture. The amount of the active energy ray-decomposing polymerization initiator added is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the hard coat material.

When the hard coat layer composition used in the present invention is curable with active energy rays (hereinafter, also referred to as "light" for convenience), examples of the photoinitiator to be added to the composition include benzoin and benzoin methyl ether. , Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroine, toluoin, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyce Carbonyls such as oxylate, ethylphenylglioxylate, 4,4'-bis (dimethylamino) benzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc. Compounds; Sulfur compounds such as tetramethylthium monosulfide and tetramethylthium disulfide; and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzoyldi Examples include phosphorus compounds such as ethoxyphosphine oxide. These can be used alone or in combination of two or more.

When the film-forming composition of the present invention is a thermosetting composition, a thermosetting agent can be blended in the composition. Examples of the heat curing agent include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 2,2'-azobis- (2,). Azo-based polymerization initiators such as 4-dimethylvaleronitrile); and lauroyl peroxide, diisopropyl peroxydicarbonate, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyneodeca. Examples thereof include organic peroxide-based polymerization initiators such as Noate and t-hexyl peroxypivalate. These can be used alone or in combination of two or more.

(Other additives)
Further, a compound or the like that expresses a function may be contained in the hard coat layer. Examples thereof include a material that imparts slipperiness to the surface, a material that changes the refractive index, a material that controls the transmission / reflection of electromagnetic waves such as light and heat, and a material that controls chargeability. These materials may be dispersed in the hard coat layer, or may be unevenly distributed on the surface or the like. Further, in order to improve the scratch resistance of the hard coat layer, hard fine particles such as silica and titania, which are generally used methods, may be mixed in the hard coat layer. Further, if necessary, various components such as a slip property improving agent, a leveling agent, inorganic fine particles, and a light stabilizer (ultraviolet absorber, HALS, etc.) can be added. The amount of the other additives to be blended is preferably 10 parts by mass or less with respect to 100 parts by mass of the solid content of the hard coat layer composition used in the present invention in terms of the transparency of the coating film.

(Diluting solvent)
In the present invention, a diluting solvent can be contained in the hard coat layer composition in order to adjust the solid content concentration of the hard coat composition of the present invention.

Examples of the diluting solvent include methyl ethyl ketone, methyl isobutyl ketone, isopropanol, ethanol, 1-methoxy-2-propanol and 2,2,3,3-tetrafluoro-1-propanol.

The solid content concentration of the hard coat layer composition of the present invention is preferably 0.1 to 50% by mass. By setting the solid content concentration of the present composition within the above range, the storage stability of the hard coat layer composition of the present invention can be improved, and the desired film thickness tends to be easily controlled.

<Primer layer and primer layer composition>
The primer layer in the present invention contains at least a primer layer component, and the primer layer composition contains at least a primer layer component and a solvent.

(Primer layer component)
The primer layer component to be blended in the primer layer is not particularly limited as long as it has adhesiveness or adhesiveness to the hard coat material. For example, an epoxy resin adhesive, a polyurethane adhesive, or a silicone adhesive. , Nitrigen rubber adhesive, vinyl acetate adhesive, polyvinyl alcohol adhesive, acrylic adhesive, ultraviolet curable adhesive, acrylic copolymer adhesive and the like.

The components of the ultraviolet curable adhesive include photopolymerizable prepolymers having (meth) acrylic loyl groups, vinyl groups, etc. at the molecular ends of epoxy, urethane, polyester, silicone, etc., photopolymerizable monomers, photoinitiators, etc. Consists of.

The acrylic copolymer adhesive is obtained by copolymerizing any monofunctional (meth) acrylic acid ester. Specific examples of the monofunctional (meth) acrylic acid ester include (meth) acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, and butyl (meth) acrylic acid. , (Meta) -2-ethylhexyl acrylate, (meth) lauryl acrylate, alkyl (meth) acrylate, such as stearyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, ( Hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, methoxybutyl (meth) acrylate, (meth) ) (Meta) alkoxyalkyl acrylate such as butoxyethyl acrylate, (meth) polyethylene glycol acrylate, (meth) ethoxypolyethylene glycol acrylate, (meth) methoxypolypropylene glycol acrylate, (meth) ethoxypolypropylene glycol acrylate, etc. Acrylic polyalkylene glycol (meth) acrylate, glycidyl acrylate, diethylaminoethyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl acrylate (meth) And so on.

(solvent)
Examples of the solvent used in the primer layer composition in the present invention include propylene glycol monomethyl ether, butyl acetate, and propylene glycol monomethyl ether acetate. Among these, propylene glycol monomethyl ether, butyl acetate, and propylene glycol monomethyl ether Those containing acetate are preferable, and a mixed solvent of propylene glycol monomethyl ether, butyl acetate, propylene glycol monomethyl ether acetate and methyl ethyl ketone is particularly preferable. The mixing ratio of the mixed solvent of propylene glycol monomethyl ether, butyl acetate, propylene glycol monomethyl ether acetate and methyl ethyl ketone is not particularly limited, and for example, propylene glycol monomethyl ether, butyl acetate and propylene glycol monomethyl ether acetate / methyl ethyl ketone are mass. The ratio is 10/90 to 90/10, preferably 20/80 to 80/20, more preferably 30/70 to 70/30, and particularly preferably 40/60 to 60/40.

Examples of the solvent used in the present invention include those containing at least one selected from solvents having a molecular weight of 80 g / mol or more, a boiling point of 120 ° C. or more, and a viscosity at 20 ° C. of 2 mPa · s or less. Here, the boiling point refers to a value measured at 1.013 × ¹⁰ 5 Pa.

In the primer layer composition, the blending ratio of the primer layer component and the solvent is not particularly limited, but for example, the solid content of the primer layer component is 1 to 50% by mass, preferably 5 to 40% by mass, and more preferably 10. A blending ratio of up to 30% by mass can be mentioned.

<Release base material layer>
The resin base material of the release base material layer used in the present invention is not particularly limited, but preferably has active energy ray permeability. A known film can be used as the active energy ray-transmitting film.

Examples of the active energy ray permeable film include synthetic resins such as polyethylene teletalate (PET) film, polyethylene naphthalate film, polypropylene film, polycarbonate film, polystyrene film, polyamide film, polyamideimide film, polyethylene film, and polyvinyl chloride film. Films, cellulose-based films such as cellulose acetate films, Western papers such as cellophane paper and glassin paper, film-like materials such as Japanese paper, composite film-like materials, composite sheet-like materials, etc., and release layers, etc. Examples thereof include those provided with a surface treatment. Of these, polyethylene terephthalate film is preferable because of its hardness, optical properties, and surface free energy.

The thickness of the release base material layer is not particularly limited and can be appropriately adjusted according to the intended use. It is preferably 4 μm or more, more preferably 12 μm or more, still more preferably 30 μm or more, and preferably 500 μm or less, more preferably 150 μm or less, still more preferably 120 μm or less. Within these ranges, it tends to be easy to produce a film or laminate without wrinkles or cracks.

When the release property of the active energy ray-permeable film is insufficient and a release layer is provided, a known polymer, wax, or the like can be appropriately selected and used as the forming material of the release layer. Further, a surfactant may be added to these.

As a method for forming the release layer, for example, acrylic-based, urethane-based, silicon-based, melamine-based, urea-based, urea-melamine-based, cellulosic, benzoguanamine-based resins, paraffin wax, etc. alone or a mixture thereof can be used. A paint dissolved in an organic solvent or water as the main component is applied onto the substrate by a normal printing method such as a gravure printing method, a screen printing method, or an offset printing method, and dried (thermosetting resin, ultraviolet curing). Examples of curable coatings such as sex resins, electron beam curable resins, and thermosetting resins are those formed by curing). The thickness of the release layer is preferably about 0.1 to 3 μm. By setting the thickness of the release layer to the above, good peelability can be ensured.

(Resin base material layer)
The resin raw material of the resin base material layer used in the present invention is not particularly limited, and various raw materials can be used. For example, when an acrylic resin is produced by cast polymerization, the resin raw material is a monomer of (meth) acrylic acid esters alone, a monomer containing this as a main component, or a single amount thereof. Examples thereof include syrup containing a mixture of the body and a polymer of this monomer.

Further, as such an acrylic resin, a homopolymer of esters of (meth) acrylic acid or a copolymer containing this as a main monomer component can be exemplified. Examples of the (meth) acrylic acid esters include methyl methacrylate (hereinafter referred to as “MMA”). For example, when copolymerizing with MMA as a main monomer component, other monomer components include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and diethylhexyl acrylate. Methacrylic acid esters other than MMA such as cyclohexyl methacrylate, phenyl methacrylate and benzyl methacrylate; aromatic vinyl compounds such as styrene, α-methylstyrene and p-methylstyrene; and the like.

When the MMA monomer or the monomer mixture containing MMA as the main component contains a partial polymer of the MMA monomer or the monomer mixture containing MMA as the main component, the MMA monomer or MMA is used. The polymer obtained by pre-polymerizing the monomer mixture as the main component may be dissolved, or the MMA monomer or the monomer mixture containing MMA as the main component may be partially polymerized. .. Examples of the initiator for polymerizing the acrylic resin raw material include known azo-based initiators, peroxide-based initiators, and the like, and cast polymerization is carried out by a known method using these initiators. A mold release agent, an ultraviolet absorber, a dyeing pigment, or the like can be added to the acrylic resin raw material, depending on other purposes.

[Manufacturing method of film and laminate]
As a method for producing a film of the present invention, for example, a primer layer composition containing a primer layer component and a solvent is applied to the surface of a hard coat layer containing an antifouling compound and a hard coat material, and then dried. Examples thereof include a method of forming a primer layer.
As a method for producing the laminate of the present invention, which will be described with reference to FIG. 1, (a) a hard coat layer composition containing an antifouling compound and a hard coat material is applied to the surface of the release material layer 2. The primer layer component and the solvent are applied to the surface of the hard coat layer 1 obtained in the steps (b) and (a) of the hard coat layer 1 on the side opposite to the surface on which the release material layer 2 is provided. The step of applying the containing primer layer composition to form the primer layer 3, and the surface of the primer layer 3 obtained in the steps (c) and (b) opposite to the surface on which the hard coat layer 1 is provided. Examples thereof include a step of laminating the resin base material layer 4, (d) a step of peeling off the mold release material layer 2, and (e) a step of irradiating the surface of the hard coat layer with energy rays.

(A) Step A hard coat layer composition containing an antifouling compound and a hard coat material is applied to the surface of the release material layer 2 to form the hard coat layer 1 to obtain a laminate I.

(B) Step A primer layer composition containing a primer layer component and a solvent is applied to a surface of the hard coat layer 1 opposite to the surface on which the release material layer 2 is provided to form a primer layer II.

(C) Step The laminate II including the release material layer 2 and the film (hard coat layer 1 and primer layer 3) is bonded to the mold. Specific examples thereof include a method of directly bonding, a method of bonding via a thermoplastic resin, a method of bonding via a thermosetting resin, and a method of bonding via an ultraviolet curable mixture. From the viewpoint of good productivity, a method of laminating via a thermoplastic resin is preferable. When forming the intermediate layer, it is preferable that the film surface in contact with the intermediate layer is easily adhered because the intermediate layer does not remain on the mold surface when peeled from the mold. Here, the easy-adhesion treatment is to provide a layer for facilitating peeling from the mold.

Examples of the method of bonding via the thermoplastic resin include a method of applying the thermoplastic resin to a mold or a film and crimping it with a rubber roll. In particular, in order to prevent air from being entrained during bonding, it is preferable to apply a paint containing an excessive amount of thermoplastic resin on the mold and apply the excess paint while squeezing it out with a rubber roll through a film.

Next, the mold to which the release material layer 2 and the laminate 2 containing the film are bonded and another mold are faced to each other so that the film side is located inside the mold to prepare a mold.

As the member constituting the mold, for example, a stainless plate having a mirror surface, a glass plate, a stainless plate having an uneven surface, a glass plate, or the like can be used. For the preparation of the mold, for example, a hollow shape material made of soft polyvinyl chloride, ethylene-vinyl acetate copolymer, polyethylene, ethylene-methyl methacrylate copolymer, etc. is used as a gasket at the end between the two molds. It can be carried out by a process such as sandwiching and assembling a mold having a structure in which the end is fixed with a clamp.

Further, the resin raw material of the resin base material layer 4 is injected into the mold to perform casting polymerization.

After completion of the polymerization, the laminate III in which the film is laminated on the resin base material layer 4, the release material layer 2 and the intermediate layer are sequentially laminated is peeled from the mold.

(D) Step The release material layer 2 is peeled off from the laminate III to expose the surface of the resin laminate to obtain the laminate IV.

(E) Step The energy curable resin is cured to obtain a laminate V. When irradiating ultraviolet rays at this time, an ultraviolet lamp may be used for the ultraviolet irradiation. Examples of the ultraviolet lamp include a high-pressure mercury lamp, a metal halide lamp, a fluorescent ultraviolet lamp and the like. Curing by ultraviolet irradiation may be performed in one step via a transfer film, or may be cured in two steps. When a curable mixture other than the ultraviolet curable mixture is used, for example, a curable mixture that is cured by irradiating an active energy ray such as an electron beam or radiation through a transfer film or is cured by heating is selected. be able to.

[Use]
Since the films and laminates produced in the present invention have an antifouling function, they are decorative films for interior and exterior of automobiles and face plates of display devices such as displays, that is, mobile phones, portable game machines, car navigation systems, and the like. It is suitable as a transparent resin film that protects the surface of products such as bootable AV equipment.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded. In the following, "parts" and "%" indicate "parts by mass" and "% by mass", respectively.

(1) Contact angle measurement In an environment of 23 ° C. and 50% relative humidity, 0.2 μL of pure water was dropped onto the target sample in one drop, and a contact angle meter (First Ten Angstroms, trade name: “FTA125”) was added. The contact angle between water and the water-repellent layer was measured using the above, and the contact angle with water was determined.

(2) Antifouling property (oil-based ink wiping property)
Draw a line on the surface of the cured film with "My Name" (registered trademark) (manufactured by Sakura Color Products Corporation) as oil-based ink (black), and after 3 minutes, "Kim Towel" (registered trademark) (manufactured by Nippon Paper Crecia) ), And the degree of wiping off the oil-based ink at that time was visually evaluated according to the following criteria.
"○": Can be completely wiped off with 5 wipes "×": Part or all of the ink remains attached after 5 wipes

Table 1 shows the physical properties of each reagent used in Examples and Comparative Examples.

<Example 1>
In a four-mouthed flask, as a hard coat material, 100 parts by mass of a (meth) acrylic resin (product name: Yupimer UV HH2150, manufactured by Mitsubishi Chemical Co., Ltd.) having an acryloyl group in the side chain, polyfunctional isocyanate (product name:: CORONATE HL (manufactured by Toso Co., Ltd.) as an antifouling compound, an antifouling agent resin (product name: KY) that is a (meth) acrylic polymer having an acryloyl group in the side chain and contains a fluorocarbon chain in its structure. -1203, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a polymerization initiator, 1-hydroxy-cyclohexyl-phenyl-ketone (product name: Omnirad 184, manufactured by IGM Resin) as a reaction catalyst. , 0.05 parts by mass of dibutyltin dilaurate, and then 20% by mass of the total solid content using a mixed solvent (mass ratio 1: 1) of propylene glycol monomethyl ether (PGM) and methyl ethyl ketone (MEK) as a diluting solvent. The hard coat layer composition (A) was obtained.

The hard coat layer composition (A) was applied to the surface of a PET film having a thickness of 50 μm as a release material layer using a No. 14 bar coater, and dried at 90 ° C. for 1 minute to form the hard coat layer 1 and the release material layer 2. Laminated body I was obtained.

A mixture of propylene glycol monomethyl ether (PGM) and methyl ethyl ketone (MEK) as a solvent is added to a (meth) acrylic resin adhesive (weight average molecular weight of about 8,000) as a primer layer component at a mass ratio of 1: 1. A pressure-sensitive adhesive layer composition (B) having a solid content concentration of 20% was prepared. The primer layer composition (B) was applied to the surface of the hard coat layer 1 of the laminate I (the surface opposite to the surface in contact with the release material layer 2) using a No. 10 bar coater. Then, it was dried at 60 ° C. for 2 minutes to form a primer layer 3, and cured in a cool and dark place for 1 day or more to obtain a laminate II (transfer film).

Acrylite EX001 (methacrylic resin plate) having a plate thickness of 1.5 mm was used as the resin base material layer, and the laminate II (transfer film) was laminated on the surface via the primer layer 3. Then, it was heated at 160 ° C. for 1 minute. The primer layer 3 was squeezed using a rubber roll having a JIS hardness of 40 ° and pressure-bonded so as not to contain air bubbles to obtain a laminate III.

Then, after the above-mentioned laminate III was sufficiently cooled, the release material layer 2 was peeled off to obtain a laminate IV. The surface of the hard coat layer 1 from which the release material layer 2 has been peeled off is passed under a metal halide lamp having an output of 2.8 kW (distance from the lamp is 5.3 cm) at a speed of 6.0 m / min to obtain a laminate V. It was. The integrated light intensity was 1000 mJ / cm ² .

The contact angle of the surface of the hard coat layer 1 of the laminate V with water was measured, and the antifouling property was evaluated. The evaluation results are shown in Table 2.

<Example 2>
The laminate was prepared in the same manner as in Example 1 except that a mixed solvent of butyl acetate (BAc) and MEK (mass ratio 1: 1) was used instead of the mixed solvent of PGM and MEK as the solvent of the primer layer composition. Obtained. The evaluation results are shown in Table 2.

<Example 3>
The same as in Example 1 except that a mixed solvent of propylene glycol monomethyl ether acetate (PGMAc) and MEK (mass ratio 1: 1) was used as the solvent of the primer layer composition instead of the mixed solvent of PGM and MEK. A laminate was obtained. The evaluation results are shown in Table 2.

<Comparative example 1>
A laminate was obtained in the same manner as in Example 1 except that a mixed solvent of isopropanol (IPA) and MEK (mass ratio 1: 1) was used instead of the mixed solvent of PGM and MEK as the solvent of the primer layer composition. It was. The evaluation results are shown in Table 2.

<Comparative example 2>
The laminate was prepared in the same manner as in Example 1 except that a mixed solvent of normal butanol (nBA) and MEK (mass ratio 1: 1) was used instead of the mixed solvent of PGM and MEK as the solvent of the primer layer composition. Obtained. The evaluation results are shown in Table 2.

From the above results, it was found that when PGM / MEK, BAc / MEK, and PGMAc / MEK were used as the solvent of the primer layer composition, the contact angle was large and good antifouling property was obtained. On the other hand, when IPA / MEK or BA / MEK was used as the solvent, it was clarified that the contact angle was small and the antifouling property was inferior.
Therefore, it can be seen that a film and a laminate having a hard coat layer having excellent antifouling properties can be obtained by selecting an appropriate solvent for the primer layer composition.

Here, the reason why a hard coat layer having excellent antifouling properties can be obtained when an appropriate solvent is selected for the primer layer composition part is not bound by the following theory, but is as follows. Can be thought of as. That is, when the primer layer composition is applied to the hard coat layer, only a specific solvent (for example, PGM or a mixed solvent of PGM and MEK) permeates the hard coat layer (does not permeate with IPA or the like), and the solvent It is conceivable that the antifouling compound in the hard coat layer moves in the permeation direction, and this antifouling compound segregates near the boundary with the release material layer. By adding a solvent having a molecular weight of 80 g / mol or more, a boiling point of 120 ° C. or more, and a viscosity of 2 mPa · s or less at 20 ° C., it is considered that the effect of segregation is promoted because it is easy to permeate and volatilization is suppressed. And / or by using a specific solvent, rearrangement of the antifouling compound occurs near the boundary between the hard coat layer and the release material layer, and the arrangement of the functional groups of the antifouling compound on the hard coat surface is changed. It is conceivable to do. It is also considered that the mode of arrangement of the functional groups at this time depends on the correlation of compatibility between the antifouling compound / solvent / release material layer.

1 Hard coat layer 2 Release material layer 3 Primer layer 4 Resin base material layer

Claims (5)

A hard coat layer containing an antifouling compound having a fluorine atom and / or a silicon atom and a hard coat material, and
A primer layer provided on the surface of the hard coat layer and
Is a method for producing a film having
A step of applying a primer layer composition containing a primer layer component and a solvent to the surface of the hard coat layer to form a primer layer is included.
The solvent contains at least one selected from a solvent having a molecular weight of 80 g / mol or more, a boiling point of 120 ° C. or more, and a viscosity at 20 ° C. of 2 mPa · s or less.
How to make a film. A hard coat layer containing an antifouling compound having a fluorine atom and / or a silicon atom and a hard coat material, and
A primer layer provided on the surface of the hard coat layer and
A resin base material layer provided on the surface of the primer layer opposite to the surface on which the hard coat layer is provided, and a resin base material layer.
It is a manufacturing method of a laminated body having
(A) A step of applying a hard coat layer composition containing an antifouling compound and a hard coat material to the surface of the release material layer to form a hard coat layer.
(B) A primer layer composition containing a primer layer component and a solvent is applied to a surface of the hard coat layer obtained in the step (a) opposite to the surface on which the release material layer is provided. The process of forming
(C) A step of laminating a resin base material layer on a surface of the primer layer obtained in the step (b) opposite to the surface on which the hard coat layer is provided.
(D) At least one selected from a solvent having a molecular weight of 80 g / mol or more, a boiling point of 120 ° C. or more, and a viscosity at 20 ° C. of 2 mPa · s or less, including a step of peeling off the release material layer. A method for producing a laminate, including. (E) The method for producing a laminate according to claim 2, further comprising a step of irradiating the surface of the hard coat layer with energy rays. The production method according to any one of claims 1 to 3, wherein the solvent contains at least one selected from the group consisting of propylene glycol monomethyl ether, butyl acetate, and propylene glycol monomethyl ether. The production method according to any one of claims 1 to 4, wherein the solvent is a mixed solvent of at least one selected from the group consisting of propylene glycol monomethyl ether, butyl acetate, and propylene glycol monomethyl ether and methyl ethyl ketone. ..

Images